TWI402004B - Methods for manufacturing heat dissipation and insulated composite substrate and heat dissipation and insulated substrate thereof - Google Patents
Methods for manufacturing heat dissipation and insulated composite substrate and heat dissipation and insulated substrate thereof Download PDFInfo
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本發明係關於一種散熱基板及其製備方法，特別係關於包含一交互穿透結構(inter-penetrating-network；IPN)之導熱絕緣高分子材料之散熱基板及其製備方法。The invention relates to a heat dissipating substrate and a preparation method thereof, in particular to a heat dissipating substrate comprising an inter-penetrating-network (IPN) thermal conductive insulating polymer material and a preparation method thereof.
近幾年來，由於電子裝置中之電路板上使用之電子元件的功率越來越高，電子元件產生的熱管理問題變成不可忽視。若電子元件之散熱不良，將使電子元件處於高溫狀態，電子元件的溫度過高，不僅大幅降低電子元件之效能，甚至影響其壽命與可靠度。因此，電子裝置在設計時，常使用導熱較佳之電路基板，以便提供電子元件較佳的散熱環境。In recent years, as the power of electronic components used on circuit boards in electronic devices has become higher and higher, thermal management problems caused by electronic components have become unnegligible. If the heat dissipation of the electronic component is poor, the electronic component will be in a high temperature state, and the temperature of the electronic component is too high, which not only greatly reduces the performance of the electronic component, but also affects its life and reliability. Therefore, the electronic device is often designed to use a circuit board with better thermal conductivity in order to provide a better heat dissipation environment for the electronic component.
習知技藝之導熱電路基板之製作係將液態環氧樹脂、導熱填料和固化劑等材料混合而成之樹脂漿塗佈於金屬基材上，然後將其加熱以形成膠態(B-stage)，最後再利用熱壓合製作成一電路板；或者，將環氧樹脂塗佈於玻璃纖維布上，加熱形成膠態(B-stage)後，再由熱壓製程製作出一玻璃纖維電路板。The conventional thermal conductive circuit substrate is prepared by coating a resin slurry obtained by mixing a liquid epoxy resin, a heat conductive filler and a curing agent onto a metal substrate, and then heating it to form a B-stage. Finally, it is fabricated into a circuit board by thermocompression bonding; or, after the epoxy resin is coated on the glass fiber cloth, heated to form a B-stage, and then a glass fiber circuit board is produced by a hot pressing process.
上述習知技藝之製程需使用較低之黏稠度之樹脂漿，然而低黏度之樹脂漿會因導熱填料沉降而產生發生固體與液體分層的現象，此現象會造成混合不均，進而影響到散熱效率，而且該樹脂漿也有儲存不易之問題。以玻璃纖維製作之電路板，由於玻璃纖維之導熱係數低(約為0.36W/mK)，故其導熱效果不佳。此外，上述習知技藝之製程均使用塗佈製程，然而塗佈製程有速度慢、產量低等問題。The above-mentioned prior art process requires the use of a resin paste having a lower viscosity. However, the low-viscosity resin slurry may cause delamination of solids and liquids due to sedimentation of the thermally conductive filler, which may cause uneven mixing and thus affect The heat dissipation efficiency, and the resin slurry also has a problem of difficulty in storage. The circuit board made of glass fiber has a poor thermal conductivity due to its low thermal conductivity (about 0.36 W/mK). In addition, the above-mentioned prior art processes use a coating process, however, the coating process has problems such as slow speed and low yield.
綜上所述，習知技藝之導熱電路基板之製作係利用塗佈製程，然塗佈製程速度慢、產量低，且因其需使用低黏度之樹脂漿，而易發生固體與液體分層的問題。此外，由於玻璃纖維之導熱係數低，因此以玻璃纖維製作之電路板導熱效果不佳。故，目前仍需一種具高導熱能力之導熱電路基板及能高速量產該具高導熱能力之導熱電路基板之製作方法。In summary, the fabrication of the thermally conductive circuit substrate of the prior art utilizes a coating process, but the coating process is slow, the yield is low, and the use of a low-viscosity resin slurry is liable to cause delamination of solids and liquids. problem. In addition, since the thermal conductivity of the glass fiber is low, the heat dissipation effect of the circuit board made of glass fiber is not good. Therefore, there is still a need for a thermally conductive circuit substrate having high thermal conductivity and a method of manufacturing the thermally conductive circuit substrate having high thermal conductivity.
本發明提供一種導熱絕緣基板及以該導熱絕緣基板製作而成之導熱絕緣複合基板及其製備方法，導熱絕緣基板係以一具有一交互穿透結構之特性而呈現橡膠狀(rubbery)之絕緣材料所製成，該絕緣材料具高導熱性，以及不發生固體與液體分層的問題，且可利用擠壓之方式製作，故可提高其製備之速度。The invention provides a thermally conductive insulating substrate and a thermally conductive insulated composite substrate prepared by using the thermally conductive insulating substrate, and a method for preparing the same, wherein the thermally conductive insulating substrate exhibits a rubbery insulating material with an interpenetrating structure. The insulating material has high thermal conductivity and does not cause delamination of solids and liquids, and can be produced by extrusion, so that the speed of preparation thereof can be improved.
本發明第一方面揭示一種導熱絕緣基板之製備方法，其包含下列步驟：對至少一陶瓷粉末進行水解縮合反應，以獲得至少一改質陶瓷粉末，其中各該至少一改質陶瓷粉末包含複數個改質粉末顆粒，而各該改質粉末顆粒之表面接枝一有機化合物；將該至少一改質陶瓷粉末、一高分子材料和一固化劑混合，以獲得一絕緣材料；將該絕緣材料擠壓通過一狹縫，以形成一板狀基材；以及分別設置第一膜材及第二膜材於該板狀基材之二板面上，而形成該導熱絕緣基板，其中該第一膜材及第二膜材係選自金屬材或離型材。A first aspect of the invention discloses a method for preparing a thermally conductive insulating substrate, comprising the steps of: performing a hydrolysis condensation reaction on at least one ceramic powder to obtain at least one modified ceramic powder, wherein each of the at least one modified ceramic powder comprises a plurality of Modifying the powder particles, and grafting an organic compound on the surface of each of the modified powder particles; mixing the at least one modified ceramic powder, a polymer material and a curing agent to obtain an insulating material; extruding the insulating material Pressing through a slit to form a plate-shaped substrate; and separately forming a first film and a second film on the two plates of the plate-like substrate to form the thermally conductive insulating substrate, wherein the first film The material and the second film are selected from metal materials or release materials.
本發明第二方面揭示一種導熱絕緣複合基板之製備方法，其包含下列步驟：對至少一陶瓷粉末進行水解縮合反應，以獲得至少一改質陶瓷粉末，其中各該至少一陶瓷粉末包含複數個粉末顆粒，而經過該水解縮合反應後，各該改質粉末顆粒之表面接枝一有機化合物；將該至少一改質陶瓷粉末、一高分子材料和一固化劑混合，以獲得一絕緣材料；將該絕緣材料擠壓通過一狹縫，以形成一板狀基材；設置一金屬材於該板狀基材之一板面上；裁切具該金屬材之該板狀基材成導熱絕緣基板；以及於一壓合溫度下，壓合複數片該導熱絕緣基板，而形成該導熱絕緣複合基板。A second aspect of the invention discloses a method for preparing a thermally conductive and insulating composite substrate, comprising the steps of: performing a hydrolysis condensation reaction on at least one ceramic powder to obtain at least one modified ceramic powder, wherein each of the at least one ceramic powder comprises a plurality of powders And granules, after the hydrolysis condensation reaction, the surface of each of the modified powder particles is grafted with an organic compound; the at least one modified ceramic powder, a polymer material and a curing agent are mixed to obtain an insulating material; The insulating material is extruded through a slit to form a plate-shaped substrate; a metal material is disposed on one of the plate-shaped substrate; and the plate-shaped substrate having the metal material is cut into a heat-conductive insulating substrate And forming a thermally conductive insulating composite substrate by pressing a plurality of the thermally conductive insulating substrates at a pressing temperature.
圖1顯示本發明一實施例之導熱絕緣複合基板之製備方法之流程示意圖。本發明一實施例揭示一導熱絕緣複合基板之製備方法，該方法包含下列步驟：在步驟S11中，對至少一陶瓷粉末進行水解縮合反應，以獲得至少一改質陶瓷粉末，其中各該至少一改質陶瓷粉末包含複數個改質粉末顆粒，而該改質粉末顆粒之表面接枝一有機化合物。於一實施例中，該有機化合物係有機矽，而該水解縮合反應係在一酸性環境下，以該有機矽對該至少一陶瓷粉末進行反應；於另一實施例中，該有機化合物係有機鈦，而該水解縮合反應係在一酸性環境下，以有機鈦對該至少一陶瓷粉末進行反應，而於上述兩實施例中之酸性環境，其酸鹼值約在PH 1至PH 5之間。在步驟S12中，將該至少一改質陶瓷粉末與一高分子材料和一固化劑(curing agent)混合，以獲得一絕緣材料，其中該絕緣材料之導熱係數大於0.5W/mK。在步驟S13中，將該絕緣材料擠壓通過一狹縫，以形成一板狀基材，其中該絕緣材料以介於50℃至150℃之溫度擠壓通過該狹縫。1 is a flow chart showing a method of preparing a thermally conductive and insulating composite substrate according to an embodiment of the present invention. An embodiment of the present invention discloses a method for preparing a thermally conductive and insulating composite substrate, the method comprising the steps of: performing a hydrolysis condensation reaction on at least one ceramic powder in step S11 to obtain at least one modified ceramic powder, wherein each of the at least one The modified ceramic powder comprises a plurality of modified powder particles, and the surface of the modified powder particles is grafted with an organic compound. In one embodiment, the organic compound is an organic hydrazine, and the hydrolytic condensation reaction is carried out by reacting the at least one ceramic powder with the organic hydrazine in an acidic environment; in another embodiment, the organic compound is organic Titanium, and the hydrolysis condensation reaction is carried out by reacting the at least one ceramic powder with organic titanium in an acidic environment, and the acidity and alkalinity in the acidic environment of the above two embodiments is between about PH 1 and PH 5 . In step S12, the at least one modified ceramic powder is mixed with a polymer material and a curing agent to obtain an insulating material, wherein the insulating material has a thermal conductivity greater than 0.5 W/mK. In step S13, the insulating material is extruded through a slit to form a plate-like substrate, wherein the insulating material is extruded through the slit at a temperature of between 50 ° C and 150 ° C.
在步驟S14中，該板狀基材之兩板面上，各設置一第一膜材與一第二膜材。第一膜材和第二膜材分別可包含離型材及金屬材。第一膜材、板狀基材和第二膜材之組合(第一膜材/板狀基材/第二膜材)可包含離型材/板狀基材/離型材(即，prepreg基板)、金屬材/板狀基材/離型材(即，樹脂包覆金屬基板；resin coated metal substrate)以及金屬材/板狀基材/金屬材(即，基板；metal core substrate)等不同組合。在步驟S15中，裁切已設置第一膜材和第二膜材之板狀基材成導熱絕緣基板，導熱絕緣基板可與其它金屬基板或印刷電路板疊合成單面板、雙面板、金屬核心板或多層基板，於一壓合溫度下，壓合成一導熱絕緣複合基板，而該壓合溫度可介於80℃至220℃。在步驟S16中，以一成型技術，修整壓合之該導熱絕緣複合基板，其中該成型技術包含裁切、剪切、衝切、鑽石切等製程。In step S14, a first film and a second film are disposed on each of the two plates of the plate-shaped substrate. The first film and the second film may respectively comprise a release profile and a metal. The combination of the first film, the plate substrate and the second film (the first film/plate substrate/second film) may comprise a release profile/plate substrate/release profile (ie, a prepreg substrate) Different combinations of metal/plate-like substrate/release material (ie, resin coated metal substrate) and metal/plate substrate/metal material (ie, metal core substrate). In step S15, the plate-shaped substrate on which the first film and the second film are disposed is cut into a thermally conductive insulating substrate, and the thermally conductive insulating substrate can be laminated with other metal substrates or printed circuit boards to form a single-panel, double-panel, metal core. The plate or the multilayer substrate is pressed into a thermally conductive and insulating composite substrate at a pressing temperature, and the pressing temperature may be between 80 ° C and 220 ° C. In step S16, the thermally conductive and insulating composite substrate is pressed and pressed by a molding technique, wherein the molding technique includes cutting, shearing, punching, diamond cutting, and the like.
高分子材料之成分包含熱塑型塑膠(thermoplastic)和熱固型環氧樹脂(thermosetting epoxy)，且該熱固型環氧樹脂可佔該高分子材料之體積百分比係介於70%至97%之間。該熱固型環氧樹脂可藉該固化劑於一固化溫度下將其固化，其中該固化溫度可高於80℃。The component of the polymer material comprises a thermoplastic and a thermosetting epoxy, and the thermosetting epoxy resin accounts for 70% to 97% by volume of the polymer material. between. The thermosetting epoxy resin can be cured by the curing agent at a curing temperature, wherein the curing temperature can be higher than 80 °C.
特而言之，該絕緣材料之混摻方法首先將包含該熱塑型塑膠及該熱固型環氧樹脂之高分子材料以200℃加熱混合大約30分鐘以生成一均勻膠體。再將改質後之陶瓷粉末加入該均勻膠體後混合均勻以形成一均勻橡膠狀材料，再將固化劑與加速劑於80℃溫度下加入該均勻橡膠狀材料，以形成一絕緣材料，其中該均勻橡膠狀材料具交互穿透結構(inter-penetrating network)，且由於該熱塑型塑膠與該熱固型環氧樹脂係彼此互溶且呈均勻相(homogeneous)，藉此使得該陶瓷粉末均勻散佈於該交互穿透結構中，以達到最佳之導熱效果。該陶瓷粉末係均勻分散於該高分子材料中，且該陶瓷粉末約佔該絕緣材料之體積百分比介於40%至70%之間。In particular, the method of blending the insulating material firstly heats the polymer material including the thermoplastic plastic and the thermosetting epoxy resin at 200 ° C for about 30 minutes to form a uniform colloid. The modified ceramic powder is added to the uniform colloid and uniformly mixed to form a uniform rubber-like material, and then the curing agent and the accelerator are added to the uniform rubber-like material at a temperature of 80 ° C to form an insulating material, wherein The uniform rubber-like material has an inter-penetrating network, and since the thermoplastic plastic and the thermosetting epoxy resin are mutually soluble and homogeneous, the ceramic powder is evenly dispersed. In the interactive penetration structure to achieve the best thermal conductivity. The ceramic powder is uniformly dispersed in the polymer material, and the ceramic powder accounts for about 40% to 70% by volume of the insulating material.
上述之熱塑型塑膠可為一超高分子量苯氧基樹脂，其中該超高分子量苯氧基樹脂之分子量可大於30000。熱塑型塑膠亦可包含一羥基-苯氧基樹脂醚高分子結構，其中該羥基-苯氧基樹脂醚高分子結構可經由雙環氧化物與雙官能基物種經聚合反應而成。該熱塑型塑膠又可分別由液態環氧樹脂與雙酚A、液態環氧樹脂與二價酸、液態環氧樹脂與胺類等方式反應而成。上述之熱固型環氧樹脂可包含未固化之液態環氧樹脂、聚合環氧樹脂、酚酫環氧樹脂或酚甲烷樹脂。The thermoplastic plastic described above may be an ultrahigh molecular weight phenoxy resin, wherein the ultrahigh molecular weight phenoxy resin may have a molecular weight of more than 30,000. The thermoplastic plastic may also comprise a monohydroxy-phenoxy resin ether polymer structure in which the hydroxy-phenoxy resin ether polymer structure is polymerized by reacting a diepoxide with a difunctional species. The thermoplastic plastic can also be formed by reacting liquid epoxy resin with bisphenol A, liquid epoxy resin and divalent acid, liquid epoxy resin and amine. The above thermosetting epoxy resin may comprise an uncured liquid epoxy resin, a polymeric epoxy resin, a phenolphthalein epoxy resin or a phenol methane resin.
因熱塑型塑膠之特性使該導熱絕緣材料可以經由熱塑型塑膠製程成形，又因含有熱固型塑膠，在高溫下得以固化交聯，而形成一熱塑型塑膠與熱固型塑膠交互穿透之結構，此結構不但可以有耐高溫不變型的熱固型塑膠特性，又擁有強韌不易脆裂的熱塑型塑膠之特性，並可與金屬電極或基板產生強力接著。Due to the characteristics of the thermoplastic plastic, the thermal conductive material can be formed through a thermoplastic plastic process, and the thermosetting plastic is cured and crosslinked at a high temperature to form a thermoplastic plastic and a thermosetting plastic. Through the structure of penetration, this structure can not only have the characteristics of thermosetting plastic which is resistant to high temperature, but also has the characteristics of thermoplastic plastic which is not tough and brittle, and can be strongly followed by metal electrodes or substrates.
參照圖2A，導熱絕緣基板11之兩板面上，一板面可設置印刷電路板12，而另一板面可設置1.0至1.5公釐的金屬基板13，該疊合結構可利用一熱壓機以200℃以25kg/cm2 之壓力壓合，形成導熱絕緣複合基板10，一實施例中，金屬基板可為一鋁基板，使壓合後之複合基板為單面雙層鋁基板。印刷電路板12可為導熱絕緣基板11之至少一表面上具有圖案化之金屬材14之組成。參照圖2B，導熱絕緣基板11之一板面上，設置一金屬材15，另依板面上設置金屬材16，該金屬材15導熱絕緣基板11金屬材16，經200℃90分鐘之熱壓後(並控制其厚度，例如0.5mm)，即形成一厚度為0.2mm之導熱絕緣複合基板10'之另一態樣，即單面金屬基板。金屬材15、金屬基材16與導熱絕緣基板11間形成物理接觸且其導熱係數係大於0.5W/mK。該導熱絕緣複合基板10'之厚度小於0.5mm且可耐大於1000伏特之電壓。Referring to FIG. 2A, on both sides of the thermally conductive insulating substrate 11, one board surface may be provided with a printed circuit board 12, and the other board surface may be provided with a metal substrate 13 of 1.0 to 1.5 mm, and the laminated structure may utilize a hot pressing The machine is pressed at a pressure of 25 kg/cm 2 at 200 ° C to form a thermally conductive and insulating composite substrate 10 . In one embodiment, the metal substrate can be an aluminum substrate, and the laminated composite substrate is a single-sided double-layer aluminum substrate. The printed circuit board 12 may be composed of a patterned metal material 14 on at least one surface of the thermally conductive insulating substrate 11. Referring to FIG. 2B, a metal material 15 is disposed on one surface of the heat-conductive insulating substrate 11, and a metal material 16 is disposed on the surface of the heat-dissipating insulating substrate 11. The metal material 15 thermally conducts the insulating material of the insulating substrate 11 and is subjected to hot pressing at 200 ° C for 90 minutes. After that (and controlling its thickness, for example, 0.5 mm), another aspect of the thermally conductive and insulating composite substrate 10' having a thickness of 0.2 mm is formed, that is, a single-sided metal substrate. The metal material 15, the metal substrate 16 and the thermally conductive insulating substrate 11 are in physical contact with each other and have a thermal conductivity greater than 0.5 W/mK. The thermally conductive and insulating composite substrate 10' has a thickness of less than 0.5 mm and can withstand a voltage greater than 1000 volts.
參照圖2C，導熱絕緣基板11可與多種不同金屬材15疊合，疊合成金屬材15/導熱絕緣基板11/金屬材15/導熱絕緣基板11/金屬材15之後再進行熱壓以形成金屬核心基板結構。Referring to FIG. 2C, the thermally conductive insulating substrate 11 may be laminated with a plurality of different metal materials 15 to form a metal core 15 / a thermally conductive insulating substrate 11 / a metal material 15 / a thermally conductive insulating substrate 11 / a metal material 15 and then hot pressed to form a metal core. Substrate structure.
於進行上述熱壓合製程時，該片狀導熱絕緣複合材料因已具交互穿透結構，故不會發生分層(separation)之現象。前述眾金屬材之材料係選自銅、鋁、鎳、銅合金、鋁合金、鎳合金、銅鎳合金及鋁銅合金。該片狀導熱絕緣複合材料之外觀呈現橡膠狀(非樹脂漿狀(slurry))因而具有方便儲存、加工之特性。此外，該導熱絕緣複合材料亦可利用一般使用於熱塑型塑膠之加工方法加以加工，藉此提高其可加工性。When the above-mentioned thermal compression bonding process is performed, the sheet-shaped thermally conductive and insulating composite material has an interaction structure, so that separation does not occur. The materials of the foregoing metal materials are selected from the group consisting of copper, aluminum, nickel, copper alloys, aluminum alloys, nickel alloys, copper-nickel alloys and aluminum-copper alloys. The sheet-like thermally conductive insulating composite material has a rubbery appearance (non-resin) and thus has the characteristics of convenient storage and processing. In addition, the thermally conductive insulating composite material can also be processed by a processing method generally used for thermoplastic molding, thereby improving workability.
本發明使用之高分子材料中，該熱塑型塑膠及該熱固型環氧樹脂係實質上彼此互溶(substantially mutually soluble)。「實質上彼此互溶」意謂當該熱塑型塑膠及該熱固型環氧樹脂混合後形成一具單一玻璃轉換溫度(single glass transition temperature)之溶液。因為該熱塑型塑膠及該熱固型環氧樹脂係彼此互溶，當二者混合時，該熱塑型塑膠將溶解至該熱固型環氧樹脂中，使得該熱塑型塑膠之玻璃轉換溫度實質地降低，並允許二者之混合發生在低於該熱塑型塑膠之正常軟化溫度(normal softening temperature)。所形成之混合物(即該高分子成分)於室溫下係呈橡膠狀(或固態)，易於稱重及儲存。例如，即使該熱固型環氧樹脂係一液態環氧樹脂，在與該熱塑型塑膠混合之後所形成之混合物，其本身雖非液態但卻可被製成一似皮革之堅韌薄膜(tough leathery film)。於25℃下，該混合物具一相當高之黏滯係數(約105 至107 泊(poise))，其係避免該高分子成分發生沈澱(settling)或重新分佈(redistribution)之重要因素。此外，該混合物在一般進行混合之溫度下(約40℃至100℃)具有一足夠低之黏滯係數(於60℃下，約104 至105 泊)，使得添加的固化劑及陶瓷粉末可均勻分佈在該混合物中並進行反應。該混合物之眾多例子可參考PCT專利公開號WO92/08073(1992年5月14日公開)(於本文中一併作為參考)。In the polymer material used in the present invention, the thermoplastic plastic and the thermosetting epoxy resin are substantially mutually soluble. "Substantially mutually soluble" means that a solution of a single glass transition temperature is formed when the thermoplastic plastic and the thermosetting epoxy resin are mixed. Because the thermoplastic plastic and the thermosetting epoxy resin are mutually soluble, when the two are mixed, the thermoplastic plastic will be dissolved into the thermosetting epoxy resin, so that the thermoplastic plastic glass is converted. The temperature is substantially reduced and allows mixing of the two to occur below the normal softening temperature of the thermoplastic. The resulting mixture (i.e., the polymer component) is rubbery (or solid) at room temperature and is easy to weigh and store. For example, even if the thermosetting epoxy resin is a liquid epoxy resin, the mixture formed after mixing with the thermoplastic plastic can be made into a leather-like tough film (tough) although it is not liquid. Leathery film). At 25 ° C, the mixture has a relatively high viscosity coefficient (about 10 5 to 10 7 poise) which is an important factor in avoiding settling or redistribution of the polymer component. In addition, the mixture has a sufficiently low viscosity coefficient (about 10 4 to 10 5 poise at 60 ° C) at a temperature at which mixing is generally carried out (about 40 ° C to 100 ° C), so that the added curing agent and ceramic powder It can be uniformly distributed in the mixture and reacted. A number of examples of such mixtures can be found in PCT Patent Publication No. WO 92/08073 (published on May 14, 1992), which is incorporated herein by reference.
本發明之導熱絕緣高分子材料中之固化劑(curing agent)之固化溫度Tcure 係高於100℃，用以固化(即交聯(crosslink)或催化聚合(catalyze polymerization))該熱固型環氧樹脂。該固化劑係在高於混合溫度Tmix 時將該熱固型環氧樹脂快速固化，其中該混合溫度Tmix 係指該熱塑型塑膠、該熱固型環氧樹脂及該固化劑混合時之溫度，且該混合溫度Tmix 一般約自25℃至100℃。該固化劑於該混合溫度Tmix 下混合時，並不會起始一實質固化過程(substantial curing)。於本發明中該固化劑之添加劑量係可使該熱固型環氧樹脂於高於該混合溫度Tmix 時被固化。較佳地，該固化劑於小於約100℃時不會起始該實質固化過程且使得該導熱絕緣高分子材料於25℃下保持在實質未固化狀態(substantially uncured)達至少半年之久。Curing temperature T cure insulating thermally conductive polymer material according to the present invention the curing agent (curing agent) of higher than 100 ℃, for curing (i.e., crosslinking (Crosslink) or catalytic polymerization (catalyze polymerization)) of the thermosetting ring Oxygen resin. The curing agent rapidly cures the thermosetting epoxy resin at a temperature higher than the mixing temperature T mix , wherein the mixing temperature T mix refers to the thermoplastic plastic, the thermosetting epoxy resin, and the curing agent when mixed The temperature, and the mixing temperature T mix is generally from about 25 ° C to 100 ° C. When the curing agent is mixed at the mixing temperature T mix , a substantial curing is not initiated. In the present invention, the amount of the curing agent is such that the thermosetting epoxy resin is cured at a temperature higher than the mixing temperature T mix . Preferably, the curing agent does not initiate the substantial curing process at less than about 100 ° C and causes the thermally conductive, insulative polymeric material to remain substantially uncured at 25 ° C for at least half a year.
除上所述外，本發明熱塑型塑膠亦可選用一實質非結晶熱塑型樹脂(essentially amorphous thermoplastic resin)，其定義請參考"Saechtling International plastic Handbook for the Technology,Engineer and User,second Edition,1987,Hanser Publishers,Munich"之第1頁。「實質非結晶」係意謂該樹脂中之「結晶性」(crystallinity)部分至多佔15%，較佳地至多佔10%，特別地至多佔5%，例如：佔0至5%的結晶性。該實質非結晶熱塑型樹脂係一高分子量之聚合物，在室溫下係呈現堅硬狀(rigid)或橡膠狀(rubbery)，其在該高分子成分於未固化狀態時(uncured state)用以提供強度(strength)及高黏滯性(high viscosity)等性質。該實質非結晶熱塑型樹脂在該高分子成分中所佔的體積百分比一般係介於10%至75%，較佳地係介於15%至60%，特別地係介於25%至45%。該實質非結晶熱塑型樹脂可以選自聚碸(polysulfone)、聚醚碸(polyethersulfone)、聚苯乙烯(polystyrene)、聚氧化二甲苯(polyphenylene oxide)、聚苯硫醚(polyphenylene sulfide)、聚醯胺(polyamide)、苯氧基樹脂(phenoxy resin)、聚亞醯胺(polyimide)、聚醚醯亞胺(polyetherimide)、聚醚醯亞胺與矽酮之塊體共聚合物(polyetherimide/silicone block copolymer)、聚氨酯(polyurethane)、聚酯樹脂(polyester)、聚碳酸酯(polycarbonate)，壓克力樹脂(acrylic resin)(例如：聚甲基丙烯酸甲酯(polymethyl methacrylate)、苯乙烯(styrene)/丙烯(Acrylonitrile)及苯乙烯塊體共聚合物(styrene block copolymers))。In addition to the above, the thermoplastic plastic of the present invention may also be selected from a substantially non-crystalline thermoplastic resin. For the definition, please refer to "Saechtling International plastic Handbook for the Technology, Engineer and User, second Edition," 1987, Hanser Publishers, Munich" page 1. "Substantially amorphous" means that the "crystallinity" portion of the resin accounts for at most 15%, preferably at most 10%, particularly at most 5%, for example, from 0 to 5% of crystallinity. . The substantially amorphous thermoplastic resin is a high molecular weight polymer which exhibits a rigid or rubbery at room temperature, and is used in an uncured state of the polymer component. To provide properties such as strength and high viscosity. The volume percentage of the substantially amorphous thermoplastic resin in the polymer component is generally from 10% to 75%, preferably from 15% to 60%, particularly from 25% to 45%. %. The substantially amorphous thermoplastic resin may be selected from the group consisting of polysulfone, polyethersulfone, polystyrene, polyphenylene oxide, polyphenylene sulfide, and poly Polyamide, phenoxy resin, polyimide, polyetherimide, polyetherimide and anthrone (polyetherimide/silicone) Block copolymer), polyurethane, polyester, polycarbonate, acrylic resin (eg polymethyl methacrylate, styrene) /Acrylonitrile and styrene block copolymers).
另該熱塑型塑膠最佳地可包含一羥基-苯氧基樹脂醚(hydroxy-phenoxyether)高分子結構。該羥基-苯氧基樹脂醚係由一雙環氧化物(diepoxide)與一雙官能基物種(difunctional species)之一適當配比混合物(stoichiometric mixture)經聚合反應(polymerization)而成。該雙環氧化物係一具環氧當量(epoxy equivalent weight)約自100至10000之環氧樹脂。例如：雙酚A二環氧甘油醚(diglycidyl ether of bisphenol A)、diglycidyl ether of 4,4'-sulfonyldiphenol、diglycidyl ether of 4,4'-oxydiphenol、diglycidyl ether of 4,4'-dihydroxybenzophenone、對苯二酚二環氧甘油醚(diglycidyl ether of hydroquinone)及diglycidyl ether of 9,9-(4-hydroxyphenyl)fluorine。該雙官能基物種係一二元酚(dihydric phenol)、一二羧酸(dicarboxylic acid)、一一級胺(primary amine)、一二胇基化物(dithiol)、disulfonamide或一雙二級胺(bis-secondary amine)。該二元酚可選自4,4'-isopropylidene bisphenol(bisphenol A)、4,4'-sulfonyldiphenol、4,4'-oxydiphenol、4,4'-dihydroxybenzophenone或9,9-bis(4-hydroxyphenyl)fluorene。該二羧酸可選自異苯二甲酸(isophthalic acid)、對苯二甲酸(terephthalic acid)、4,4'-biphenylenedicarboxylic acid或2,6-naphthalenedicarboxylic acid。該雙二級胺可選自比陪拉辛(piperazine)、dimethylpiperazine或1,2-bis(N-methylamino)ethane。該一級胺可選自對甲氧基苯胺(4-methoxyaniline)或乙醇胺(2-aminoethanol)。該二胇基化物可為4,4'-dimercaptodiphenyl ether。該disulfonamide可選自N,N'-dimethyl-1,3-benzenedisulfonamide或N,N'-bis(2-hydroxyethyl)-4,4-biphenyldisulfonamide。此外，該雙官能基物種亦可是包含兩種可與環氧基群(epoxide group)反應之不同功能團(functionality)之混合物；例如；水楊酸(salicylic acid)及4一羥基苯甲酸(4-hydroxybenzoic acid)。In addition, the thermoplastic plastic may optimally comprise a hydroxy-phenoxyether polymer structure. The hydroxy-phenoxy resin ether is formed by a polymerization of a stoichiometric mixture of a diepoxide and a difunctional species. The diepoxide is an epoxy resin having an epoxy equivalent weight of from about 100 to 10,000. For example: diglycidyl ether of bisphenol A, diglycidyl ether of 4, 4'-sulfonyldiphenol, diglycidyl ether of 4, 4'-oxydiphenol, diglycidyl ether of 4, 4'-dihydroxybenzophenone, p-benzene Diglycidyl ether of hydroquinone and diglycidyl ether of 9,9-(4-hydroxyphenyl)fluorine. The bifunctional species is a dihydric phenol, a dicarboxylic acid, a primary amine, a dithiol, a disulfonamide or a pair of secondary amines ( Bis-secondary amine). The dihydric phenol may be selected from the group consisting of 4,4'-isopropylidene bisphenol (bisphenol A), 4,4'-sulfonyldiphenol, 4,4'-oxydiphenol, 4,4'-dihydroxybenzophenone or 9,9-bis (4-hydroxyphenyl). Fluorene. The dicarboxylic acid may be selected from the group consisting of isophthalic acid, terephthalic acid, 4,4'-biphenylenedicarboxylic acid or 2,6-naphthalenedicarboxylic acid. The bis-second amine can be selected from the group consisting of piperazine, dimethylpiperazine or 1,2-bis(N-methylamino)ethane. The primary amine may be selected from the group consisting of 4-methoxyaniline or 2-aminoethanol. The dimercapto compound can be 4,4'-dimercaptodiphenyl ether. The disulfonamide may be selected from N,N'-dimethyl-1,3-benzenedisulfonamide or N,N'-bis(2-hydroxyethyl)-4,4-biphenyldisulfonamide. In addition, the bifunctional species may also be a mixture comprising two different functionalities that can react with an epoxide group; for example, salicylic acid and 4-hydroxybenzoic acid (4) -hydroxybenzoic acid).
本發明導熱絕緣高分子材料中之熱塑型塑膠亦可選自一液態環氧樹脂與雙酚A(bisphenol A)、雙酚F(bisphenol F)或雙酚S(bisphenol S)之生成物(reaction product)、一液態環氧樹脂與一二價酸(diacid)之生成物或一液態環氧樹脂與一胺類(amine)之生成物。The thermoplastic plastic in the thermally conductive insulating polymer material of the present invention may also be selected from the group consisting of a liquid epoxy resin and a bisphenol A, a bisphenol F or a bisphenol S. Reaction product), a liquid epoxy resin and a diacid product or a liquid epoxy resin and an amine product.
本發明導熱絕緣高分子材料中之熱固型環氧樹脂除表一所述之材料外，亦可選自"Saechtling International plastic Handbook for the Technology,Engineer and User,Second Edition,1987,Hanser Publishers,Munich"之第1頁及第2頁中所定義之熱固型樹脂(thermosetting resin)。該熱固型樹脂在該高分子成分中所佔的體積百分比一般係介於90%至25%，較佳地係介於85%至40%，特別地係介於75%至55%。且該高分子成分中之該實質非結晶熱塑型樹脂與該熱固型樹脂之體積比係大約介於1：9至3：1。該熱固型樹脂較佳地係具有大於2之官能團基。於室溫之下，該熱固型樹脂係呈現液態或固態。若該熱固型樹脂在不加入熱塑型樹脂之條件下而固化，則該熱固型樹脂將呈現堅硬狀(rigid)或橡膠狀(rubbery)。較佳之熱固型樹脂係一未固化環氧樹脂(uncured epoxy resin)，特別是定義於ASTM D 1763之未固化之液態環氧樹脂。關於液態之環氧樹脂可參考"Volume 2of Engineered Materials Handbook,Engineering Plastics,published by ASM International"第240~241頁之敘述。有關「環氧樹脂」一詞係指包含至少兩個環氧官能基(epoxy functional group)之傳統二聚環氧樹脂(dimeric epoxy)、單體環氧樹脂(oligomeric epoxy)或聚合環氧樹脂(polymeric epoxy)。該環氧樹脂之種類可以是雙酚A(bisphenol A)與環氧氯丙烷(epichlorohydrin)之生成物、酚(phenol)與甲醛(formaldehyde，其係一種酚醛清漆樹脂(novolacresin))之生成物、環氧氯丙烷(epichlorohydrin)、環烷類(cycloaliphatic)、過酸環氧樹脂(peracid epoxy)及縮水甘油醚(glycidyl ester)、環氧氯丙烷與對氨基苯酚(p-amino phenol)之生成物、環氧氯丙烷與glyoxal tetraphenol之生成物、酚酫環氧樹脂(novolac epoxy)或酚甲烷樹脂(bisphenol A epoxy)。商用上可取得的環氧化酯(epoxidic ester)較佳地係3,4-epoxycyclohexyl methy13,4-epoxycyclohexane-carboxylate(例如：Union Carbide公司之ERL 4221或Ciba Geigy公司之CY-179)或bis(3,4-epoxycyclohexylmethyl)adipate(例如：Union Carbide公司之ERL 4299)。商用上可取得的diglycidic ether of bisphenol-A(DGEBA)可選自Ciba Geigy公司之Araldite 6010、陶氏化學公司之DER 331及殼牌化學公司(Shell Chemical Company)之Epon 825、828、826、830、834、836、1001、1004或1007等。另，聚環氧化酚甲醛預聚合物(polyepoxidized phenol formaldehyde novolac prepolymer)可選自陶氏化學公司之DEN 431或438及Ciba Geigy公司之CY-281。而polyepoxidized cersol for maldehyde novolac prepolymer則可選自Ciba Geigy公司之ENC 1285、1280或1299。Polyglycidyl ether of polyhydric alcohol可選自Ciba Geigy公司之Araldite RD-2(係以butane-1,4-diol為基礎)或選自殼牌化學公司之Epon 812(係以甘油(glycerin)為基礎)。一合適之diepoxide of an alkylcycloalkyl hydrocarbon係乙烯基環已烷之氧化物(vinyl cyclohexane dioxide)，例如：Union Carbide公司之ERL 4206。另，一合適之diepoxide of a cycloalkyl ether係bis(2,3-diepoxycyclopentyl)-ether，例如：Union Carbide公司之ERL 0400。此外，商用上可取得之軟性環氧樹脂(flexible epoxy resin)包含polyglycol diepoxy(例如：陶氏化學公司之DER 732及736)、diglycidyl ester of linoleic dimer acid(例如：殼牌化學公司之Epon 871及872)及diglycidyl ester of a bisphenol，其中芳香環(aromatic ring)係藉由一長脂肪鍵(long aliphatic chain)連接(例如：Mobay Chemical company之Lekutherm X-80)。The thermosetting epoxy resin in the thermally conductive insulating polymer material of the present invention may be selected from the materials described in Table 1, "Saechtling International plastic Handbook for the Technology, Engineer and User, Second Edition, 1987, Hanser Publishers, Munich." "The thermosetting resin as defined on pages 1 and 2. The volume percentage of the thermosetting resin in the polymer component is generally from 90% to 25%, preferably from 85% to 40%, particularly from 75% to 55%. And the volume ratio of the substantially amorphous thermoplastic resin to the thermosetting resin in the polymer component is about 1:9 to 3:1. The thermosetting resin preferably has a functional group of more than 2. The thermosetting resin exhibits a liquid or solid state at room temperature. If the thermosetting resin is cured without adding a thermoplastic resin, the thermosetting resin will exhibit a rigid or rubbery shape. A preferred thermoset resin is an uncured epoxy resin, particularly an uncured liquid epoxy resin defined in ASTM D 1763. For the epoxy resin of the liquid state, refer to "Volume 2 of Engineered Materials Handbook, Engineering Plastics, published by ASM International", pages 240 to 241. The term "epoxy resin" means a conventional dimeric epoxy, an oligomeric epoxy or a polymeric epoxy resin comprising at least two epoxy functional groups. Polymeric epoxy). The type of the epoxy resin may be a product of bisphenol A and epichlorohydrin, a product of phenol and formaldehyde, which is a novolac resin. Epichlorohydrin, cycloaliphatic, peracid epoxy and glycidyl ester, epichlorohydrin and p-amino phenol , a product of epichlorohydrin and glyoxal tetraphenol, novolac epoxy or bisphenol A epoxy. Commercially available epoxidic esters are preferably 3,4-epoxycyclohexyl methy 13,4-epoxycyclohexane-carboxylate (for example: ERL 4221 from Union Carbide or CY-179 from Ciba Geigy) or bis (3) , 4-epoxycyclohexylmethyl)adipate (eg, ERL 4299 from Union Carbide). Commercially available diglycidic ether of bisphenol-A (DGEBA) may be selected from Aribaite 6010 from Ciba Geigy, DER 331 from The Dow Chemical Company, and Epon 825, 828, 826, 830 from Shell Chemical Company. 834, 836, 1001, 1004 or 1007, etc. Alternatively, the polyepoxidized phenol formaldehyde novolac prepolymer may be selected from DEN 431 or 438 of The Dow Chemical Company and CY-281 of Ciba Geigy Corporation. The polyepoxidized cersol for maldehyde novolac prepolymer may be selected from Ciba Geigy's ENC 1285, 1280 or 1299. The Polyglycidyl ether of polyhydric alcohol may be selected from Aribaite RD-2 of Ciba Geigy Corporation (based on butane-1,4-diol) or Epon 812 (based on glycerin) selected from Shell Chemical Company. A suitable diepoxide of an alkylcycloalkyl hydrocarbon is a vinyl cyclohexane dioxide such as ERL 4206 from Union Carbide. Further, a suitable diepoxide of a cycloalkyl ether is bis(2,3-diepoxycyclopentyl)-ether, for example, ERL 0400 of Union Carbide. In addition, commercially available flexible epoxy resins include polyglycol diepoxy (eg, DER 732 and 736 from The Dow Chemical Company) and diglycidyl ester of linoleic dimer acid (eg, Epon 871 and 872 from Shell Chemical Company). And diglycidyl ester of a bisphenol, wherein the aromatic ring is linked by a long aliphatic chain (for example: Lekutherm X-80 of Mobay Chemical company).
此外，上述具有複數個功能團之熱固型樹脂可選自陶氏化學公司之DEN 4875(其係一固態酚醛樹脂型環氧樹脂，solid epoxy novolac resin)、殼牌化學公司之Epon 1031(其係一四功能固態環氧樹脂，tetrafunctional solid epoxy resin)及Ciba-Geigy公司之Araldite MY 720(N,N,N',N'-tetraglycidyl-4,4'-methylenebisbenzenamine)。另，雙官態基環氧樹脂(difunctional epoxy resin，其係一雙環氧化物)可選自殼牌化學公司之HPT 1071(係一固態樹脂，N,N,N',N'-tetraglycidyl-a,a'-bis(4-aminophenyl)p-diisopropylbenzene)、HPT 1079(係一固態diglycidyl ether of bisphenol-9-fluorene)或Ciba-Geigy公司之Araldite 0500/0510(triglycidylether of para-aminophenol)。In addition, the above thermosetting resin having a plurality of functional groups may be selected from DEN 4875 of Tow Chemical Co., Ltd. (which is a solid epoxy novolac resin), and Epon 1031 of Shell Chemical Co., Ltd. A tetrafunctional solid epoxy resin and Araldite MY 720 (N, N, N', N'-tetraglycidyl-4, 4'-methylenebisbenzenamine) from Ciba-Geigy. In addition, a difunctional epoxy resin (a double epoxide) may be selected from Shell Chemical Company's HPT 1071 (a solid resin, N, N, N', N'-tetraglycidyl-a, A'-bis(4-aminophenyl)p-diisopropylbenzene), HPT 1079 (either a solid diglycidyl ether of bisphenol-9-fluorene) or Ciba-Geigy's Araldite 0500/0510 (triglycidylether of para-aminophenol).
使用於本發明之該固化劑可選自isophthaloyl dihydrazide、benzophenone tetracarboxylic dianhydride、二乙基甲苯二胺(diethyltoluene diamine)、3,5-dimethylthio-2,4-toluene diamine、雙氰胺(dicyandiamide，可取自American Cyanamid公司之Curazol 2PHZ)或DDS(diaminodiphenyl sulfone，可取自Ciba-Geigy公司之Calcure)。該固化劑亦可選自一取代雙氰胺(substituted dicyandiamides，例如2,6-xylenyl biguanide)、一固態聚醯胺(solid polyamide，例如：Ciba-Geigy公司之HT-939或Pacific Anchor公司之Ancamine 2014AS)、一固態芳香胺(solid aromatic amine，例如：殼牌化學公司之HPT 1061及1062)、一固態酐硬化劑(solid anhydride hardener，例如：苯均四酸二酐(pyromellitic dianhydride；PMDA))、一酚醛樹脂硬化劑(phenolic resin hardener，例如：聚對氫氧基苯乙烯(poly(p-hydroxy styrene)、咪唑(imidazole)、2-phenyl-2,4-dihydroxymethylimidazole及2,4一diamino-6[2'-methylimidazolyl(1)]ethyl-s-triaxine isocyanate adduct)、三氟化硼(boron trifluoride)及一胺基複合物(amine complex，例如：Pacific Anchor公司之Anchor 1222及1907)及三甲醇基丙烷三丙稀酸脂(trimethylol propane triacrylate)。The curing agent used in the present invention may be selected from the group consisting of isophthaloyl dihydrazide, benzophenone tetracarboxylic dianhydride, diethyltoluene diamine, 3,5-dimethylthio-2, 4-toluene diamine, and dicyandiamide. From American Cyanamid's Curazol 2PHZ) or DDS (diaminodiphenyl sulfone, available from Ciba-Geigy's Calcure). The curing agent may also be selected from the group consisting of substituted dicyandiamides (for example, 2,6-xylenyl biguanide), solid polyamide (for example: HT-939 of Ciba-Geigy Co., Ltd. or Ancamine of Pacific Anchor Co., Ltd.). 2014AS), a solid aromatic amine (for example, HPT 1061 and 1062 of Shell Chemical Company), a solid anhydride hardener (for example, pyromellitic dianhydride (PMDA)), A phenolic resin hardener (eg, poly(p-hydroxy styrene), imidazole, 2-phenyl-2,4-dihydroxymethylimidazole, and 2,4-diamino-6 [2'-methylimidazolyl(1)]ethyl-s-triaxine isocyanate adduct), boron trifluoride and amine complex (for example: Pacific Anchor's Anchor 1222 and 1907) and trimethylol Trimethylol propane triacrylate.
針對該熱固型環氧樹脂而言，一較佳之固化劑係上述之雙氰胺(dicyandiamide)，且可配合一固化加速劑(curing accelerator)使用。常用之固化加速劑包含尿素(urea)或尿素之化合物(urea compound)。例如：3-phenyl-1,1-dimethylurea、3-(4-chlorophenyl)-1,1-dimethyl urea、3-(3,4-dichlorophenyl)-1,1-dimethyl urea、3-(3-chloro-4-methylphenyl)一1,1-dimethyl urea及咪唑(imidazole)(例如：2-heptadecylimidazole、1-cyanoethyl-2-phenylimidazole-trimellitate或2-[.beta.-{2'-methylimidazoyl-(1')}]-ethyl-4,6-diamino-s-triazine)。For the thermosetting epoxy resin, a preferred curing agent is the above-mentioned dicyandiamide, and can be used in combination with a curing accelerator. Commonly used curing accelerators include urea (urea) or urea compound (urea compound). For example: 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethyl urea, 3-(3,4-dichlorophenyl)-1,1-dimethyl urea, 3-(3-chloro -4-methylphenyl)-1,1-dimethyl urea and imidazole (eg 2-heptadecylimidazole, 1-cyanoethyl-2-phenylimidazole-trimellitate or 2-[.beta.-{2'-methylimidazoyl-(1') )}]-ethyl-4,6-diamino-s-triazine).
若該熱固型環氧樹脂係一氨基鉀酸脂(urethane)，則該固化劑可使用一阻隔性異氰酸酯(blocked isocyanate)(例如：烷基酚阻隔性異氰酸酯(alkyl phenol blocked isocyanate)，其可取自Mobay Corporation之Desmocap 11A)或一酚阻隔性聚異氰酸酯加成物(phenol blocked polyisocyanate adduct)(例如：Mobay Corporation之Mondur S)。若該熱固型環氧樹脂係一非飽合聚酯樹脂(unsaturated polyester resin)，則該固化劑可使用一過氧化物(peroxide)或其他自由基催化劑(free radical catalyst)，例如：過氧化二異丙苯(dicumyl peroxide)、2,5-dimethyl-2,5-di(t-butylperoxy)hexane、t - butyl cumyl peroxide及2,5-dimethyl-2,5-di(t- butylperoxy)hexyne-3。此外，該非飽合聚酯樹脂可利用放射線照射(irradiation，例如：紫外線照射、高能電子束照射或γ輻射)以產生交聯。If the thermosetting epoxy resin is urethane, the curing agent may use a blocked isocyanate (for example, an alkyl phenol blocked isocyanate). Desmocap 11A) from Mobay Corporation or a phenol blocked polyisocyanate adduct (for example: Mondur S from Mobay Corporation). If the thermosetting epoxy resin is an unsaturated polyester resin, the curing agent may use a peroxide or a free radical catalyst, for example, peroxidation. Dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl cumyl peroxide and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne -3. Further, the non-saturated polyester resin may be irradiated (radiation, for example, ultraviolet irradiation, high-energy electron beam irradiation, or gamma irradiation) to cause crosslinking.
某些熱固型環氧樹脂不需使用固化劑即可固化。例如：若該熱固型環氧樹脂係一雙馬來醯亞胺(bismaleimide，BMI)，則該雙馬來醯亞胺將於一高溫下產生交聯且一共固化劑(co-curing agent)，例如O,O'-diallyl bisphenol A，可一起添加使得已固化之雙馬來醯亞胺更加堅韌。Some thermoset epoxy resins cure without the use of a curing agent. For example, if the thermosetting epoxy resin is a double bismaleimide (BMI), the bismaleimide will crosslink at a high temperature and a co-curing agent. For example, O, O'-diallyl bisphenol A, can be added together to make the cured bismaleimide tougher.
上述可利用過氧化物交聯劑(peroxide crosslinking agent)、高能電子束或γ輻射以產生交聯之樹脂較佳地可以添加非飽合交聯助益劑(unsaturated crosslinking aid)，例如：三丙烯異三聚氰酸(triallyl isocyanurate，TAIC)、三聚氰酸三丙烯酯(triallyl cyanurate，TAC)或三羥甲基丙烷三丙烯酸酯(trimethylol propanetriacrylate，TMPTA)。The above-mentioned peroxide crosslinking agent, high energy electron beam or gamma radiation may be used to produce a crosslinked resin. Preferably, a non-saturated crosslinking aid may be added, for example, tripropylene. Trimeric isocyanurate (TAIC), triallyl cyanurate (TAC) or trimethylol propanetriacrylate (TMPTA).
絕緣材料中可包含一種或多種陶瓷粉末，陶瓷粉末可選自氮化物、氧化物或前述氮化物與前述氧化物之混合物。該氮化物可以使用氮化鋯、氮化硼、氮化鋁或氮化矽。該氧化物可以使用氧化鋁、氧化鎂、氧化鋅、二氧化矽或二氧化鈦。One or more ceramic powders may be included in the insulating material, and the ceramic powder may be selected from the group consisting of nitrides, oxides, or a mixture of the foregoing nitrides and the foregoing oxides. As the nitride, zirconium nitride, boron nitride, aluminum nitride or tantalum nitride can be used. As the oxide, alumina, magnesia, zinc oxide, ceria or titania can be used.
圖3顯示本發明一實施例之連續式射出成型裝置20之示意圖。連續式射出成型裝置20包含一入料機構21、一送料機構22、具一狹縫32之一模頭23、一壓輪裝置24及一裁切裝置25。入料機構21係用於提供製作用之絕緣材料26。送料機構22將該絕緣材料26擠壓通過該模頭23之該狹縫32，藉以形成一板狀基材27，其中該絕緣材料26擠壓通過該狹縫32時之溫度可介於50℃至150℃。壓輪裝置24包含鋼輪28，該鋼輪28上分別繞轉第一膜材29與第二膜材30。當板狀基材27通過該鋼輪28時，該第一膜材29與該第二膜材30分別壓附於板狀基材27之兩板面。裁切裝置25係用於將該板狀基材27裁切成導熱絕緣基板31。Figure 3 shows a schematic view of a continuous injection molding apparatus 20 in accordance with one embodiment of the present invention. The continuous injection molding apparatus 20 includes a feeding mechanism 21, a feeding mechanism 22, a die 23 having a slit 32, a pressure roller device 24, and a cutting device 25. The feeding mechanism 21 is for providing an insulating material 26 for production. The feeding mechanism 22 presses the insulating material 26 through the slit 32 of the die 23 to form a plate-like substrate 27, wherein the temperature of the insulating material 26 when pressed through the slit 32 can be between 50 ° C To 150 ° C. The pressure roller device 24 includes a steel wheel 28 on which the first film 29 and the second film 30 are wound, respectively. When the plate-like substrate 27 passes through the steel wheel 28, the first film 29 and the second film 30 are respectively pressed against the two plate faces of the plate-like substrate 27. The cutting device 25 is used to cut the plate-like base material 27 into a thermally conductive insulating substrate 31.
本發明之技術內容及技術特點已揭示如上，然而熟悉本項技術之人士仍可能基於本發明之教示及揭示而作種種不背離本發明精神之替換及修飾。因此，本發明之保護範圍應不限於實施例所揭示者，而應包括各種不背離本發明之替換及修飾，並為以下之申請專利範圍所涵蓋。The technical and technical features of the present invention have been disclosed as above, and those skilled in the art can still make various substitutions and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the present invention should be construed as being limited by the scope of the appended claims
S11~S16．．．流程步驟S11~S16. . . Process step
10、10'、10"．．．導熱絕緣複合基板10, 10', 10"... Thermally Conductive Insulation Composite Substrate
11．．．導熱絕緣基板11. . . Thermally conductive insulating substrate
12．．．印刷電路板12. . . A printed circuit board
13．．．金屬基板13. . . Metal substrate
14、15．．．金屬材14,15. . . Metal
20．．．連續式射出成型裝置20. . . Continuous injection molding device
21．．．入料機構twenty one. . . Feeding mechanism
22．．．送料機構twenty two. . . Feeding mechanism
23．．．模頭twenty three. . . Die
24．．．壓輪裝置twenty four. . . Pressure roller device
25．．．裁切裝置25. . . Cutting device
26．．．絕緣材料26. . . Insulation Materials
27．．．板狀基材27. . . Plate substrate
28．．．鋼輪28. . . Steel wheel
29．．．第一膜材29. . . First film
30．．．第二膜材30. . . Second film
31．．．導熱絕緣基板31. . . Thermally conductive insulating substrate
32．．．狹縫32. . . Slit
圖1顯示本發明一實施例之導熱絕緣基板之製備方法之流程示意圖；1 is a flow chart showing a method of preparing a thermally conductive insulating substrate according to an embodiment of the present invention;
圖2A至圖2C顯示本發明一實施例之導熱絕緣複合基板之剖面示意圖；及2A to 2C are schematic cross-sectional views showing a thermally conductive and insulating composite substrate according to an embodiment of the present invention; and
圖3顯示本發明一實施例之連續式射出成型裝置之示意圖。Fig. 3 is a view showing a continuous injection molding apparatus according to an embodiment of the present invention.
S11~S16．．．流程步驟S11~S16. . . Process step
Claims (29)
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| TW302372B (en) * | 1994-08-19 | 1997-04-11 | Asahi Chemical Ind | |
| TW500655B (en) * | 1999-07-07 | 2002-09-01 | Shinetsu Chemical Co | Heat-resistant silicone rubber composite sheet having thermal conductivity and method of producing the same |
| TW200623490A (en) * | 2004-12-31 | 2006-07-01 | Ind Tech Res Inst | Battery separator and method of making the same |
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| TW302372B (en) * | 1994-08-19 | 1997-04-11 | Asahi Chemical Ind | |
| TW500655B (en) * | 1999-07-07 | 2002-09-01 | Shinetsu Chemical Co | Heat-resistant silicone rubber composite sheet having thermal conductivity and method of producing the same |
| TW200623490A (en) * | 2004-12-31 | 2006-07-01 | Ind Tech Res Inst | Battery separator and method of making the same |
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