200817481 九、發明說明： t發明所屬之技術領域；j 發明領域 本發明係有關於一種導熱性糊（硬化性導熱性樹脂組 5成物），詳而言之，係有關於一種可做為基板絕緣材料使用 之導熱性糊。 【先前技術：> 發明背景 10 15 2〇 近年來，隨著對電子機器之高性能化、小型薄型化之 要求增加，晶片零件、半導體之高密度化顯著進步，且安 裝用電路基板之高散熱性機能亦日漸重要。 如刚述之同散熱性電路基板，一般來說，係將财熱性 =劑塗布於發熱零件，並裝設散減扇。另外，耐熱性 '丨係於熱硬化性或熱可歸樹脂内大量填充無機填 定球_而言’特開2__217861號公報揭示有利用含有特 熱硬Γ氧偏8、錢垸改質聚_醯亞胺、熱硬化性樹脂、 屬（气2祕體q狀耐熱性接著騎銅或料之散熱風 政熱板)接著於電路基板之方法。 劍，因述方去由於含有用以使接著劑呈片狀之溶 另外，亦ί於阻塞處時，會有產生孔隙或龜裂之虞。 忠）、使用金屬板做為騎之基板製作方法(金屬 等。牙孔續之方法、及將金屬板貼附於基板之方法 但是 ，有蓉於更加㈣散歸性之需求，所以在 前述 5 200817481 10 迄今製作前述高散熱性電路基板之方法，—般而士 ==接著散熱片。又’散熱片係將大量填充有;傳 、充狀聚合物加4片狀之散熱材，其特色係容易 舉例而言’特開平1()_183嶋號公報揭示有—種 s有環氧樹脂與其硬化劑、預定之高分子量樹脂、促進 2匕Μ &無機填狀接著性纟 1成物卿a的導熱性接著 仁疋使用別述散熱片之方法具有對被接著材之凹凸 適應性不充分的缺點。尤其是近年來對散熱特性之要求漸 趨嚴格’大量填充陶究粒子的結果造成硬度上升，導致凹 凸適應性不足之情形更加嚴重。另外，前述特開平 15 1〇-1請86號公報揭示之發明由於含有高分子量樹脂，所以 亦有耐熱性不足的問題。 第1圖係顯示使用導熱性糊之基板成型例的標準截面 圖其中付说1為铭板、2為導熱性糊、3為零件、4為設置 於零件上之圖案。如第1(a)圖所示，在利用印刷法塗布填埋 〇零件3之圖案4的導熱性糊2後，再透過加壓製程加壓接著銘 板1 〇 因此，導熱性糊被要求具備可利用印刷法或加壓法如 第1圖所示般填埋零件3之圖案4的流動性、可使用於阻塞處 之不含溶劑性、以及可接著固定零件之密著性等特性。 6 200817481 但是，為了賦予充分散熱性必須添加大量高導熱性填 料，糊的黏度會隨著填料分量增加而提高，導致流動性降 低。又，若於糊添加難燃劑以賦予基板難燃性，會造成前 述黏度提高的問題更加嚴重。如果欲藉由選擇環氧樹脂以 5改善前述黏度提高之問題，反而會出現物理特性降低的情 形。 另外，隨著基板生產據點之全球化，對延長導熱性糊 之適用期，即，更提高其保存穩定性之需求亦逐漸增加。 【專利文獻1】特開平10-183086號公報 1〇 【專利文獻2】特開2004-217 8 61號公報 C 明内】 發明揭示 本發明欲解決之問題 為了解決前述問題，本發明之目的在於提供一種不僅 散熱性良好’且具有適用於網版印刷之低黏度，更具備優 異保存穩定性及硬化物之物理特性之導熱性糊。 解決問題之方法 為解決前述問題，本發明係將含有丙烯酸樹脂與環氧 樹脂硬化劑之A液、與含有環氧樹脂與丙烯酸樹脂硬化劑之 δ液分離’並將導熱性填料以相對於1〇〇重量份前述丙稀酸 樹脂與前述環氧樹脂合計量為100〜1000重量份之比例摻合 至前述Α液及Β液之其中一者或兩者内，再於使用前以前述 丙烯酸樹脂與前述環氧樹脂之混合比率（重量％)為1〇 ·· 9〇〜90 : 10之比例混合前述A液與B液後，製成導熱性糊。 7 200817481 前述導熱性糊中，丙烯酸樹脂可使用丨種或2種以、 自於由異戊基丙烯酸酯、新戊二醇二丙烯酸酯、三^上選 丙烧三丙稀酸_、二三㈣基丙烧四丙稀酸_、笨^基 甘油_丙騎六亞甲二異氰酸g旨胺基f㈣旨預聚合^佑水 酚A二縮水甘油醚丙烯酸添加物、乙二醇二甲美丙烯 雙 及二乙二醇二曱基丙烯酸酯所構成之群者。 、次S曰、 另外，環氧樹脂硬化劑可使用丨種或2種以上選 紛系硬化劑硬化劑、陽離子系硬化劑所構成於由 10 15 又，丙烯酸樹脂硬化劑可使用i種或2種以上選自。 銨系硬化劑及自由基系硬化劑所構成之群者。 於由 並且，可應需要m種或2種以上選自於由醇酸樹脂、 三聚氰胺職n苯樹賴構成之群之細旨以小:前 述A液及B液之樹脂成分總量之40重量％的比率與a液及b 液之其中一者或兩者換合。 本發明所使用之導熱性糊填充劑，以1種或2種以上選 自於由A1203、Si02、C、BN及A1N所構成之群者為佳。 本發明中’前述A液及B液之其中一者或兩者可摻合賦 予難燃性劑。 發明效果 本發明之導熱性糊具有高散熱性，並具備可在未使用 溶劑之情況下用於網版印刷之低黏度，更具備優異保存穩 定性。硬化本發明所製成之硬化物亦具有良好物理特性。 圖式簡單說明 第1圖係顯示使用導熱性糊之基板成型例的標準截面 8 200817481 圖，且第1(a)圖係顯示將導熱性糊塗布（印刷）於表面形成有 圖案之零件後之基板，而第1(b)圖係顯示將銘板加壓接著於 第1(a)圖之基板並硬化後的狀態。 t實施方式】 5 較佳實施例之詳細說明 本發明之導熱性糊，如前所述，在使用前為含有丙烯 酸樹脂與環氧樹脂硬化劑之A液、及與A液分離之含有環氧 樹脂與丙烯酸樹脂硬化劑之B液。由於A液與B液分離，分 別促進前述兩種樹脂硬化之硬化劑在兩液混合前亦可與前 10 述兩種樹脂分離，所以本發明具有優異保存穩定性。又， 因為具備前述兩種樹脂用之硬化劑，所以兩液混合後可快 速硬化。 A液所含有之丙烯酸樹脂具有1或2個以上分子構造式 ⑴所記載之反應基，且亦可併用2種以上丙烯酸樹脂。 15 【化1】 〇200817481 IX. Description of the invention: The technical field to which the invention belongs; j FIELD OF THE INVENTION The present invention relates to a thermal conductive paste (curable thermal conductive resin group 5), and more specifically, a substrate can be used as a substrate Thermal paste for insulation materials. [Prior Art: Inventive Background 10 15 2 In recent years, with the increase in the demand for higher performance and smaller size of electronic equipment, the density of wafer parts and semiconductors has significantly improved, and the mounting circuit board has been high. Heat dissipation performance is also becoming increasingly important. As described above, the heat-dissipating circuit board is generally coated with a heat-generating agent on a heat-generating component, and a fan is installed. In addition, the heat resistance '丨 is a large amount of inorganic filler ball filled in the thermosetting or heat-returnable resin. _ Unexamined-Japanese-Patent No. 2__217861 discloses that the use of the special hot-hardened oxygen-oxygen partial 8 A method in which a bismuth imine, a thermosetting resin, or a genus (a heat-resistant wind-heating plate of a gas or a heat-resistant wind-heating plate) is applied to a circuit board. The sword, because it is contained, is used to make the adhesive into a sheet form, and when it is blocked, there will be pores or cracks. Loyalty, using a metal plate as a substrate for making a ride (metal, etc.. The method of continuing the hole and the method of attaching the metal plate to the substrate. However, there is a need for further (4) dispersion, so in the above 5 200817481 10 So far, the method for fabricating the above-mentioned high heat dissipation circuit substrate is as follows: the general heat == followed by the heat sink. The heat sink is filled with a large amount; the heat transfer material is filled with four sheets, and the characteristics are It is easy to exemplify the 'Special Kaiping 1()_183 公报 揭示 揭示 揭示 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂The thermal conductivity is followed by the use of a heat sink, which has the disadvantage of insufficient adaptability to the unevenness of the material to be bonded. In particular, the demand for heat dissipation characteristics has become stricter in recent years. In addition, the invention disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. 86 discloses a problem that the heat resistance is insufficient due to the high molecular weight resin. A standard cross-sectional view showing a substrate molding example using a thermal conductive paste, wherein 1 is a nameplate, 2 is a thermal conductive paste, 3 is a component, and 4 is a pattern provided on the component. As shown in Fig. 1(a) After the thermal conductive paste 2 of the pattern 4 of the entangled part 3 is applied by a printing method, and then pressed through a pressurizing process, the nameplate 1 is pressed. Therefore, the thermal conductive paste is required to have a printing method or a pressurizing method. As shown in Fig. 1, the fluidity of the pattern 4 of the landfill part 3, the solvent-free property of the blockage portion, and the adhesion of the component can be fixed. 6 200817481 However, in order to impart sufficient heat dissipation When a large amount of high thermal conductive filler is added, the viscosity of the paste increases as the filler component increases, resulting in a decrease in fluidity. Further, if a flame retardant is added to the paste to impart flame retardancy to the substrate, the problem of the aforementioned viscosity increase is more serious. If the problem of the above-mentioned viscosity improvement is to be improved by selecting an epoxy resin, the physical properties may be lowered. In addition, as the substrate production base is globalized, the application period of the thermal conductive paste is extended, that is, In addition, the demand for the storage stability of the present invention is increasing. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Solution to Problem In order to solve the above problems, an object of the present invention is to provide a thermally conductive paste which has not only good heat dissipation but also has low viscosity suitable for screen printing, and has excellent storage stability and physical properties of a cured product. In order to solve the above problems, the present invention separates the liquid A containing the acrylic resin and the epoxy resin hardener, and the delta liquid containing the epoxy resin and the acrylic resin hardener, and the thermal conductive filler is relative to 1 〇〇. a part by weight of the above-mentioned acrylic resin and the above epoxy resin in a ratio of 100 to 1000 parts by weight, which is blended into one or both of the above-mentioned mash and mash, and before the use, the aforementioned acrylic resin and the aforementioned The mixing ratio (% by weight) of the epoxy resin is a ratio of 1 〇·· 9 〇 to 90:10, and the liquid A and the liquid B are mixed to prepare a thermally conductive paste. 7 200817481 In the above thermal conductive paste, the acrylic resin may be used in the form of two or two kinds, from isoamyl acrylate, neopentyl glycol diacrylate, and triglyceride. (4) propyl propylene tetrapropyl acid _, stupid glycerol _ propylene riding hexamethylene diisocyanate g amino group f (four) pre-polymerization water phenol A diglycidyl ether acrylic acid additives, ethylene glycol A group of propylene propylene and diethylene glycol dimercapto acrylate. In addition, the epoxy resin curing agent may be composed of two or more kinds of hardener hardeners and cationic hardeners, and may be used for 10 15 or 15 or less. More than one species selected. A group consisting of an ammonium hardener and a radical hardener. In view of the above, it is possible to use m or two or more kinds selected from the group consisting of alkyd resin and melamine n-phenyl lysine to be small: 40 weight of the total amount of the resin components of the liquids A and B described above. The ratio of % is changed with one or both of liquid a and liquid b. The thermal conductive paste filler used in the present invention is preferably one or more selected from the group consisting of A1203, SiO2, C, BN and A1N. In the present invention, one or both of the above-mentioned liquids A and B may be blended to impart a flame retardant. EFFECTS OF THE INVENTION The thermally conductive paste of the present invention has high heat dissipation properties, and has a low viscosity for screen printing without using a solvent, and has excellent storage stability. Hardening of the hardened material produced by the present invention also has good physical properties. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a standard cross section 8 200817481 of a substrate molding example using a thermal conductive paste, and Fig. 1(a) shows a method of coating (printing) a thermal conductive paste on a surface on which a patterned part is formed. The substrate, and the first (b) diagram shows a state in which the nameplate is pressed against the substrate of the first (a) and hardened. t Embodiments] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermally conductive paste of the present invention, as described above, is an A liquid containing an acrylic resin and an epoxy resin hardener, and an epoxy containing a liquid separated from the A liquid before use. Liquid B of resin and acrylic resin hardener. Since the liquid A and the liquid B are separated, the hardener which promotes the hardening of the above two resins can be separated from the above two resins before the two liquids are mixed, so that the present invention has excellent storage stability. Further, since the above two resins are used as a curing agent, the two liquids can be quickly cured after being mixed. The acrylic resin contained in the liquid A has one or two or more reactive groups described in the molecular structural formula (1), and two or more kinds of acrylic resins may be used in combination. 15 【化1】 〇
II ch2 = C — c — 0 — ⑴II ch2 = C — c — 0 — (1)
II
R 在式(I)中，R代表Η或烴基，又，並未特別限定烴基之 碳數，一般為1〜3個。 適用於本發明之丙烯酸樹脂，具體而言，可舉例如： 20異戊基丙烯酸酯、新戊二醇二丙烯酸酯、三羥甲基丙烷三 丙烯酸酯、二三羥甲基丙烷四丙烯酸酯、苯基縮水甘油醚 丙烯醆六亞甲二異氰酸酯胺基甲酸酯預聚合物、雙酚Α二縮 200817481 水甘油_丙稀酸添加物、乙m -知:甲基丙稀酸酿等’且可併用2種以上前述丙稀酸樹 本發明因為使用前述丙稀酸_，可在不使用溶劑的 5 10 15 大量填純傳祕填錄，所以可㈣散熱性 貫現適用於網版印刷之低黏度。 另液所含有之環氧樹脂，只要分子内含有i個以 可二者即可，亦可併用2種以上環氧樹脂。具體來說， :如.雙粉人型每氧樹脂、演化環氧樹脂、雙盼F型環 氧樹脂、紛酸:型環負科日匕 、 虱树月日、月曰裱環氧樹脂、縮水甘油胺型 ㈣树脂、縮水甘油_環氧樹脂、縮水甘油酯型環 月曰、及雜環式環氧樹脂等。 胁Γ边丙稀酸樹脂與環氧樹脂之混合比率（重量％)係丙 喊树脂:環氧樹脂為叫㈣’又⑽:时 40為佳。丙烯酸樹脂之比率小於10重量％時黏度變化會增 又超過9〇重1〇/0時硬化後之物理特性會降低。 在本糾之導熱性糊中，可將醇酸樹脂、三聚氛胺樹 二广—f苯樹脂其中1或2種以上分別作為樹脂成型劑混 5後使用於前述丙稀酸樹脂、環氧樹脂内，亦可適當選擇 可作為前述樹月旨成型劑之其他樹脂，並未特別限制。 另外’前述作為樹脂成型劑之樹脂可添加至A液及B液 之其中一方，或兩液皆添加。 ^醇酉文㈣、二聚氰胺樹脂、及二甲苯樹脂其中^種以 ”引述AM烯酸樹脂及/或6液環氧樹脂混合時的混合 比’以A液丙烯酸樹脂及峨環氧樹脂占樹脂成份總重量之 20 200817481 6〇重量。/°以上為佳，又以9〇重量％以上更好。也就是說，作 為成型劑混合之樹脂的比率以小於樹脂成份總重量之4〇重 里竓為j土，又以小於重量％更好。 A液所含之環氧樹脂硬化劑，舉例而言，可使用如：酚 系硬化劑、咪唾硬化劑、陽離子系硬化劑等，且前述硬化 劑可單獨使用，亦可使用2種以上。 B液所含之丙稀酸樹脂硬化劑（聚合反應起始劑）可舉 逆如·銨系硬化劑、自由基系硬化劑等，且可單獨使用！種 前述物質，亦可使用2種以上。 酚系硬化劑可舉例如：酚醛樹脂、萘酚系化合物等。 咪唑系硬化劑，可舉例如：咪唑、2_十一基咪唑、厶 十七基咪唑、2-乙基咪唑、2-苯咪唑、2-乙基-4-甲基-咪唑、 h氰乙-2-十一基咪唑、2_苯咪唑、2,心二胺基_&[2、甲基咪 11 坐基-(1’)]•乙基_s_三啡等。 、 陽離子系硬化劑，可舉例如：三氟化硼之胺基塩、五 氟化銻-乙醯氯錯合物、含有苯乙基或烯丙基之疏鹽等。 銨系硬化劑，可舉例如：p-甲氧重氮苯六氟磷酸、二 笨鑷六氟磷酸、三苯疏、四·η-丁鱗四苯硼酸、四_n_丁磷_〇、 乙基二硫代石粦酸酯（ο-diethylphosphorodithioate)等。 自由基系硬化劑可舉例如：過氧化二異丙苯、過氧化 第二丁基異丙基苯、過氧化三級丁基、氫過氧化異丙苯 等。 硬化劑使用量雖然因種類而異，但是大致上來說，相 對於100重量份環氧樹脂與丙烯酸樹脂合計量，硬化劑使用 11 200817481 量為1〜40重量份左右。若使用量過少會導致硬化不良，過 多則會造成保存穩定性降低、物理特性降低等問題。 導熱性填料可與前述A液與B液之任一方混合，亦可與 雙方混合。又，可使用Al2〇3、Si02、C、BN及A1N之其中1 5種或2種以上作為導熱性填料。另外，填料之粒徑以平均粒 徑為0.1〜50μηι左右為佳。 填料混合量雖然因種類而異，但是通常相對於ι〇〇重量 份環氧樹脂與丙烯酸樹脂合計量，填充劑混合量以 100〜1000重量份左右為佳，又以3〇〇〜900重量份更好。 10 依照前述導熱性填料劑種類與量之選擇，可得到導熱 率約0.2〜2.8W/m · Κ之硬化物。 丨王州艰加難燃性賦予劑。並 未特別限定難燃性賦予劑之種類，可使用迄今普遍用於樹 脂添加劑之難燃劑。舉例而言，可使用如：磷酸三苯酯、 15磷酸三甲苯醋、嶙酸甲苯二苯酯等碟酸酉旨系化合物；^化 石壤等氯系化合物；六演苯等漠系化合物；經化鎮、經化 氧化紹等經化物；漠化銨；三氫化二錄等無機難_等， 但考慮到環保問題，在前述物質中，以經化物系、構系、 或碟酸系難燃劑為佳。 ,、 20 雖然難燃性職予劑之添加量與種類皆因需要而異, =上來說，相對於10。重量份樹脂成分以w㈧重量份 一叙^ ’若於劃旨組成物添加_難性劑會導致 高黏度化’但是由於本發明導熱性糊之成分如前所二，所 12 200817481 以即使添加有難燃性賦予劑，亦可保有可在未使用溶劑之 情形下進行網版印刷之低黏度。 又，在不超過本發明目的之範圍内，亦可於本發明導 熱性糊内添加消泡劑、增黏劑、顏料等添加劑。 5 、本發明導熱性糊，係分別調製以預定量摻合、混合前 ^各成77後製成之錄抑液，再於使用前摻合前述兩液並 進仃混合以形成前述預定比率之環氧樹脂與丙烯酸樹脂。 然後，利用網版印刷等塗布混合後製成之糊，並使其 硬化後成為所需形狀之基板。硬化條件雖然因所使用之樹 1〇 脂而異，彻 , 〜一般而言，以150〜200°C硬化30〜120分鐘左右。 (實施例） 以下為本發明之實施例，但本發明並未僅限定為以下 之實施例。 [實施例] 15 合， 不 〇 :表1所顯示之各成分以該表所示之比率（重量比）混 分別調製A液與B液。另外，各成分之詳細内容如下所 丙烯酸樹脂：2-羥-3-丙稀醯氧基甲基丙烯酸酯（8〇重量 二伸甘醇二丙烯酸酯（20重量❾/〇)。 1環氣樹脂：環氧樹脂EP_4901E(旭電化工業株式会社穿 (80重量％)、ED_529(旭電化工f株式会社製造）⑼重量 醇酸樹脂：EZ-3020-60-S(大日本彳y丰化学 会社製造）。 +菜株式 13 200817481 工業株式会 三聚氰胺樹脂：L-121-60(大日本4 >牛化学 社製造）。 二曱笨樹脂··二力/ _^PH54〇(商品名）（日本力、只化学 株式会社製造）。 二氧化矽粉：FB-24(電気化学工業株式会社製造）。 酚系硬化劑··夕γ y小758(商品名）(荒川化学工業株式会 社製造）。 咪唑硬化劑：2-乙基咪唑(四国化成工業株式会社製造）。 銨系硬化劑：四丁鱗四苯硼酸。 10 自由基系硬化劑：氫過氧化異丙苯。 用ΒΗ型黏度計轉子N〇 7(10rpm)分別測量a液及β液之 初期黏度(V〇)及置於常溫下14天後之黏度(V14)，並用下列 算式求出14天後之黏度變化率（％)。黏度變化率（％)在 -20%〜20%内為合格。 15 14天後之黏度變化率（％)=<(v14- V〇)/ VG>x 1 〇〇 【表1】 實施例No _ ΙΑ 1B 2A 2B 3A 3B 4A 4B 5A 5B 6A 6B 丙 80 轉 20 50 爹 50 - 50 - 50 - _ - 20 麵 80 一 40 - 40 - 40 - 50 一 10 一 - - - - - . 一—_— 10 - - - - 一 咖 —- - - 10 - - 400 100 100 400 250 250 150 250 250 250 250 250 ri'l^ nrif -------^ ^ 15 15 15 15 15 15 - 15 - 一 - - - - - . 5 5 5 - - - 5 - 5 化劑 - - - - - - 14 天/ -20 -15 15 •20 -15 -5 -15 -15 -15 -10 -15 -10 14 200817481 --——~~-— 丙 7A 7B 8A 8B 9A 9B 10A 10B 11A 11B 50 - 50 - 50 - 50 - 50 一 - 50 - 50 • 50 - 50 _ 50 -脂 二努 -— - - - 脂 - - - • - - -粉 250 15 250 50 1 c 50 500 500 250 250 250 250 X w/ - I j • 15 15 35 1 —μ不A无化劑 自 VH Trft /1 %- ^ - 5 - 5 - 5 - 1 一 化率(0/〇) -15 丄 15 — -5 _ -10 20 20 -15 -10 20 丄 -20 於使用前混合前述A液與β液做成導熱性糊，再將其塗 布於銅板上’用160它加熱60分鐘後可製成硬化物。 5 評價製成之導熱性糊及硬化物之印刷性、有無產生孔 隙、抗剪強度、耐濕實驗及耐熱實驗後之變化率、黏度變 化率、及導熱率。結果如表2所示。另外，實驗、測量方法 如下所示。 印刷性，係利用120網孔之聚酯篩網版對設置於厚度 1〇 l.6mm之基板上，且厚200Pm、寬1mm、長1〇0111之銅箔溝 進行印刷，然後調查糊之填充性。糊可完全填充者為〇， 未完全填充者為X。 有無產生孔隙，係用16〇°c硬化60分鐘後，研磨表層， 並用光學顯微鏡進行觀察，將500μιη以上之空隙判斷為孔 15 隙。 抗剪強度，係以JISK6850為標準，並以銅板作為實驗 片，用160°C硬化60分鐘後進行測量。 15 200817481 耐濕實驗及耐熱實驗後之變化率，前者係將實驗料放 置於85°C、85%之恆溫恆濕槽内10〇小時，而後者係將實驗 料以260°C之烤爐加熱30秒，再分別測量其抗剪強度，然後 用下述算式求出。變化率(％)在-20%〜20%之範圍内為合格。 5 變化率(％M<(實驗後強度)-(初期強度）>/(初期強度)]χ 100 黏度變化率（％)，係用ΒΗ型黏度計轉子No.7(10rpm)分 別測量初期黏度(V0)及置於常溫下3天後之黏度(V3)，並用 10 下列算式求出。變化率（％)在-20%〜20%内為合格。 3天後之黏度變化率(％)=<(V3- V〇)/ VG〉x 100 導熱率，係用雷射閃光測定法測量用160°C硬化60分鐘 後之硬化物。 【表2】 實施例No. 1 2 3 4 5 6 7 8 9 10 11 丙烯酸樹脂 80 20 50 50 50 50 50 50 50 50 50 環氧樹脂 20 80 40 40 40 50 50 50 50 50 50 醇酸樹脂 • _ 10 - - - - - - - - 三聚氰胺樹脂 • — 10 - - - - - - - 二甲苯樹脂 嫌 瞧 • - 10 - - - - - - 二氧化矽粉 500 500 500 500 500 500 500 100 1000 500 500 酚系硬化劑 15 15 15 15 15 15 15 15 15 15 35 咪唑硬化劑 - 一 - 一 - - - - - - 1 錢系硬化劑 5 5 5 5 5 5 5 5 5 1 - 自由基系硬化劑 麵 參 • • - - 1 - - - 1 印刷性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 有無孔隙 無 無 無 無 無 無 無 無 無 無 無 抗#強度iN/cm2) 600 900 850 900 870 880 850 1100 750 800 900 耐濕實驗後變 化率（％) -20 -5 -5 -5 -3 -5 -5 -6 -13 -10 -5 耐熱實驗後變 化率（％) -20 15 8 8 7 5 5 -12 -15 -12 -3 3曰後黏度變 化率（％) 10 15 15 17 14 12 18 8 20 3 8 導熱率(W/m · K) 1.2 1.2 1.2 1.2 1.2 1.3 1.3 0.5 1.7 1.4 1.1 16 200817481 將表3所顯示之各成分以該表所顯示之比率（重量比 口 ^周製導熱性糊，再將其、塗布於銅板上，以⑽。c加熱的 一“ Ί成硬化物。各*份之詳細内容與前述實施例相 同。接著，與前述實施例相同，評價製成之導熱性糊及硬 化物之卩刷性、有無產生孔隙、抗剪強度、财濕實驗及耐 熱實驗後之變化率、黏度變化率、及導熱率。結果如表3所 示0 【表3】R In the formula (I), R represents an anthracene or a hydrocarbon group, and the carbon number of the hydrocarbon group is not particularly limited, and is usually from 1 to 3. Specific examples of the acrylic resin to be used in the present invention include 20 isoamyl acrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and ditrimethylolpropane tetraacrylate. Phenyl glycidyl ether propylene hexamethylene diisocyanate urethane prepolymer, bisphenol hydrazine condensate 200817481 glycerol _ acrylic acid additive, b m - know: methyl acrylate acid brewing, etc. Two or more kinds of the above-mentioned acrylic acid trees can be used in combination. Since the above-mentioned acrylic acid_ can be used, it can be filled in a large amount of 5 10 15 without using a solvent, so that (4) heat dissipation can be applied to screen printing. Low viscosity. The epoxy resin contained in the additional liquid may be one or two in the molecule, and two or more epoxy resins may be used in combination. Specifically, such as: double powder type per oxygen resin, evolution epoxy resin, double expectation F type epoxy resin, acid: type ring negative sundial, eucalyptus, day, epoxy resin, Glycidylamine type (IV) resin, glycidol_epoxy resin, glycidyl ester type cycloglycan, and heterocyclic epoxy resin. The mixing ratio (% by weight) of the acrylic resin to the epoxy resin is propylene resin: epoxy resin is called (four)' and (10): time 40 is preferred. When the ratio of the acrylic resin is less than 10% by weight, the viscosity change increases. When the ratio exceeds 9 Torr, the physical properties after hardening are lowered. In the thermal conductive paste of the present invention, one or more of the alkyd resin and the trimeric amine bis-f-phenyl resin may be mixed as a resin molding agent, and then used in the above-mentioned acrylic resin or epoxy. In the resin, other resins which can be used as the molding agent for the above-mentioned tree can be appropriately selected, and are not particularly limited. Further, the resin as the resin molding agent may be added to one of the A liquid and the B liquid, or both liquids may be added. ^Alcohol (4), melamine resin, and xylene resin, among which "mixing ratio of AM olefinic resin and / or 6 liquid epoxy resin mixed" with liquid A acrylic resin and bismuth epoxy resin 20% of the total weight of the resin component 200817481 6 〇 weight. / ° or more is better, and more preferably 9% by weight or more. That is, the ratio of the resin mixed as a molding agent is less than 4 总 of the total weight of the resin component.竓为j土, and more preferably less than the weight%. The epoxy resin hardener contained in the liquid A, for example, may be used, for example, a phenolic hardener, a sodium saliva hardener, a cationic hardener, etc., and the foregoing The curing agent may be used singly or in combination of two or more kinds. The acrylic resin curing agent (polymerization initiator) contained in the liquid B may be, for example, an ammonium-based curing agent or a radical curing agent, and may be used. Two or more kinds of the above-mentioned substances may be used. Examples of the phenolic curing agent include a phenol resin and a naphthol compound. Examples of the imidazole curing agent include imidazole, 2-11-imidazole, and hydrazine. Heptadecyl imidazole, 2-ethylimidazole, 2-benzimidazole 2-ethyl-4-methyl-imidazole, h-cyanoethyl-2-undecylimidazole, 2-benzimidazole, 2, cardinylamine _&[2, methyl meth 11 syl--(1' )] ethyl _s_ trimorphine, etc., a cationic hardener, for example, an amino group of boron trifluoride, a ruthenium pentachloride-acetamidine complex, a phenethyl group or an allylic group The salt-based salt or the like. The ammonium-based hardener may, for example, be p-methoxydiazonium hexafluorophosphoric acid, diazepam hexafluorophosphoric acid, triphenyl spar, tetra-n-butyl-tetraphenylboronic acid, tetra-n _Butylphosphonium, ethyl oxadithiophosphorodiate, etc. The radical hardener may, for example, be dicumyl peroxide or dibutyl cumene peroxide. Oxidation of tertiary butyl, cumene hydroperoxide, etc. The amount of hardener used varies depending on the type, but in general, the amount of hardener used is 11 200817481 for 100 parts by weight of epoxy resin and acrylic resin. It is about 1 to 40 parts by weight. If the amount used is too small, it will cause poor curing, and if it is too large, the storage stability will be lowered and the physical properties will be lowered. The thermally conductive filler can be combined with the above-mentioned liquid A. Any one of the B liquids may be mixed with the two, and one or more of Al2〇3, SiO2, C, BN and A1N may be used as the thermal conductive filler. The particle size is preferably from about 0.1 to 50 μm. The amount of the filler to be mixed varies depending on the type, but it is usually from 100 to 1000 parts by weight based on the total amount of the epoxy resin and the acrylic resin. Further, it is preferably from 3 to 900 parts by weight. 10 According to the selection of the type and amount of the above-mentioned thermally conductive filler, a cured product having a thermal conductivity of about 0.2 to 2.8 W/m · Κ can be obtained. Sexual imparting agent. The type of the flame retardant imparting agent is not particularly limited, and a flame retardant which has hitherto been commonly used for a resin additive can be used. For example, a tribasic phosphate such as triphenyl phosphate, trimethyl sulphate 15 or phenyldiphenyl phthalate; a chlorine compound such as fossil; a desert compound such as benzene; Huazhen, Huahua Oxidation and so on; crystallization of ammonium; trihydrogenation and other inorganic difficulties _ and so on, but considering environmental issues, in the above substances, by the chemical system, structure, or dish acid is difficult to burn The agent is better. , , 20 Although the amount and type of inflammable prescribing agents vary according to needs, = above, relative to 10. The parts by weight of the resin component are w (eight) parts by weight. If the composition is added to the composition, the refractory agent will result in high viscosity. However, since the composition of the thermal conductive paste of the present invention is as described above, 12 200817481 is difficult to add even if it is added. The flammability imparting agent also retains a low viscosity which can be screen printed without using a solvent. Further, an additive such as an antifoaming agent, a tackifier or a pigment may be added to the heat conductive paste of the present invention within a range not exceeding the object of the present invention. 5. The thermal conductive paste of the present invention is prepared by separately mixing and mixing the precursors into 77 in a predetermined amount, and blending the two liquids before use and mixing them to form a ring of the predetermined ratio. Oxygen resin and acrylic resin. Then, the paste obtained by coating and mixing by screen printing or the like is hardened and then formed into a substrate of a desired shape. Although the hardening conditions vary depending on the tree used, it is hard, and it is generally cured at 150 to 200 ° C for 30 to 120 minutes. (Embodiment) The following are examples of the invention, but the invention is not limited to the following examples. [Examples] 15 parts, no 〇: The components shown in Table 1 were mixed in a ratio (weight ratio) shown in the table to prepare liquids A and B, respectively. Further, the details of each component are as follows: acrylic acid: 2-hydroxy-3-propyl decyloxy methacrylate (8 〇 weight of diethylene glycol diacrylate (20 weight ❾ / 〇). : Epoxy resin EP_4901E (Asahi Kasei Kogyo Co., Ltd. wears (80% by weight), ED_529 (manufactured by Asahi Chemical Co., Ltd.) (9) Weight Alkyd Resin: EZ-3020-60-S (Manufactured by Dainippon Yoshito Chemical Co., Ltd. + 菜菜式 13 200817481 Industrial plant type melamine resin: L-121-60 (Greater Japan 4 > manufactured by Niu Chemical Co., Ltd.) Two 曱 树脂 resin··二力 / _^PH54〇 (trade name) (Japan Force)只 二 : : FB FB FB FB FB FB FB FB FB FB FB FB 758 758 758 758 758 758 758 758 758 758 758 758 758 758 758 758 758 758 758 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑 咪唑Hardener: 2-ethylimidazole (manufactured by Shikoku Chemicals Co., Ltd.) Ammonium-based hardener: tetrabutyltetradecylborate 10 Radical-based hardener: cumene hydroperoxide. Rotary N with a ΒΗ-type viscometer 〇7 (10 rpm) measured the initial viscosity (V〇) of the liquid a and the liquid β, respectively Viscosity after 14 days at room temperature (V14), and the viscosity change rate (%) after 14 days was obtained by the following formula. The viscosity change rate (%) was qualified within -20%~20%. 15 Viscosity after 14 days Rate of change (%) = < (v14 - V〇) / VG > x 1 〇〇 [Table 1] Example No _ ΙΑ 1B 2A 2B 3A 3B 4A 4B 5A 5B 6A 6B C 80 rpm 20 50 爹 50 - 50 - 50 - _ - 20 faces 80 - 40 - 40 - 40 - 50 - 10 - - - - - . - - - 10 - - - - One coffee - - - - 10 - - 400 100 100 400 250 250 150 250 250 250 250 250 ri'l^ nrif -------^ ^ 15 15 15 15 15 15 - 15 - One - - - - - . 5 5 5 - - - 5 - 5 Chemicals - - - - - - 14 days / -20 -15 15 •20 -15 -5 -15 -15 -15 -10 -15 -10 14 200817481 --——~~-— C 7A 7B 8A 8B 9A 9B 10A 10B 11A 11B 50 - 50 - 50 - 50 - 50 - 50 - 50 • 50 - 50 _ 50 - 脂二努-- - - - Grease - - - • - - - Powder 250 15 250 50 1 c 50 500 500 250 250 250 250 X w/ - I j • 15 15 35 1 —μ不A无化剂from VH Trft /1 %- ^ - 5 - 5 - 5 - 1 rate (0/〇) -15 丄15 — -5 _ -10 20 20 -15 -10 20 丄-20 Mix the above liquid A and β solution to form a thermal paste before use. It can be made into a hardened material by heating it on a copper plate for 60 minutes. 5 Evaluation of the printability of the prepared thermally conductive paste and cured product, presence or absence of voids, shear strength, moisture resistance test, rate of change after heat resistance test, viscosity change rate, and thermal conductivity. The results are shown in Table 2. In addition, the experiment and measurement methods are as follows. The printing property is printed on a copper foil groove having a thickness of 200 pm, a width of 1 mm, and a length of 1 〇0111 by using a polyester mesh screen of 120 mesh, and then investigating the filling of the paste. Sex. The paste can be completely filled with 〇, and the one that is not completely filled is X. The presence or absence of voids was hardened at 16 ° C for 60 minutes, and the surface layer was polished and observed with an optical microscope to determine a void of 500 μm or more as a pore gap. The shear strength was measured by using JIS K6850 as a standard, and a copper plate was used as a test piece, which was hardened at 160 ° C for 60 minutes. 15 200817481 Change rate after moisture resistance test and heat resistance test. The former placed the test material in a constant temperature and humidity chamber at 85 ° C and 85% for 10 , hours, while the latter heated the test material at 260 ° C. After 30 seconds, the shear strength was measured separately and then determined by the following formula. The rate of change (%) is within the range of -20% to 20%. 5 Rate of change (%M<(intensity after experiment)-(initial strength)>/(initial strength)] χ 100 viscosity change rate (%), measured by the ΒΗ-type viscometer rotor No. 7 (10 rpm) Viscosity (V0) and viscosity (V3) after 3 days at room temperature, and obtained by the following formula: The rate of change (%) is within -20%~20%. The rate of change of viscosity after 3 days (% )=<(V3-V〇)/ VG>x 100 Thermal conductivity, which was measured by laser flash measurement using a cured product after hardening at 160 ° C for 60 minutes. [Table 2] Example No. 1 2 3 4 5 6 7 8 9 10 11 Acrylic resin 80 20 50 50 50 50 50 50 50 50 50 Epoxy 20 80 40 40 40 50 50 50 50 50 50 Alkyd resin • _ 10 - - - - - - - - Melamine resin • — 10 — - - - - - - Xylene Resin Dispelling • - 10 - - - - - - Ceria Powder 500 500 500 500 500 500 500 100 1000 500 500 Phenolic Hardener 15 15 15 15 15 15 15 15 15 15 35 Imidazole hardener - one - one - - - - - - 1 money hardener 5 5 5 5 5 5 5 5 5 1 - free radical hardener facial ginseng • • - - 1 - - - 1 printing Sexuality 〇〇〇With or without voids No no no no no no no no no no anti-strength #strength iN/cm2) 600 900 850 900 870 880 850 1100 750 800 900 Change rate after moisture resistance test (%) -20 -5 -5 - 5 -3 -5 -5 -6 -13 -10 -5 Change rate after heat resistance test (%) -20 15 8 8 7 5 5 -12 -15 -12 -3 After 3 曰 viscosity change rate (%) 10 15 15 17 14 12 18 8 20 3 8 Thermal conductivity (W/m · K) 1.2 1.2 1.2 1.2 1.2 1.3 1.3 0.5 1.7 1.4 1.1 16 200817481 The ratios shown in Table 3 are shown in the table (weight ratio) ^ Weekly thermal conductive paste, which is applied to a copper plate, and a "cured material" which is heated by (10).c. The details of each * part are the same as those of the foregoing embodiment. Next, the evaluation is the same as in the previous embodiment. The heat-sensitive paste and cured product are brushed, have pores, shear strength, moisture test and heat change test rate, viscosity change rate, and thermal conductivity. The results are shown in Table 3 [Table 3]
10 產業上之可利用性 本發明之導熱性糊可使用於如各種電子機器之電路基 板的絕緣材料。 【圖式簡單說^明】 第1圖係顯示使用導熱性糊之基板成型例的標準截面 15圖，且第1(a)圖係顯示將導熱性糊塗布（印刷)於表面形成有 圖案之零件後之基板，而第丨⑻圖係顯示將艇板加壓接著於 第1(a)圖之基板並硬化後的狀態。 17 200817481 【主要元件符號說明】 1...I呂板 2···導熱性糊 3.. .零件 4.. .圖案 1810 Industrial Applicability The thermally conductive paste of the present invention can be used for an insulating material such as a circuit board of various electronic machines. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a standard cross section 15 of a substrate molding example using a thermal conductive paste, and Fig. 1(a) shows that a thermal conductive paste is coated (printed) on a surface to form a pattern. The substrate behind the part, and the figure (8) shows the state in which the boat is pressed against the substrate of Fig. 1(a) and hardened. 17 200817481 [Description of main component symbols] 1...I Lu board 2···thermal paste 3.. .parts 4.. pattern 18