201008778 • 六、發明說明： 【發明所屬之技術領域】 本發明是有關使用於各種電子機器用之電路基板領域 的層積板’特別是放熱性優良之層積板，以及使用該層積 板製造之貼金屬箔層積板，電路基板以及搭載於發光二極 體之電路基板。 【先前技術】 e 玻璃布（Glass clothes)含浸於環氧樹脂等的樹脂成 分的預浸料坯（prepreg)積層成形而得之統稱為FR4形式 的積層板，廣泛使用於代表作為電子機器用的印刷電路基 板之層積板。FR-4的名稱是以美國的國際電器製造業協會 (National Electrical Manufactures Ass〇ciati〇n)之規 格分類之。該FR-4型的層積板，具有沖孔加工性和鑽孔加 工性差的等缺點1以解決上述缺點的印刷電路板，已知 眷有將含浸樹脂成分的不織布層作為芯材層，於該芯材層的 兩表面各自積層含浸樹脂成分的玻璃布作為表面層而構 成稱為CEM-3形式的複合（c〇fflp〇si te)層積板。 例如，下述專利文件即記載層間接著強度高，耐鹼性， 耐,、、、H冲孔加工性優異之複合層積板，其於不織布以及/ 或紙含，於樹脂清漆（varnish)的樹脂含浸材芯材的兩 面’貼著玻璃布含浸於樹脂清漆的樹脂含浸表層材，再貼 附金屬箱而成。該複合層積板中，芯材使用的樹脂清漆， 包3有滑石與虱氧化紹合併的填充劑，滑石與氣氧化銘的 3 201008778 配合比為〇. 15~Q 65 且氨氧化銘為勃姆石型。 如，下述專利文獻2中，即揭露由含浸樹脂之 玻璃織布組成的表面層以及含浸硬化性樹月旨之玻璃不織布 、、1層構成之印刷電路基板用層積材作為熱穩定且 難燃性優異的複合層積板。該層積材中，中間層是包含有 以中間層中的樹脂基準200重量%〜275重量%之量的分子式 Ah〇3 nH2〇(式中，n大於2. 6且小於2· 9)氫氧化鋁。 再者，近年來隨著電子機器的輕薄短小化，印刷電路 板實裝的電子零件往高密度實裝化發展，且亦安裝複數個 要求放熱性之發光二極體⑽）等作為實裝之電子零件。用 於該等用途的基板，習知的層積板會有放熱性不充足的問 題。^ ’實裝方法是以迴焊谭錫（reflQw sQlder)為主流， 特別疋A 了減輕對環境的負荷則以必須使用高溫迴焊處 理之使用無料錫的迴焊焊錫為主流。因&，使用無錯鲜 =之迴焊烊錫步驟，要求用以抑制氣泡（blister)發生等的 同耐熱性。再者’亦要求維持鑽孔加工性。又，從安全面 來看’亦要求滿足UL-94之V-0程度的難燃性。 專利文獻 專利文獻1特開昭62_173245號公報 專利文獻2特表2001-508002號公報 【發明内容】 有鑑於上述問題’本發明之目的為提供具有優良熱傳 導性’耐熱性’鑽孔加工性’以及難燃性之層積板。 201008778 本發明之一方面係有關於由不織布纖維基材含浸於熱 硬化性樹脂組成物而得之芯材層，與分別積層於前述芯材 層之兩表面的表材層積層一體化之層積板，前述熱硬化性 樹脂組成物是含有對熱硬化性樹脂100體積部之無機填充 材80〜150體積部，其中前述無機充填材，包含（A)具有2〜15 私m之平均粒子控（Ds°)的三水鋁礦（gibbsi te)型氫氧化銘 粒子（B)至少1種擇自具有2〜15 之平均粒子徑（d50) φ的勃姆石（Boehmite)粒子、以及具有2〜15/ζπι之平均粒子 徑（D一，且游離開始溫度4〇〇t以上的含結晶水或者未 含有結晶水之無機粒子的無機成分，以及（c)具有15以肌 ，下之平均粒子徑的氧化銘粒子，前述三水銘礦型氫氧化 鋁粒子（A)與前述勃姆石粒子以及至少丨種擇自前述無機 粒子之無機成分（B)與前述氧化鋁粒子（C)之配合比（體積 比），為 1:0.1 〜1:014。 本發月之另一方面係有關於在前述層積板之至少 ❹#表面上貼附金屬箔之貼金屬箔層積板’還有在該貼金屬 >白層積板上形成電路而得之電路基板’以及前述電路基板 構成之搭載發光二極體之電路基板。 本發明之目的、特徵、局面以及優點將藉由以下詳述 說明與附圖而更明白。 [熱硬化性樹脂組成物] 首先說明本發明之較佳實施型態的熱硬化性樹脂組成 物。 據本發月人等的檢討’為了賦予層積板放熱性，在 201008778 配合優良熱傳導性之氫氧化鋁的場合，層積板的放熱性提 尚了。又，難燃性也提升。但是’在配合過多氫氧化鋁的 場合，層積板的耐熱性大幅降低，而容易產生焊錫迴焊時 產生氣泡等問題。又，以優良放熱性氧化鋁配合取代氫氧 化銘的場β，則發生明顯的鑽孔加工性的鑽孔刀磨損，需 要頻繁更換鑽孔刀的問題，和難燃性降低之問題。又在 為了抑制鑽孔刀的磨損而減量氧化鋁的配合量的場合，導 致熱傳導性不充分的問題。因此’難以得到完全滿足高熱 傳導性，高对熱性，錢孔加工性以及高難燃性的層積板。 本發明之熱硬化性樹脂組成物是含有對熱硬化性樹脂 1〇0體積部之無機填充材，150體積部，其中前述無機充 填材’包含（Α)具有2〜15/im之平均粒子徑⑼。）的三水銘礦 型氫氧化銘粒子，⑻至少1種擇自具有2〜15口之平均粒 子徑㈤的勃姆石粒子、以及具有215…平均粒子徑 ㈤，且游離開始溫度·上的含結晶水，或者未含 有結晶水之無機粒子的無機成分，以及⑹具有U… 下之平均粒子徑的轰^ 鋁粒子，别述三水鋁礦型氫氧化鋁 ΠΑ)與前述勃姆石粒子以及至少！種擇自前述無機粒 =機成分⑻與前述氧化銘粒子(c)之配合比(體積 匕）為 l.〇.l~l:〇.i〜1。 r , 、 旳具體乾例如環氧樹脂；不飽和聚酯 J yester樹月曰’乙烯酯樹脂等的自由基 樹脂；等的液狀熱硬化性樹脂。又，熱硬化性樹：= 需要配合硬化劑和硬化觸媒 使用自由基聚合型熱硬 201008778 化性樹脂的場合，亦可視需要適量配合笨乙烯、酞酸二烯 丙酯（(^&1171?1!1；1^13士6)等的自由基聚合性單體等。又， 為了調整黏度和改良生產性，上述兩者皆可視需要配合溶 劑0 本實施型態的無機填充材，是含有包括三水鋁礦型氫 氧化鋁粒子（A)，與至少1種擇自由勃姆石粒子、游離開始 溫度400°C以上的結晶水’或者未含有結晶水之無機粒子 所組成之群組的無機成分（B)，以及氧化鋁粒子（c)。 前述三水銘礦型氫氧化鋁粒子（^)，是a1(〇H\或 Α1ζ〇3· 3Η2〇表示之鋁化合物，是用以賦予層積體熱傳導性， 難燃性，鑽孔加工性均衡的成分。 ❹ 三水鋁礦型氫氧化鋁粒子（Α)的平均粒子徑（Dy為 2〜15/z m，較佳為3〜10" m。三水鋁礦型氫氧化鋁粒子 的平均粒子徑（D5。）超過15em時鑽孔加工性會降低，未滿 2em的話熱傳導性降低同時生產性也降低。又，三水鋁礦 型氫氧化鋁粒子（A)，是使用平均粒子徑（D5e)2〜1〇#m之第 1三水鋁礦型氫氧化鋁與平均粒子徑（1)5。）1〇〜15以阳之第2 三水鋁礦型氫氧化鋁的化合物，以提高放熱性來說最好是 將填充材緊密填充。 & 再者，本實施型態之平均粒子徑（Ds。），是指以雷射折 射式粒度分布測定裝置測定而得之粉體的全體積丨〇〇%求出 累積曲線’而該累積曲線為50%的點即為粒子徑。 前述無機成分（B)，是至少丨種擇自勃姆石粒子，以及 游離開始溫度400°C以上之含有結晶水，或未含結晶水之 7 201008778 無機粒子所組成之群組。 前述勃姆石粒子，是（A100H)或（ΜΑ. H2〇)表示之鋁 化合物，是可在不降低層積體的耐熱性下賦予熱傳導性與 難燃性之成分。 勃姆石粒子的平均粒子徑（D5。）為2~15ym’較佳為 3〜l〇vm。勃姆石粒子的平均粒子徑（I。）超過時鑽孔 加工性會降低，未滿2/zm的話熱傳導性降低同時生產性也 降低。 又，含有游離開始溫度4〇〇。(：以上之結晶水，或未含 結晶水之無機粒子，是可在不降低電路基板的耐熱性下賦 予熱傳導性與難燃性之成分。 無機粒子的具體範例如氧化鋁（無結晶水）、氧化鎂（無 結晶水）、結晶性二氧化矽（無結晶水）等的無機氧化物丨氮 化领（無結晶水）、氮化銘（無結晶水）、氮化梦（無結晶水） 等的無機氮化物；碳化矽（無結晶水）、等的無機碳化物； 以及滑石（游離開始溫度95〇。〇、燒結高嶺土（無結晶水）、 黏土（游離開始溫度5〇〇〜1〇〇(rc)等的天然礦物等。該等可 單獨使用，或| 2種以上組合使用。該等之中，以優異熱 傳導來說較佳為結晶妙二氧化珍，滑石，黏土等。 再者，結晶水的游離開始溫度，可使用加熱重量減分 析（TGA)或熱分析儀（DSC)測定之。 無機粒子的平均粒子徑⑺一為2〜15私m，較佳為31〇 以"1。無機粒子的平均粒子徑（D5。）超過15 時鑽孔加工性 會降低。 201008778 氧化銘粒子（c)，是可賦予芻媒 ^ 〃 于襄得之層積板高熱傳導性的 成分。氧化銘粒子（C)的平均粒子徑（D5〇為1 一以下， 較佳為0.4〜U”。氧化銘粒子的平均粒子徑㈤超過 1.5/zm時’層積板需填充充分配合 重 又，鐵孔加工性亦 降低。且氧化鋁的平均粒子徑過 ^ 合，層積板的熱傳 導率變的不充足。 前述三水鋁礦型氫氧化鋁粒子 祖千（A)，前述無機成分 (B)，以及前述氧化銘粒子（〇 0 卞的配合比（體積比）是 1:0. 1-1:0. 1 〜1 ’ 較佳是 1:0 ho 5.0 〗n C； ^ υ· 3·υ·卜〇· 5。對三水鋁礦 型氫氧化鋁粒子⑴的配合量卜無機成分⑻的配合量超 過1時，得到的層積板的鑽孔加工性和放熱性降低，未滿 〇·1的場合’耐熱性則降低。又，對三㈣礦型氫氧化銘 粒子（Α)的配合量卜氧化铭粒子（c)的配合量超過】時， 鑽孔加工性降低，未滿〇.丨時則熱傳導率降低。 對熱硬化性樹脂100體積部的無機填充材的配合比率 ❹為150體積部，較佳為90〜140體積部，更佳為jooqgo 體積部。無機填充材的配合比率未滿8〇體積部的場合，製 得之層積板的熱傳導性降低，超過15〇體積部的場合，鑽 孔加工性降低同時層積板的製造性（樹脂含浸性、成形性） 亦降低。又，特別是三水鋁礦型氫氧化鋁粒子（4)配合比例 過多時，具體言之在超過1〇〇體積部時，結晶水變多而有 耐熱性降低的傾向。 再者’無機成分（B)是勃姆石粒子，與游離開始溫度 400C以上之含結晶水或未含結晶水之無機粒子配合時，無 9 201008778 機粒子的配合比例，是無機填充材全量的50體積%以下， 再更佳為3。體她下，特佳是2。體積%以下,“下 入=硬化性樹脂組成物，是在液狀的熱硬化性樹脂中， 配《 3有上述三水鋁礦型氫氧化鋁（A)，與無機成分（B)， 與氧化銘粒子（G)之無機填充材，藉由使用分散法、球磨 法、滾筒磨法等，使各無機粒子分散之習知的調製方法調 製之，。再者’亦可視需要配合用以調整黏度的有機溶劑和 各種添加劑。[Technical Field] The present invention relates to a laminated board used in the field of circuit boards for various electronic devices, in particular, a laminated board excellent in heat dissipation, and the use of the laminated board. A metal foil laminated board, a circuit board, and a circuit board mounted on the light emitting diode. [Prior Art] Glass cloth is a laminate of a prepreg impregnated with a resin component such as an epoxy resin, and is collectively referred to as a laminated board of the FR4 type, and is widely used as a representative for electronic equipment. A laminated board of printed circuit boards. The name of the FR-4 is categorized by the National Electrical Manufactures Ass〇ciati〇n. The FR-4 type laminated board has a disadvantage of 1 such as punching workability and poor drilling workability, and a printed circuit board which solves the above disadvantages is known as a core layer which is a non-woven fabric layer impregnated with a resin component. A glass cloth impregnated with a resin component is laminated on both surfaces of the core material layer as a surface layer to form a composite (c〇fflp〇si te) laminated board called CEM-3. For example, the following patent document describes a composite laminated board having high interlayer bonding strength, alkali resistance, resistance, and H punching workability, which is contained in non-woven fabric and/or paper, in resin varnish. The two sides of the core material of the resin impregnated material are impregnated with a glass lining resin impregnated with a resin varnish, and then attached to a metal box. In the composite laminated board, the resin varnish used in the core material, the package 3 has the filler of talc and bismuth oxide, the talc and the gas oxidation Ming 3 201008778 ratio is 〇. 15~Q 65 and the ammonia oxidation is Bo Mushi type. For example, in the following Patent Document 2, a surface layer composed of a glass woven fabric impregnated with a resin and a glass non-woven fabric impregnated with a resin, and a laminated material for a printed circuit board having a single layer are disclosed as heat stable and difficult. Composite laminate with excellent flammability. In the laminated material, the intermediate layer is a molecular formula of Ah 〇 3 nH 2 〇 (where n is greater than 2.6 and less than 2. 9) hydrogen in an amount of from 200% by weight to 275 % by weight based on the resin in the intermediate layer. Alumina. Furthermore, in recent years, with the miniaturization and miniaturization of electronic devices, electronic components mounted on printed circuit boards have been developed in high-density, and a plurality of light-emitting diodes (10) requiring exothermicity have been installed as mountings. Electronic parts. Conventional laminated sheets have a problem that the heat dissipation property is insufficient for the substrates for such applications. ^ ‘The mounting method is based on reflow soldering tin reel (reflQw sQlder), especially 减轻A. To reduce the load on the environment, it is necessary to use the reflow solder which is used in the high-temperature reflow process. Because of &, the step of reflow soldering tin is used to suppress the heat resistance of the occurrence of bubbles (blister). Furthermore, it is also required to maintain drilling processability. Also, from the point of view of safety, it is also required to meet the flame retardancy of the V-0 level of UL-94. In the light of the above problems, the object of the present invention is to provide an excellent heat conductivity 'heat resistance' drilling processability and A flame retardant laminate. 201008778 One aspect of the present invention relates to a core material layer obtained by impregnating a nonwoven fabric substrate with a thermosetting resin composition, and a laminated layer of a surface layer laminated on both surfaces of the core material layer, respectively. In the plate, the thermosetting resin composition is an 80 to 150-volume portion containing an inorganic filler of 100 parts by volume of the thermosetting resin, wherein the inorganic filler contains (A) an average particle size of 2 to 15 cc ( Ds °) gibbsi te type hydroxide particles (B) at least one selected from Boehmite particles having an average particle diameter (d50) φ of 2 to 15, and having 2~ The average particle diameter of 15/ζπι (D1, and the inorganic component containing the crystal water or the inorganic particles not containing the crystal water having a free starting temperature of 4 〇〇t or more, and (c) the average particle diameter of the muscle with 15 Oxidation-incorporated particles, the above-mentioned Sanshui Ming-type aluminum hydroxide particles (A) and the foregoing boehmite particles and at least the inorganic component (B) selected from the inorganic particles and the aluminum oxide particles (C) (volume ratio), from 1:0.1 to 1:014 Another aspect of the present month relates to a metal foil laminated board in which a metal foil is attached to at least the surface of the laminated board, and a circuit is formed on the metal sheet and the white laminated board. The circuit board of the present invention and the circuit board on which the light-emitting diodes are formed by the circuit board. The objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description and the accompanying drawings. First, a thermosetting resin composition according to a preferred embodiment of the present invention will be described. According to the review of the Japanese, et al., in order to impart heat dissipation to the laminated sheet, in 201008778, in combination with aluminum hydroxide having excellent thermal conductivity, The heat dissipation of the laminated board is improved. Moreover, the flame retardancy is also improved. However, when the excessive amount of aluminum hydroxide is blended, the heat resistance of the laminated board is greatly lowered, and problems such as generation of bubbles during solder reflow are likely to occur. In addition, when the field β of the hydroxide is replaced by the excellent exothermic alumina, the drilling process of the drilling process is obviously drilled, the problem of frequent replacement of the drilling knives, and the reduction of the flame retardancy are required. Further, when the amount of alumina is reduced in order to suppress the wear of the boring blade, the thermal conductivity is insufficient. Therefore, it is difficult to obtain a high thermal conductivity, high heat resistance, money hole processability, and high flame retardancy. The thermosetting resin composition of the present invention is an inorganic filler containing a volume of a thermosetting resin of 1 〇 0, and a volume of 150 parts, wherein the inorganic filler s contains (2) /im average particle diameter (9).) Sanshui mineralized type hydroxide particles, (8) at least one selected from boehmite particles with an average particle diameter of 2 to 15 (five), and with a 215... average particle diameter (five) And the inorganic component containing the crystal water or the inorganic particles not containing the crystal water at the free starting temperature, and (6) the aluminum particles having an average particle diameter of U..., and the gibbsite-type aluminum hydroxide ΠΑ) with the aforementioned boehmite particles and at least! The ratio (volume 匕) selected from the above inorganic particle = machine component (8) to the aforementioned oxidized particle (c) is l. ~.l~l: 〇.i~1. r , , 旳 specific dry such as epoxy resin; unsaturated polyester J yester tree 曰 曰 乙烯 vinyl ester resin and other free radical resins; liquid thermosetting resin. Further, the thermosetting tree: = When a curing agent and a curing catalyst are required to use a radical polymerization type thermosetting 201008778-based resin, an appropriate amount of stupid ethylene or diallyl citrate may be blended as needed ((^&1171) ?1!1;1^13士6) and other radical polymerizable monomers, etc. Further, in order to adjust the viscosity and improve the productivity, both of these may be combined with the solvent. a group comprising gibbsite-type aluminum hydroxide particles (A), and at least one selective free boehmite particle, crystallization water having a free onset temperature of 400 ° C or higher, or inorganic particles not containing crystal water Inorganic component (B), and alumina particle (c). The above-mentioned Sanshui mineralized aluminum hydroxide particle (^) is an aluminum compound represented by a1 (〇H\ or Α1ζ〇3·3Η2〇). A component that imparts thermal conductivity, flame retardancy, and uniform drilling performance to the laminate. 平均 Average particle diameter of gibbsite-type aluminum hydroxide particles (Dy) is 2 to 15/zm, preferably 3 to 10" m. The average particle diameter (D5.) of the gibbsite-type aluminum hydroxide particles exceeds 1 At 5em, the drilling processability is lowered. When the temperature is less than 2em, the thermal conductivity is lowered and the productivity is also lowered. Also, the gibbsite-type aluminum hydroxide particles (A) are the average particle diameter (D5e) 2~1〇# m of the first gibbsite-type aluminum hydroxide with an average particle diameter (1) 5)) 1 〇 15 15 to the second gibbsite aluminum hydroxide compound, to improve exothermicity is best The filler is tightly packed. Also, the average particle diameter (Ds.) of the present embodiment refers to the total volume 粉% of the powder measured by the laser refractive particle size distribution measuring device. The cumulative curve 'and the point where the cumulative curve is 50% is the particle diameter. The inorganic component (B) is at least selected from the boehmite particles, and contains crystal water having a free onset temperature of 400 ° C or higher, or 7: 201008778 A group consisting of inorganic particles. The above-mentioned boehmite particles are aluminum compounds represented by (A100H) or (ΜΑ.H2〇), which can be imparted without lowering the heat resistance of the laminate. Component of thermal conductivity and flame retardancy. Average particle diameter of boehmite particles (D5.) It is preferably 2 to 15 μm', and is preferably 3 to 10 μm. When the average particle diameter (I.) of the boehmite particles is exceeded, the drilling processability is lowered. When the particle diameter is less than 2/zm, the thermal conductivity is lowered and the productivity is also lowered. In addition, the free starting temperature is 4 〇〇. (The above-mentioned crystallization water or inorganic particles not containing crystallization water is a component which can impart thermal conductivity and flame retardancy without lowering the heat resistance of the circuit board. Specific examples are inorganic oxides such as alumina (no crystal water), magnesium oxide (no crystal water), crystalline cerium oxide (no crystal water), etc. (no crystal water), nitriding (no crystal Inorganic nitrides such as water), nitriding dreams (no crystal water), inorganic carbides such as niobium carbide (no crystal water), and the like; and talc (free starting temperature 95 〇). 〇, sintered kaolin (no crystal water), clay (natural minerals such as a free starting temperature of 5 〇〇 to 1 〇〇 (rc), etc. These may be used singly or in combination of two or more kinds. In terms of excellent heat conduction, it is preferably crystallization, talc, clay, etc. Further, the free starting temperature of the crystal water can be measured by a heating weight loss analysis (TGA) or a thermal analyzer (DSC). The average particle diameter (7) is 2 to 15 private m, preferably 31 Å to " 1. The average particle diameter (D5.) of the inorganic particles exceeds 15 and the drilling processability is lowered. 201008778 Oxidation Ming particles (c) It is a component which can impart high thermal conductivity to the laminated plate of the sputum. The average particle diameter of the oxidized particle (C) is D1 1 1 or less, preferably 0.4 to U. When the average particle diameter (five) exceeds 1.5/zm, the laminated plate needs to be filled with sufficient weight and the iron hole workability is also lowered. The average particle diameter of the alumina is excessively controlled, and the thermal conductivity of the laminated plate is insufficient. The aforementioned gibbsite-type aluminum hydroxide particles Zu (A), The inorganic component (B), and the above-mentioned oxidized particle (volume ratio of 〇0 卞 is 1:0. 1-1:0. 1 〜1 ' is preferably 1:0 ho 5.0 〗 n C; ^ υ·3·υ·卜〇·5. For the amount of the aluminum sulphate-type aluminum hydroxide particles (1), when the amount of the inorganic component (8) is more than 1, the drilling processability and heat release property of the obtained laminated plate are obtained. When the temperature is less than 〇·1, the heat resistance is lowered. In addition, when the compounding amount of the three (four) mineral type hydroxide particles (Α) is exceeded, the drilling processability is exceeded. When the temperature is less than 丨, the thermal conductivity is lowered. The mixing ratio ❹ of the inorganic filler in the 100-volume portion of the thermosetting resin is 150 volume portions, preferably 90 to 140 volume portions, more preferably jooqgo volume portions. When the mixing ratio of the inorganic filler is less than 8 〇, the thermal conductivity of the obtained laminated plate is lowered, and when the volume exceeds 15 〇, the drilling processability is lowered and the manufacturing property of the laminated plate (resin impregnation property) And the formability) is also lowered. In addition, especially when the gibbsite-type aluminum hydroxide particles (4) have a too large proportion Specifically, when it exceeds one 〇〇 volume, the amount of crystal water increases and the heat resistance tends to decrease. Further, 'the inorganic component (B) is a boehmite particle, and the crystal water containing or not having a free starting temperature of 400 C or more When the inorganic particles containing the water of crystallization are blended, the blending ratio of the particles of the ninth 201008778 is 50% by volume or less of the total amount of the inorganic filler, and more preferably 3. The volume of the inorganic filler is preferably 2. vol% or less. In the curable resin composition, it is contained in a liquid thermosetting resin, and has the above-mentioned gibbsite-type aluminum hydroxide (A), inorganic component (B), and oxidized crystal particles (G). The inorganic filler is prepared by a conventional preparation method in which each inorganic particle is dispersed by using a dispersion method, a ball milling method, a barrel grinding method, or the like. Furthermore, organic solvents and various additives for adjusting the viscosity may be used as needed.
[芯材層] 接著使用上述熱硬化性樹脂組成物，說明用以形成 芯材層之預浸料坯（以下稱為芯材層預浸料坯）。 芯材層預浸料坯，是藉由將玻璃不織布、玻璃紙、合 成樹脂不織布、紙、等的不織纖維基材，含浸於使包含上 述三水鋁礦型氫氧化鋁粒子（A)，與無機成分（B),以及氧 化銘粒子⑹之無機填充材分散之熱硬化性樹脂組成物之 塗料中而得。[Core Material Layer] Next, a prepreg (hereinafter referred to as a core material layer prepreg) for forming a core material layer will be described using the above thermosetting resin composition. The core material layer prepreg is impregnated with a non-woven fiber substrate such as glass non-woven fabric, cellophane, synthetic resin nonwoven fabric, paper, or the like to contain the gibbsite-type aluminum hydroxide particles (A), and The inorganic component (B) and the coating of the thermosetting resin composition in which the inorganic filler of the oxidized particle (6) is dispersed are obtained.
不織纖維基材的種類沒有特別限制，可舉例如使用无 璃不織布和玻璃紙、聚醯胺（aramid)纖維、聚醋纖維、^ 龍纖維等的合成樹脂纖維之合成樹脂不織布、紙等。該$ 不織纖維基材與織纖維基材相比因為較粗，使得複合層 體的鑽孔加工性提高。 一範例為10〜300 不織纖維基材的厚度，沒有特別限制 V m左右》 用以形成芯材層預浸料坯 的熱硬化性樹脂塗料的具體 10 201008778 範例如含有環氧樹脂；不飽和聚酯樹脂，乙烯酯樹脂等的 自由基聚合型熱硬化性樹脂；等的熱硬化性樹脂之樹脂塗 料。使用環氧樹脂做為熱硬化性樹脂時，可視需要配合硬 化劑和硬化觸媒。又，使用自由基聚合型熱硬化性樹脂的 場合，亦可視需要適量配合苯乙烯、酞酸二烯丙酯等的自 由基聚合性單體等。又，為了調整黏度，上述兩者皆可視 需要配合溶劑。 ❹ ^忍材層預浸料坯，是藉由使上述不織纖維基材含浸及 半硬化於上述熱硬化性樹脂組成物中而得。具體言之，是 藉由將不織纖維基材含浸熱硬化性樹脂組成物，再將纖維 基材含熱硬化性樹脂组成物加熱乾燥，使熱硬化性樹脂 成為半硬化狀態的芯材層預浸料坯。 [表材層] 接著，說明用以形成表材層的預浸料坯（以下稱為表材 層預浸料坯）。 參 表材層預浸料坯，是將使用玻璃纖維（織布），聚酿胺 纖維’聚s旨纖維，尼龍纖維等的合成纖維的合成纖維布（織 布）而成之織纖維基材，含浸樹脂塗料而得。如此，藉由使 用，纖維基材作為表材層，可使製得之複合層積板的尺寸 穩定性和耐熱性提高。 用以形成表材層預浸料择的樹脂塗料，K吏用用以製 造芯材層預浸料枉時同樣的環氧樹脂，不飽和聚醋樹脂， 乙烯^樹月曰等的自由基聚合型的熱硬化性樹脂為樹脂成分 的樹月曰塗料。再者，用以形成表材層預浸料堪的樹脂塗料 11 201008778 中，與用以形成怒材層賤料述的樹脂塗料同樣，可視需 要’適量配合各種反應開始劑和硬化劑，填充材。亦可視 需要，適量配合不損於本發明效果之範圍的填充材。 ❹ 在含浸織纖維基材之樹脂塗料所含之熱硬化性樹脂組 成物’較佳是與用以形成芯材層預浸料_樣的熱硬化性 樹脂組成物。也就是說，對熱硬化性樹脂1〇〇體積部含有 無機填充材80~150體積部，且無機填充材，較佳是使用包 含具有2〜15p之平均粒子徑（D5D)的三水銘礦型氫氧化銘 粒子（A)’至少i種擇自具有2〜15/zm之平均粒子徑（D5〇) 的勃姆石粒子、以及具有2〜15/zm之平均粒子徑（I。），且 游離開始溫度40(TC以上的含結晶水，或者未含有結晶水 之無機粒子的無機成分。），與具有l5/zm以下之平均粒 子徑的氧化鋁粒子（c)，前述三水鋁礦型氫氧化鋁粒子（A) 與無機成分（B)與前述鋁粒子（C)之配合比（體積比）為 1: 0. 1〜1: 0 · 1〜1的熱硬化性樹脂組成物。 [層積板] ❹ 以下參照第1圖說明本發明之一實施型態之複合層積 板10。 複合層積板10,具有芯材層1，與層積於芯材層 兩表面的表材層2層積一體化的層構造。因此在該表層， 在層積金屬箔3而構成貼金屬箔層積板。 芯材層1，是由包含不織纖維基材13與無機填充材之 熱硬化性樹脂組成物lb所構成，表材層2，則由織纖維基 材2a與樹脂組成物2b所構成。 12 201008778 心材層l，是使玻璃不織布和玻璃紙等的不織纖維基 材1 a 3浸於熱硬化性樹脂組成物丨b中。熱硬化性樹脂組 成物lb，是在熱硬化性樹脂中’包含具有2~i5ym之平均 粒子徑（D5。）的三水鋁礦型氫氧化鋁粒子（A)，至少i種擇自 具有2 15以m之平均粒子徑（j)5。）的勃姆石粒子、以及具有 2~15 a m之平均粒子徑（Dy，且游離開始溫度4〇(rc以上的 含結晶水，或者未含有結晶水之無機粒子的無機成分（b)，The type of the nonwoven fabric substrate is not particularly limited, and examples thereof include a synthetic resin nonwoven fabric such as a non-woven fabric and a cellophane, an aramid fiber, a polyester fiber, a polyester fiber, or the like, and paper. The $nonwoven fiber substrate is thicker than the woven fiber substrate, so that the drilling processability of the composite layer is improved. An example is a thickness of 10 to 300 non-woven fiber substrates, and there is no particular limitation on V m. The specific 10 201008778 of the thermosetting resin coating for forming a core layer prepreg, for example, contains an epoxy resin; A resin coating of a thermosetting resin such as a polyester resin or a radically polymerizable thermosetting resin such as a vinyl ester resin. When an epoxy resin is used as the thermosetting resin, a hardener and a hardening catalyst may be blended as needed. When a radical polymerization type thermosetting resin is used, a free radical polymerizable monomer such as styrene or diallyl phthalate may be blended in an appropriate amount. Moreover, in order to adjust the viscosity, both of them can be mixed with a solvent as needed. The forging material layer prepreg is obtained by impregnating and semi-curing the nonwoven fabric substrate into the thermosetting resin composition. Specifically, the nonwoven fabric substrate is impregnated with a thermosetting resin composition, and the fiber substrate containing the thermosetting resin composition is heated and dried to form a thermosetting resin in a semi-hardened core layer. Dip blank. [Surface layer] Next, a prepreg (hereinafter referred to as a surface layer prepreg) for forming a surface layer will be described. The reference layer prepreg is a woven fiber substrate obtained by using a synthetic fiber cloth (woven fabric) of synthetic fibers such as glass fiber (woven fabric), polyacrylic fiber fiber, polystyrene fiber, and nylon fiber. , impregnated with resin coatings. Thus, by using the fibrous base material as the surface layer, the dimensional stability and heat resistance of the obtained composite laminated board can be improved. A resin coating for forming a prepreg of a skin layer, and a radical polymerization of the same epoxy resin, an unsaturated polyester resin, an ethylene resin, etc. for the production of a core layer prepreg. The thermosetting resin of the type is a resin component of a tree sap coating. Further, in the resin coating 11 201008778 for forming the surface layer prepreg, as in the case of the resin coating for forming the anger layer, it is possible to mix various reaction initiators and hardeners, and fillers as needed. . It is also possible to mix and match the filler in a range which does not impair the effect of the present invention as needed. The thermosetting resin composition contained in the resin coating impregnated with the woven fiber substrate is preferably a thermosetting resin composition for forming a core layer prepreg. In other words, the thermosetting resin has a volume of 80 to 150 parts by volume of the inorganic filler, and the inorganic filler is preferably a Sanshui mine containing an average particle diameter (D5D) of 2 to 15 p. The type of hydroxide particles (A)' are at least one selected from the group consisting of boehmite particles having an average particle diameter (D5〇) of 2 to 15/zm and an average particle diameter (I.) having 2 to 15/zm. And a free starting temperature of 40 (a crystalline water containing TC or more, or an inorganic component containing no inorganic water of crystal water), and an alumina particle (c) having an average particle diameter of 1/5 m or less, the gibbsite The thermosetting resin composition of the aluminum hydroxide particles (A) and the inorganic component (B) and the aluminum particles (C) in a ratio (volume ratio) of 1:0 to 1 :1 ·1 to 1. [Laminated Board] ❹ A composite laminated board 10 according to an embodiment of the present invention will be described below with reference to Fig. 1. The composite laminated board 10 has a core material layer 1 and a layer structure in which the surface layer 2 laminated on both surfaces of the core material layer is laminated. Therefore, in this surface layer, the metal foil 3 is laminated to form a metal foil laminated board. The core material layer 1 is composed of a thermosetting resin composition lb including a nonwoven fabric base material 13 and an inorganic filler, and the surface layer 2 is composed of a woven fiber base material 2a and a resin composition 2b. 12 201008778 The core material layer 1 is obtained by immersing the nonwoven fabric substrate 1 a 3 such as glass nonwoven fabric and cellophane in the thermosetting resin composition 丨b. The thermosetting resin composition lb is a gibbsite-type aluminum hydroxide particle (A) having an average particle diameter (D5) of 2 to 5 μm in the thermosetting resin, and at least one type is selected from 2 The average particle diameter (j) of 15 is m. Boehmite particles and an inorganic component (b) having an average particle diameter of 2 to 15 am (Dy and a free starting temperature of 4 〇 (including crystallization or more, or inorganic particles not containing crystal water)
與具有1.5/ζιη以下之平均粒子徑的氧化鋁粒子（c)之無機 填充材，配合而成。 另一方面，表材層2，是使玻璃布之織纖維基材2a中 含浸樹脂組成物2b而成。 於疋，藉由在芯材層i的兩表面上分別層積表材層2, 再於表材層2的表面層積金屬鶴3,而層積成形該層積體， 製得貼附金屬箱之複合層積板1〇。再者，芯材層預浸料述 以及表材層預浸料述可為i層，複數層，具體言之可視目 ❹ 的需要調整為1〜3層重疊者。 金屬箔沒有特別限制，可使用如銅箔、鋁箔、鎳箔等。 又，金屬箔可在兩表面配置，亦可僅配置於一面。再者， 未配置金屬羯的那一面，亦可配置離形薄膜而加熱加壓成 型層積體取代金屬箔。 因此，對於以此形成之複合層積板1〇,可藉由施加加 成（additive)法和負過程（subtractive)法等習知的配線 加工處理和穿孔加工而得印刷電路板。 此時，本實施型態的複合層積板1G，由於是在構成芯 13 201008778 材層1之樹脂組成物中，配合三水鋁礦型氫氧化鋁粒子 (A)，又配合既定量的平均粒子徑小的氧化鋁粒子（c)，因 此可抑制層積板鑽孔加工時鑽孔刀刃的磨損。也因此，能 夠使鐵孔刀刃增加使用壽命。又，不僅適用於用以形成穿 孔的鑽孔加工’亦不易在形成之孔的内面形成凹凸，可形 成平滑的該孔内面。所以在孔的内面施加沖孔形成穿孔的 場合可賦予該穿孔高的導通可靠性。又，藉由配合優良熱 傳導性的氧化鋁粒子（C)，能夠使層積板的熱傳導性明顯提 升。再者，因為配合小粒子徑的氧化鋁粒子（c),層積板的❹ 鑽孔加工性亦不會明顯降低。又，藉由配合前述無機成分 (B )’耐熱性以及鑽孔加工性部會明顯降低，且能賦予熱傳 導性。 本實施型態的熱傳導性和鑽孔加工性優良之複合層積 板，可適用於要求高放熱性之用途如液晶顯示器搭載之發 光一極體背光的印刷基板，和發光二極體照明的印刷基板 等。 具體言之，可舉例如第2圖中所示之搭載於液晶顯示 器之發光二極體背光裝置20為發光二極體之一用途。第2 圖中的發光二極體背光裝置2〇,藉由在印刷電路基板21 上配置實裝複數個（第2圖中是3個）的發光二極體22之發 光二極體模組23多數配列而構成，並背面配設於液晶顯示 器上’而作為液晶顯示器等的背光裝置。習知以來普遍種 類的液晶顯不器’可廣泛使用冷陰極管（CCFL)作為液晶顯 不器的背光裝置，近年來’與冷陰極管方式的背光裝置相 14 201008778 比因為可廣泛増加色域而提升晝質’又以不使用水銀降低 環境負荷的觀點來說，還有可再更薄型化，而開發出如上 述之發光二極體背光裝置。 發光二極體模組’一般而言，與冷陰極管相比消耗電 力大’因此發熱量也多。因此藉由使用本發明之複合層積 ，板作為需要高放熱性之印刷電路基板21可大幅改善放教 的問題。因此能提高發光二極體的發光效率。 接著以實施例具體詳細說明本發明。然而，本發明並 不限於下列實施例。 【實施方式】 (實施例1) (層積板之製造） 對包含雙酚A型環氧樹脂與二氰二醯胺（Dicy)系硬化 劑之熱硬化性樹脂清漆的熱硬化性樹脂分1 〇 〇體積部，配 ❹ 合三水鋁礦型氫氧化鋁（住友化學（股）製造、〇5。：5.4以 髏積部，三水鋁礦型氫氧化鋁（住友化學（股）製造、D5():12 6 /zm)35體積部，勃姆石（Ι)5β:5.5//ιη)15體積部，以及氧化 銘（住友化學（股）製造、D5D:0.76em)15體積部，使其平均 分散。將密度60g/m2、厚度400/zm之玻璃不織布（vi iene(股） 製造之玻璃不織布），含浸於配合填充材之樹脂清漆中得至,】 芯材層預浸料坯。 另一方面，將密度200g/m2、厚度18〇em之破璃布（織 布）（日東紡（股）製造之7628)含浸於含有硬化劑之環氧樹 15 201008778 脂清漆中而不配合填充材，而得到表材層預浸料枉。 於是，將2枚芯材層預浸料堪，分別在其兩外表面， 依次附載表材層預浸料^枚與〇.〇18随的銅落而得層積 體。將該層積體炎住於2枚的金屬薄板中間，在溫度刚 t：’壓力·g/m、條件下加熱成型，而得厚度U随之 貼銅箱複合層積板。 根據下列評價方法評價製得之貼銅落複合層積板的熱 傳導率、22G°C烤箱耐熱性試驗、26()t焊錫耐熱試驗、壓 力鍋試驗（PCT)、鑽孔磨損率、以及難燃性。其結果示於下春 述表卜再者，下述表1以及表2中，各實施例以及各比 較例的括弧中所示的值，是表示對每i體積部的三水銘礦 型氫氧化銘粒子之勃姆石粒子、各無機粒子或氧化銘粒子 的配合比。 〈熱傳導率〉 以水中置換法測定製得之貼銅箔複合層積板的密度， 又，以DSC(掃描顯示熱量測定）檢測比熱，再以雷射閃光 法測定熱擴散率。 ® 於是從以下的算式算出熱傳導率。 熱傳導率（W/m. K)=密度（kg/m3)x比熱（kJ/kg. Κ)χ熱 擴散率（m2/S)xlO〇〇 <220°C烤箱耐熱試驗> 使用製得之貼銅箔複合層積板，將根據JISC6481製作 之試驗片在設定於220。(：之附有空氣循環裝置之恆溫槽中 處理一小時’銅箔以及層積板沒有產生膨脹以及脫皮時判 16 201008778 定為「優」，產生膨脹或脫皮時判定為「劣」。 <260°C焊錫耐熱試驗〉 使用製得之貼銅箔複合層積板，將根據JISC6481製作 之試驗片浸潰於26(TC的焊錫浴中，測定銅箔以及層積板 未產生膨脹或脫皮時的最大時間。 〈壓力鍋試驗（PCT)> 使用製得之貼銅箔複合層積板，將根據JISC6481製作 瘳 之試驗片’在121 °C ’ 2氣壓的殺菌鋼（autoc 1 ave)中處理 60分鐘。於是將處理之層積板浸潰於26〇〇c的焊錫槽中， 測定銅箔以及層積板產生膨脹或脫皮時的最大時間。 〈鑽孔磨損率〉 將製得之層積體3枚重疊，鑽孔（鑽孔徑〇. 5mm、振動 角度35。）以60000旋轉/min穿設3000個孔後的鑽孔刀刀 的磨知率，以對鑽孔加工前的鑽孔刀刃的大小（面積）之鑽 孔加工磨損的鑽孔刀刃的（面積）的比率（百分率）評價之。 φ 〈難燃性〉 將製得之貼銅箔複合層積板以既定大小切割，根據 UL94的燃燒試驗方法進行燃燒試驗，判定之。 (實施例2〜7、以及比較例1 ~ 14) 製造芯材層預浸料坯時，除了變更樹脂組成物之組成 如表1或表2之外與實施例1同樣地製得層積體，評價之。 實施例1以及實施例2〜7的結果示於表1，以及比較例1〜14 的結果不於表2。 再者’實施例4以及實施例6令，是使用平均粒子徑 17 201008778 (Dm)6. 5// m的滑石（富士滑石工業（股）製造），而比較例8 是使用平均粒子徑（D5〇)0. 76 // m的氧化鋁（住友化學（股） 製造）。It is blended with an inorganic filler having alumina particles (c) having an average particle diameter of 1.5/inch or less. On the other hand, the surface layer 2 is obtained by impregnating the woven fiber base material 2a of the glass cloth with the resin composition 2b.疋, by laminating the surface layer 2 on both surfaces of the core layer i, and laminating the metal crane 3 on the surface of the surface layer 2, the laminated body is laminated to obtain a metal The composite laminate of the box is 1 inch. Further, the core layer prepreg and the surface layer prepreg may be i layers, plural layers, specifically, the need to adjust the number of layers to 1 to 3 layers. The metal foil is not particularly limited, and for example, a copper foil, an aluminum foil, a nickel foil, or the like can be used. Further, the metal foil may be disposed on both surfaces or may be disposed only on one surface. Further, the side on which the metal crucible is not disposed may be provided with a release film and a heat and pressure type laminate instead of the metal foil. Therefore, for the composite laminated board 1 thus formed, a printed circuit board can be obtained by applying a conventional wiring processing and a punching process such as an additive method and a subtractive method. At this time, the composite laminated plate 1G of the present embodiment is blended with the gibbsite-type aluminum hydroxide particles (A) in the resin composition constituting the core layer 13 201008778, and is combined with a quantitative average. Since the alumina particles (c) having a small particle diameter can suppress the abrasion of the drilling blade during the drilling of the laminated plate. Therefore, it is possible to increase the service life of the iron hole blade. Further, it is not only applicable to the drilling process for forming the perforations, but also it is difficult to form irregularities on the inner surface of the formed hole, and a smooth inner surface of the hole can be formed. Therefore, in the case where a punch is formed in the inner surface of the hole to form a perforation, it is possible to impart high conduction reliability to the perforation. Further, by blending the alumina particles (C) having excellent thermal conductivity, the thermal conductivity of the laminated sheet can be remarkably improved. Further, since the alumina particles (c) having a small particle diameter are blended, the boring processability of the laminated board is not significantly lowered. Further, the heat resistance and the drilling processability portion of the inorganic component (B)' are significantly lowered, and the heat conductivity can be imparted. The composite laminated board excellent in thermal conductivity and drilling processability of the present embodiment can be applied to a printing substrate requiring a high exothermic property such as a light-emitting one-electrode backlight mounted on a liquid crystal display, and printing of a light-emitting diode illumination. Substrate, etc. Specifically, for example, the light-emitting diode backlight unit 20 mounted on the liquid crystal display shown in Fig. 2 is used for one of the light-emitting diodes. In the light-emitting diode backlight device 2 of FIG. 2, a plurality of light-emitting diode modules 23 of a plurality of light-emitting diodes 22 (three in FIG. 2) are disposed on the printed circuit board 21. Most of them are arranged in a line, and the back side is disposed on a liquid crystal display, and is used as a backlight device such as a liquid crystal display. Since the conventional type of liquid crystal display device has been widely used, a cold cathode tube (CCFL) can be widely used as a backlight device for a liquid crystal display device. In recent years, compared with the cold cathode tube type backlight device phase 14 201008778, the color gamut can be widely used. In the case of improving the enamel, it is possible to further reduce the environmental load without using mercury, and to develop a light-emitting diode backlight device as described above. The light-emitting diode module 'generally consumes a larger amount of power than a cold cathode tube' and thus generates a large amount of heat. Therefore, by using the composite laminate of the present invention, the board can greatly improve the problem of teaching as a printed circuit board 21 requiring high heat dissipation. Therefore, the luminous efficiency of the light-emitting diode can be improved. Next, the present invention will be specifically described in detail by way of examples. However, the invention is not limited to the following examples. [Embodiment] (Example 1) (Production of laminated board) Thermosetting resin of a thermosetting resin varnish containing a bisphenol A type epoxy resin and a dicyandiamide (Dicy) type hardening agent is classified into 1 〇〇 Volume, equipped with gibbsite-type aluminum hydroxide (manufactured by Sumitomo Chemical Co., Ltd., 〇5.: 5.4 in the hoarding department, gibbsite-type aluminum hydroxide (Sumitomo Chemical Co., Ltd.) D5 (): 12 6 /zm) 35 volume, boehmite (Ι) 5β: 5.5 / / ιη) 15 volume, and oxidation Ming (Sumitomo Chemical (stock), D5D: 0.76em) 15 volume, Make it evenly dispersed. A glass non-woven fabric (glass non-woven fabric manufactured by vi iene) having a density of 60 g/m 2 and a thickness of 400/zm was obtained by impregnating a resin varnish mixed with a filler to obtain a core layer prepreg. On the other hand, a woven fabric (woven fabric) having a density of 200 g/m 2 and a thickness of 18 〇em (7628 manufactured by Ridong Textile Co., Ltd.) was impregnated in an epoxy tree 15 201008778 grease varnish containing a hardener without filling. The material is obtained, and the surface layer prepreg is obtained. Then, the two core material layers are prepreg, and the two layers of the outer layer are sequentially attached with the surface layer prepreg and the copper falling with the 〇.〇18 to obtain a layered body. The laminate was placed in the middle of two metal sheets and heated under the condition of a temperature t: 'pressure·g/m, and the thickness U was applied to the copper box composite laminate. According to the following evaluation methods, the thermal conductivity of the prepared copper-clad composite laminated board, the 22G °C oven heat resistance test, the 26 ()t solder heat resistance test, the pressure cooker test (PCT), the drilling wear rate, and the flame retardancy were evaluated. . The results are shown in the following table. In Tables 1 and 2 below, the values shown in the parentheses of the respective examples and comparative examples are the waters of the Sanshui minerals for each volume. The mixing ratio of the boehmite particles, the inorganic particles or the oxidized particles of the oxidized particles. <Thermal Conductivity> The density of the copper-clad laminate laminated plate obtained by the underwater displacement method was measured, and the specific heat was measured by DSC (scanning display calorimetry), and the thermal diffusivity was measured by a laser flash method. ® Then calculate the thermal conductivity from the following formula. Thermal conductivity (W/m. K) = density (kg/m3) x specific heat (kJ/kg. Κ) χ thermal diffusivity (m2/S) xlO 〇〇 < 220 ° C oven heat test > use For the copper foil composite laminate, the test piece prepared according to JIS C6481 was set at 220. (: One hour of treatment in the constant temperature bath with air circulation device) The copper foil and the laminated plate did not cause swelling and peeling when the judgment was made on 2010 201008778, and it was judged as "excellent" when it was expanded or peeled off. 260 ° C solder heat resistance test 〉 Using the prepared copper foil composite laminated board, the test piece prepared according to JIS C6481 was immersed in a solder bath of 26 (TC), and the copper foil and the laminated board were not expanded or peeled. The maximum time of the pressure cooker test (PCT)> Using the prepared copper foil composite laminate, the test piece prepared according to JIS C6481 was treated at 2 °C sterilization gas (autoc 1 ave) at 121 °C. For 60 minutes, the laminated laminate was then immersed in a 26 ° C solder bath to determine the maximum time for the copper foil and the laminated sheet to expand or peel. <Drilling wear rate> The resulting laminate 3 pieces of overlap, drilling (drilling aperture 〇 5 mm, vibration angle 35.) The wear rate of the drilling knife after 3,000 holes is rotated at 60,000 rotations/min to drill the holes before drilling Drilling knives for the size of the blade (area) The ratio (percentage) of the blade (area) was evaluated. φ <flammability> The prepared copper foil composite laminate was cut to a predetermined size, and the combustion test was carried out according to the UL94 combustion test method. Examples 2 to 7 and Comparative Examples 1 to 14) When a core material layer prepreg was produced, a laminate was obtained in the same manner as in Example 1 except that the composition of the resin composition was changed as shown in Table 1 or Table 2, and evaluation was performed. The results of Example 1 and Examples 2 to 7 are shown in Table 1, and the results of Comparative Examples 1 to 14 are not shown in Table 2. Further, in Example 4 and Example 6, the average particle diameter 17 201008778 was used. (Dm) 6.5 ohmite (manufactured by Fuji Talc Industry Co., Ltd.), and Comparative Example 8 is alumina using average particle diameter (D5 〇) 0. 76 // m (Sumitomo Chemical Co., Ltd.) ).
18 201008778 實施例7 20(0.50) 20(0.50) c=> oo CZ5 ο CNI |· 1··· i 1 1 〇〇 LO 〇) 實施例6 Ο 60(0. 50) 10(0.14) s ο ο 1.52 丄 49.2 〇 1 > 實施例5 § 30(0.50) 10(0.16) <r> CD ο ο ，丨丨丨Η csa cn» CD 丄 CX) 〇〇 CO CD 1 > 實施例4 | LO CO 35(1.0) 30(0.86) CD g ο ο 卜 C<l τ—Η CNI C^* LO CD 1 > 實施例3 I CNI CD 15(0.21) 1 o CD ◦ 〇) τ-Ή 1.02 1 CO 〇 實施例2 ο 1 15(0.21) 15(0.21) 1 CD c=> <=> τ—ί D— 05 <〇 44.5 〇 1 > 實施例1 LO CO LO CO 15(0.21) 15(0.21) [ g CZ5 ο 1.04 § 〇〇 卜 〇 1 > 實施例號碼 (A1)三水鋁礦型氫氧化鋁 (D5〇:5. 4/zni) (A2)三水鋁礦型氫氧化鋁 (Ds〇: 12. 6^m) (B)勃姆石（D5〇:5. 5"m) (C)氧化鋁(D5D:0.76/zm) 滑石（D5〇:6. 5//m) 無機填充材合計(部） 環氧樹脂 熱傳導率(W/m · Κ) 220°C烤箱耐熱性(1小時） 260°C焊錫耐熱性(秒） PCT(121°C、2 氣壓、60 分鐘） 鑽孔磨損率(％) 難燃性OJL-94) 芯材層之 樹脂組成物 (體積部） 評價結果 2 表 比較例號碼 比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 比較例 7 比較例 8 比較例 9 比較例 10 比較例 11 比較例 12 比較例 13 比較例 14 芯材層 之樹脂 組成物 (體積部） 無 機 填 充 材 (A1)三水鋁礦型氫氧化鋁 (D5〇:5.4"m) — 100 - 70 70 122 103 35 35 - - 40 35 80 (A2)三水鋁礦型氫氧化鋁 (Ds〇: 12. 6//m) - — 100 - - - - 35 - - 一 - - 40 (B)勃姆石（1)50:5. 5" m) — - - 30 (0.43) - — - 15 (0.21) 50 (1.4) 70 70 15 (0. 37) 25 (0. 71) 一 (C)氧化銘（Dai:0· 76/·ίπι) - - — - 30 (0.43) - - - 15 (0.21) 15 30 15 (0. 37) 40 (1.1) 15 (0.13) 氧化銘 〇>5〇:4"πι) 15 (0.21) 滑石（1)50:6. 5" m) — 15 無機填充材合計(部） 0 100 100 100 100 122 103 100 100 100 100 70 100 150 環氧樹脂 100 100 100 100 100 100 100 100 100 100 100 100 100 100 評價結果 熱傳導率(W/m· Κ) 0.62 0.90 0.98 0. 92 1.22 1.04 0.9 1.45 1.12 1.15 1.25 0.38 0.8 1.23 220°C烤箱耐熱性(1小時） - 劣 劣 優 優 劣 劣 優 優 優 優 優 優 劣 260°C焊錫耐熱性(秒） - 106 72 180 180 79 106 180 180 180 180 180 180 60 PCT(121°C、2 氣壓、60 分鐘) - 64 41 180 180 41 64 180 180 180 180 180 180 28 鑽孔磨損率00 51.5 22.5 28 27.3 57.2 31.2 22.6 100 44.5 44.5 57.5 37.5 65.5 51.3 難燃性(UL-94) 一 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-1 V-1 V-1 V-1 V-1 V-0 201008778 φ 20 ❹ 201008778 由表1以及表2所示之結果’本發明之實施例1 ~7之 貼銅箱複合層積板均具有〇. 97W/m .K以上的高熱傳導，且 财熱性，鑽孔耐磨損性，難燃性皆高。另一方面，使用一 般粒子住之氧化銘之比較例8的貼銅箱複合層積板，與使 用細微粒子徑之氧化鋁之實施例1的貼銅箔複合層積板相 比’鐵孔耐磨損性非常劣化。又，實施例2與比較例4比 較’若未配合氧化鋁即無法得到充分的熱傳導率。又，未 ® 配合二水铭礦型氧化铭之比較例1 0以及比較例11的話難 燃性是V-1的程度。又，無機填充材的合計量對環氧樹脂 1 〇〇質量部為70質量部的比較例1 2，熱傳導率明顯降低。 又，未含有勃姆石的比較例2、3、6、7以及14,烤箱耐 熱性以及焊錫難熱性均降低。 (實施例8〜1 6、及比較例1 5〜2 7) 芯材層預浸料坯的製造，除了如表3或表4之樹脂組 成物的組成之外，是以與實施例1同樣地方式製得層積 〇 體。實施例8~ 16之結果示於表3，比較例15〜27的結果示 於表4。 再者，實施例14是使用平均粒子徑（ίο6· 5以m的結 晶二氧化矽，實施例15使用平均粒子徑（D5D)6,5//m的氧 化鎂（日本輕金屬（股）製造），實施例丨6是使用平均粒子^ (D5〇6.6em的氮化銘（古河電子（股）製造），比較例2〇以 及比較例22 ’則使用平均粒子徑（DwM/zm的氧化銘（住友 化學（股）製造）。 21 3 表 實施例號碼 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 芯材層 之樹脂 組成物 (體積部） 無 機 填 充 材 (A1)三水鋁礦型氫氧化鋁 (Ds〇:5. 4^m) 35 70 - 55 - 25 35 35 35 (A2)三水鋁礦型氫氧化鋁 (Ds〇: 12. 6//m) 35 - 70 — 60 25 35 35 35 (81)滑石（〇5。：5.5私111) 15 (0.21) 15 (0.21) 15 (0.21) 35 (0.64) 30 (0. 50) 10 (0.14) — - - (B2)結晶性二氧化矽 (Ds〇:6. 5//ra) — — 一 - - - 15 (0.21) - 一 (B4)氧化鎂(Dm : 6. 5 // m) - - - - 一 — — 15 (0.21) - (B5)氮化i呂（D5〇:6. 6"m) - - - - - - — - 15 (0.22) (C)氧化銘(D5d:0. 76；αιπ) 15 (0.21) 15 (0.21) 15 (0.21) 20 (0.36) 10 (0.16) 20 (0.40) 15 (0.21) 15 (0.21) 15 (0.21) 無機填充材合計(部） 100 100 100 110 100 80 100 100 100 環氧樹脂 100 100 100 100 100 100 100 100 100 士采/番έ士里 熱傳導率(w/m . K) 1.07 1.05 1.10 1.20 1.06 0.93 1.08 1.07 1.1 220°C烤箱耐熱性（1小時） 優 優 優 優 優 優 優 優 優 260°C焊錫耐熱性(秒） 180 180 180 180 180 180 180 180 180 貝箱木 PCT(121°C、2 氣壓、60 分鐘) 180 180 180 180 180 180 180 180 180 鑽孔磨損率(％) 41.7 41.0 42.4 49.7 36.5 42.9 42 41.7 42.3 難燃性(UL-94) V-0 V-0 V-0 V-0 V-0 V-0 V-0 Υ-0 V-0 201008778 ❹ 22 θ 4 表 參 ο 比較例號碼 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 15 16 17 18 19 20 21 22 23 24 25 26 27 (A1)三水鋁礦型氫氧化鋁 (1>5〇: 5.4 y m) - 100 一 - — - 122 35 35 - 35 80 40 (A2)三水鋁礦型氫氧化鋁 (Ds〇: 12. 6^m) - - 100 — - - - 35 — - 一 40 - 無 (B1)滑石 〇>5。： 5· 5 " m) - - - 100 - - - 15 (0.21) 50 (1.4) 70 25 (0.71) 15 (0.13) 15 (0. 37) 怒材層 之樹脂 機 填 (C)氧化銘(〇5。:0· 76"m) - - - - 100 - - - 15 (0.21) 30 40 (1.1) 15 (0.13) 15 (0. 37) 組成物 (體積部） 充 材 氧化IS(D5〇:4//in) — - - - - 100 - 15 (0.21) - - - - - 無機填充材合計(部） 0 100 100 100 100 100 122 100 100 100 100 150 70 環氧樹脂 100 100 100 100 100 100 100 100 100 100 100 100 100 熱傳導率(W/m.K) 0.45 0. 90 0.98 0. 98 1.80 2.10 1.10 1.12 1.07 1.22 1.28 1.53 0. 78 220°C烤箱耐熱性(1小時） 優 劣 劣 優 優 優 劣 優 優 優 劣 劣 優 評價結果 260°C焊錫耐熱性(秒） 180 106 72 180 180 180 79 180 180 180 180 80 180 PCT(121°C、2 氣壓、60 分鐘） 180 84 41 180 180 180 41 180 180 180 180 28 180 鑽孔磨損率(％) 51.5 22.8 24.7 24.7 100 100 27.8 63.1 41.7 60.0 71.2 53.2 34.2 難燃性(UL-94) V-0 V-0 V-0 V-1 V-1 V-1 V-0 V-0 V-1 V-1 V-1 V-0 V-1 201008778 23 201008778 由表3之結果’本發明之實施例8-16之層積板，均具 有優異的高熱導率’烤箱耐熱性以及PCT耐熱性。又，鑽 孔磨損率也低，難燃性亦達到v_〇。另一方面，由表4的 結果’如比較例1 6以及比較例17的層積板，含有多三水 鋁礦型氫氧化鋁的場合，耐熱性降低。又，僅含有滑石和 氧化紹的比較例18〜2〇的層積板，難燃性是v—丨。又，使 用平均粒子徑4/zm之氧化鋁取代實施例8的平均粒子徑 〇_ 76 y m的氧化銘的比較例22，鑽孔磨損率明顯提高。又， 在對二水銘礦型氫氧化鋁1體積部之滑石的配合比高如 β 1. 4之比較例23的層積板，鑽孔磨損性明顯提高。又，未 含有三水鋁礦型氫氧化鋁之比較例24之層積板的鑽孔磨 損率亦高，又，難燃性也是V—i。又，即使對三水鋁礦型 氫氧化鋁體積部1之平均粒子徑〇.76//111之氧化鋁的配合 比高如1. 1之比較例25的層積板，鑽孔磨損性明顯增加， 且難燃性亦為V-1。 如以上說明，本發明之另一方面，是由不織布纖微基 材含浸於熱硬化性樹脂組成物而得之芯材層與分別積層 於前述芯材$之兩表自的表材層積層一體化之層積板，前 述熱硬化性樹脂組成物對熱硬化性樹脂100體積部含有無 機填充材80〜150體積部，前述無機充填材，包含（A)具有 15// m之平均粒子控d)的三水鋁礦型氫氧 匕鋁粒子（B)至J 1種擇自具有2〜15ym之平均粒子徑（d5〇) 的勃姆石（Boehmite)粒子、以及具有2〜15//m之平均粒子 k(D5«)，且游離開始溫度4〇〇<>c以上的含結晶水或者未 24 201008778 含有結晶水之無機粒子的盔 的無機成分’以及(C)具有l.5"m 平均粒子控（Ds。）的氧化.獻早 ^ _ 乳化銘粒子，則述三水銘礦型氫 氧化銘粒子（A)與至少1種 义 種擇自則述勃姆石粒子以及前述 無機粒子之無機成分（B)兄 與則述氧化鋁粒子（C)之配合比 (體積比），為1:0. 1十〇. W。 、如上述構造，可得到熱傳導性，耐熱性，鐵孔加工性， 以及難燃性優良的廢接 積板。因為高熱傳導性’在熱硬化性 參 樹脂組成物配合一般的氧化銘時鐵孔加工性明顯降低。因 為氧化銘高硬度。本發明，藉由以既定比例配合粒子徑極 小的氧化铭，在不降柄m文丨上 降低鑽孔加工性的情況下耐熱性明顯提 高。 又，鋁化合物如三水鋁礦型氳氧化鋁或 3h2g)疋賦予熱傳導性，錢孔加卫性，以及難燃性平 、成刀—水鋁礦型氫氧化鋁，因為具有放出約2〇〇~230 C的、、明水的潛在特性，因而賦予難燃性的效果特別高。 ❹因此’配合比例過多時，焊錫迴焊時會是產生氣泡等的 因。 再者，鋁系化合物之勃姆石（A100Η)，能給予層積體熱 2導性與耐熱性。勃姆石，因為具有放出約45(N50(TC的 曰曰X的潛在特性’比三水銘礦型氳氧化銘财熱型更優。 更能發揮在高溫時的難燃性。 又游離開始溫度40(TC以上的含結晶水，或者未含 有、’·〇明水之無機粒子，同樣地能給予層積體熱傳導性與耐 ' ^。如此的無機粒子，可抑制電路基板之迴焊 25 201008778 焊錫時產生氣泡。又，能使高溫時的耐燃性發揮。 本發明，藉由使用以上述既定比例配合具有既定之平 均粒子徑（D5。）的三水鋁礦型氫氧化鋁粒子（A)，與具有既定 之平均粒子徑（Ds。）的至少1種擇自勃姆石粒子、以及游離 開始溫度400°C以上的含結晶水，或者未含有結晶水之無 機粒子所組成之群組的無機成分（B)，以及粒子徑小的氧化 鋁粒子（C)，製得用以製作具有優異熱傳導率，優良耐熱 性，優良鑽孔加工性，以及難燃性兼具之層積板的熱硬化 性樹脂組成物。 使用如此熱硬化性樹脂組成物而得之層積板，較佳是 用於要求高放熱性之各種基板，特別是發熱量多的搭載複 數個發光二極體的發光二極體搭載用基板。如上之層積板 組成之印刷電路基板，在各種電子零件表面實裝的場合， 即使在無錯迴焊焊錫溫I 26Gt的程度，亦不會在金屬落 產生氣泡。 ❹ 則述二水鋁礦型氫氧化鋁粒子（A)，較佳是具有 2〜10”之平均粒子徑㈤之第1三水銘礦型氫氧化銘， 具有10〜15心之平均冑子徑（1)5〇)之第2三水銘碌型氯氧化 «物根據上述構造，藉由緊密填充無機填充材， 可得到熱傳導性特別優良之層積板。 前述無機成分⑻之1種無機粒子，為至少1種擇自氧 化鋁、氧化鎂、結 擇目氧 虱氧化銨、氮化硼、氮 梦、碳化石夕、滑石、燒結高嶺土、以及黏土等 所組成之群組。 久勒土导 26 201008778 又’較佳是將織纖維基材含浸 性樹脂組成物相同成分以同樣的組 樹脂組成物而得之表材層， 面而得層積一體化之層積板 熱傳導率’優良耐熱性，優 的層積板。 於與上述記載之熱硬化 成比率配合之熱硬化性 分別層積於上述芯材層之兩表 。根據上述構造，可得到優異 良鑽孔加工性以及難燃性兼具 由上述層積板製得之電路基板，耐熱性，難燃性，特 別是鑽孔加工性均優異1此，適用於搭載發光二極體般 要求放熱性之電子零件的電路基板。 產業上可利用性 根據本發明可製得，熱傳導性，耐熱性，鑽孔加工性， 以及難燃性均優異的層積板或電路基板。 【圖式簡單說明】 第1圖係本發明之一實施型態的複合層積板的模式剖 面圖。 第2圖係發光二極體背光體的模式構造圖。 【主要元件符號說明】 1〜芯材層； la〜不織纖維基材； 2〜表材層； 2a〜織纖維基材； 27 201008778 2b〜樹脂組成物； 3 ~·•金屬箱； 10~複合層積板； 20〜發光二極體背光裝置； 21 ~印刷電路基板； 22~發光二極體； 23〜發光二極體模組。18 201008778 Example 7 20(0.50) 20(0.50) c=> oo CZ5 ο CNI |· 1··· i 1 1 〇〇LO 〇) Example 6 Ο 60(0. 50) 10(0.14) s ο ο 1.52 丄 49.2 〇 1 > Example 5 § 30(0.50) 10(0.16) <r> CD ο ο , 丨丨丨Η csa cn» CD 丄CX) 〇〇CO CD 1 > Example 4 LO CO 35(1.0) 30(0.86) CD g ο ο 卜 C<l τ-Η CNI C^* LO CD 1 > Example 3 I CNI CD 15(0.21) 1 o CD ◦ 〇) τ-Ή 1.02 1 CO 〇 Example 2 ο 1 15(0.21) 15(0.21) 1 CD c=><=> τ_ί D— 05 <〇44.5 〇1 > Example 1 LO CO LO CO 15 (0.21) 15(0.21) [ g CZ5 ο 1.04 § 〇〇 〇 1 > Example No. (A1) gibbsite-type aluminum hydroxide (D5 〇: 5. 4/zni) (A2) aluminum trihydrate Mineral aluminum hydroxide (Ds〇: 12. 6^m) (B) Boehmite (D5〇: 5. 5"m) (C) Alumina (D5D: 0.76/zm) Talc (D5〇: 6. 5//m) Total inorganic filler (part) Epoxy resin thermal conductivity (W/m · Κ) 220 °C oven heat resistance (1 hour) 260 °C solder heat resistance (seconds) PCT (121 ° C, 2 Air pressure, 60 minutes) Loss ratio (%) Flame retardant OJL-94) Resin composition of core material layer (volume portion) Evaluation result 2 Table comparison example number Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Resin composition of core material layer (volume portion) Inorganic filler (A1) gibbsite-type aluminum hydroxide (D5〇 :5.4"m) — 100 - 70 70 122 103 35 35 - - 40 35 80 (A2) gibbsite-type aluminum hydroxide (Ds〇: 12. 6//m) - 100 - - - - 35 - - One - - 40 (B) Bomstone (1) 50:5. 5" m) — - - 30 (0.43) - — - 15 (0.21) 50 (1.4) 70 70 15 (0. 37) 25 (0. 71) One (C) Oxidation (Dai:0·76/·ίπι) - - - - 30 (0.43) - - - 15 (0.21) 15 30 15 (0. 37) 40 (1.1) 15 ( 0.13) Oxidation inscriptions>5〇:4"πι) 15 (0.21) Talc (1) 50:6. 5" m) — 15 Total inorganic fillers (parts) 0 100 100 100 100 122 103 100 100 100 100 70 100 150 Epoxy 100 100 100 100 100 100 100 100 100 100 100 10 0 100 100 Evaluation results Thermal conductivity (W/m· Κ) 0.62 0.90 0.98 0. 92 1.22 1.04 0.9 1.45 1.12 1.15 1.25 0.38 0.8 1.23 220 °C oven heat resistance (1 hour) - Inferior superiority and inferior superiority and superiority 260 ° C solder heat resistance (seconds) - 106 72 180 180 79 106 180 180 180 180 180 180 60 PCT (121 ° C, 2 air pressure, 60 minutes) - 64 41 180 180 41 64 180 180 180 180 180 180 28 drill Hole wear rate 00 51.5 22.5 28 27.3 57.2 31.2 22.6 100 44.5 44.5 57.5 37.5 65.5 51.3 Flame retardancy (UL-94) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V- 1 V-1 V-1 V-1 V-1 V-0 201008778 φ 20 ❹ 201008778 The results shown in Table 1 and Table 2 'The copper-clad composite laminated sheets of Examples 1 to 7 of the present invention have 〇. High heat conduction above 97W/m .K, and heat resistance, drilling resistance and flame retardancy are high. On the other hand, the copper-clad composite laminated board of Comparative Example 8 using the general particle-based oxidation was compared with the copper-clad composite laminated board of Example 1 using the fine-particle-diameter alumina. The wear resistance is very degraded. Further, in Example 2, Comparative Example 4 was compared. If sufficient alumina is not blended, sufficient thermal conductivity cannot be obtained. In addition, in the case of Comparative Example 10 and Comparative Example 11 in which Shuangsong was combined with the sulphur dioxide, the flame retardancy was about V-1. Further, in the comparative example 1 2 in which the amount of the inorganic filler was 70 parts by mass in the epoxy resin, the thermal conductivity was remarkably lowered. Further, in Comparative Examples 2, 3, 6, 7, and 14 which did not contain boehmite, the heat resistance of the oven and the heat resistance of the solder were both lowered. (Examples 8 to 16 and Comparative Examples 1 to 5) The production of the core material layer prepreg was the same as in Example 1 except for the composition of the resin composition of Table 3 or Table 4. The layered carcass is produced in the ground manner. The results of Examples 8 to 16 are shown in Table 3, and the results of Comparative Examples 15 to 27 are shown in Table 4. Further, in Example 14, the average particle diameter (crystalline cerium oxide of ίο6·5 was used, and in Example 15, magnesium oxide (manufactured by Nippon Light Metal Co., Ltd.) having an average particle diameter (D5D) of 6,5/m was used. Example 丨6 is the use of the average particle ^ (D5 〇 6.6em of Niobium (manufactured by Furukawa Electronics Co., Ltd.), Comparative Example 2 〇 and Comparative Example 22 ' using the average particle diameter (DwM / zm of oxidation ( Sumitomo Chemical Co., Ltd.) 21 3 Table Example Number Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Resin Composition of Core Material Layer (Volume Part) Inorganic filler (A1) gibbsite-type aluminum hydroxide (Ds〇: 5. 4^m) 35 70 - 55 - 25 35 35 35 (A2) gibbsite-type aluminum hydroxide (Ds〇: 12. 6//m) 35 - 70 — 60 25 35 35 35 (81) Talc (〇5.: 5.5 private 111) 15 (0.21) 15 (0.21) 15 (0.21) 35 (0.64) 30 (0. 50 ) 10 (0.14) — — — (B2) Crystalline cerium oxide (Ds〇: 6.5//ra) — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — // m) - - - - one - 15 (0.21) - (B5) nitrided i (D5〇:6. 6"m) - - - - - - - - 15 (0.22) (C) Oxidation (D5d:0. 76;αιπ) 15 (0.21) 15 (0.21) 15 (0.21) 20 ( 0.36) 10 (0.16) 20 (0.40) 15 (0.21) 15 (0.21) 15 (0.21) Inorganic filler total (part) 100 100 100 110 100 80 100 100 100 Epoxy 100 100 100 100 100 100 100 100 100 Shicai / Panyu Lithermal Conductivity (w/m. K) 1.07 1.05 1.10 1.20 1.06 0.93 1.08 1.07 1.1 220 °C oven heat resistance (1 hour) Youyou Youyou Youyou Youyou 260 °C solder heat resistance (seconds) 180 180 180 180 180 180 180 180 180 BOX PCT (121 ° C, 2 psi, 60 min) 180 180 180 180 180 180 180 180 180 Drilling wear rate (%) 41.7 41.0 42.4 49.7 36.5 42.9 42 41.7 42.3 Flame retardant (UL-94) V-0 V-0 V-0 V-0 V-0 V-0 V-0 Υ-0 V-0 201008778 ❹ 22 θ 4 Reference ο Comparative example number comparison example Comparison example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example 15 16 17 18 19 20 21 22 23 24 25 26 27 (A1) gibbsite-type aluminum hydroxide (1 > 5 〇: 5.4 ym) - 100 one - — - 122 35 35 - 35 80 40 (A2) gibbsite aluminum hydroxide (Ds〇: 12. 6^m) - - 100 — - - - 35 — - one 40 - no (B1) talc >5. : 5· 5 " m) - - - 100 - - - 15 (0.21) 50 (1.4) 70 25 (0.71) 15 (0.13) 15 (0. 37) Resin machine filling of anger material layer (C) Oxidation (〇5.:0· 76"m) - - - - 100 - - - 15 (0.21) 30 40 (1.1) 15 (0.13) 15 (0. 37) Composition (volume) Filled oxide IS (D5 〇:4//in) — - - - - 100 - 15 (0.21) - - - - - Total inorganic filler (part) 0 100 100 100 100 100 122 100 100 100 100 150 70 Epoxy 100 100 100 100 100 100 100 100 100 100 100 100 100 Thermal conductivity (W/mK) 0.45 0. 90 0.98 0. 98 1.80 2.10 1.10 1.12 1.07 1.22 1.28 1.53 0. 78 220 °C oven heat resistance (1 hour) Good or bad good and bad excellent and excellent Good and bad evaluation results 260 ° C solder heat resistance (seconds) 180 106 72 180 180 180 79 180 180 180 180 80 180 PCT (121 ° C, 2 air pressure, 60 minutes) 180 84 41 180 180 180 41 180 180 180 180 28 180 Drilling wear rate (%) 51.5 22.8 24.7 24.7 100 100 27.8 63.1 41.7 60.0 71.2 53.2 34.2 Flame retardancy (UL-94) V-0 V-0 V-0 V-1 V-1 V-1 V- 0 V-0 V-1 V-1 V-1 V-0 V-1 201008778 23 201008778 by Table 3 Results 'embodiment of the present invention the laminated plates 8-16, were excellent in having a high thermal conductivity' PCT oven heat resistance and heat resistance. In addition, the wear rate of the drill hole is also low, and the flame retardancy also reaches v_〇. On the other hand, when the laminated sheets of Comparative Example 16 and Comparative Example 17 contained the results of Table 4 and the gibbsite-type aluminum hydroxide, the heat resistance was lowered. Further, the laminated sheets of Comparative Examples 18 to 2, which contained only talc and oxidized, had a flame retardancy of v-丨. Further, in Comparative Example 22 in which the alumina having an average particle diameter of 4/zm was used instead of the oxide having an average particle diameter of 〇 76 μm in Example 8, the drilling wear rate was remarkably improved. Further, in the laminated plate of Comparative Example 23 in which the mixing ratio of the talc in the first volume of the dihydrate mineral aluminum hydroxide was as high as β 1.4, the drilling wear resistance was remarkably improved. Further, the laminated plate of Comparative Example 24 which did not contain gibbsite-type aluminum hydroxide had a high drilling wear rate, and the flame retardancy was also V-i. Further, even in the laminated plate of Comparative Example 25 in which the mixing ratio of the alumina having an average particle diameter of 76.76//111 of the gibbsite-type aluminum hydroxide volume portion 1 is as high as 1.1, the drilling wear resistance is conspicuous. Increased, and the flame retardancy is also V-1. As described above, in another aspect of the present invention, the core material layer obtained by impregnating the nonwoven fabric micro-substrate with the thermosetting resin composition and the surface layer laminated on the surface of each of the core materials respectively are integrated. In the laminated board, the thermosetting resin composition contains 80 to 150 parts by volume of the inorganic filler to the volume of the thermosetting resin 100, and the inorganic filler contains (A) an average particle size of 15/m. The gibbsite-type oxyhydroxide aluminum particles (B) to J 1 are selected from Boehmite particles having an average particle diameter (d5 〇) of 2 to 15 μm, and have 2 to 15/m The average particle k (D5«), and the free starting temperature of 4 〇〇<> or more containing the crystal water or the inorganic component of the helmet of the inorganic particles not containing the water of the crystal water of 24 201008778 and (C) having 1.55";m oxidation of average particle control (Ds.). Xian early ^ _ emulsified Ming particles, said Sanshui Ming ore type hydroxide particles (A) and at least one species selected from the description of boehmite particles and the aforementioned The mixing ratio (volume ratio) of the inorganic component (B) of the inorganic particles and the alumina particles (C) is 1 :0. 1 十〇. W. According to the above configuration, a heat-suppressing plate having excellent heat conductivity, heat resistance, iron hole workability, and flame retardancy can be obtained. Because of the high thermal conductivity, the iron hole workability is markedly lowered when the thermosetting styrene resin composition is combined with the general oxidation. Because of the oxidation of high hardness. According to the present invention, the heat resistance is remarkably improved by reducing the workability of the drill without lowering the shank by oxidizing the particles having a small particle diameter at a predetermined ratio. In addition, aluminum compounds such as gibbsite-type lanthanum alumina or 3h2g) lanthanum impart thermal conductivity, money hole reinforced, and flame retardant flat, kiln-alumina-type aluminum hydroxide, because it has a release of about 2〇 The potential characteristics of 230~230 C and Mingshui are particularly high. Therefore, when the mixing ratio is too large, bubbles may be generated during solder reflow. Further, the boehmite (A100Η) of the aluminum compound can impart thermal conductivity and heat resistance to the laminate. Bom stone, because it has a release of about 45 (N50 (TC's potential characteristics of 曰曰X is better than Sanshui Ming type 氲 铭 铭 铭 铭 热 。 。 。 。 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更 更At a temperature of 40 (containing or containing TC or more, or inorganic particles not containing water, the thermal conductivity and resistance of the laminate can be similarly applied. Such inorganic particles can suppress reflow of the circuit board. 201008778 Air bubbles are generated during soldering, and the flame resistance at high temperatures can be exhibited. In the present invention, gibbsite-type aluminum hydroxide particles having a predetermined average particle diameter (D5) are blended at a predetermined ratio described above (A). And a group consisting of at least one selected from the group consisting of boehmite particles having a predetermined average particle diameter (Ds), and crystal water containing a free starting temperature of 400 ° C or higher, or inorganic particles not containing crystal water The inorganic component (B) and the alumina particles (C) having a small particle diameter are produced to produce a laminated board having excellent thermal conductivity, excellent heat resistance, excellent drilling processability, and flame retardancy. Thermosetting resin composition A laminated board obtained by using such a thermosetting resin composition is preferably used for various substrates requiring high heat dissipation, in particular, a substrate for mounting a plurality of light-emitting diodes having a plurality of light-emitting diodes In the case where the printed circuit board composed of the laminated board as described above is mounted on the surface of various electronic components, even if the temperature of the solderless solder reflow is I 26 Gt, no bubbles are generated in the metal drop. The ore type aluminum hydroxide particles (A) are preferably the first three waters of the average particle diameter (5) having a particle diameter of 2 to 10", having an average enthalpy diameter of 10 to 15 hearts (1) 5 〇. According to the above-mentioned structure, the second sulphate-type sulphuric acid oxidizing material is obtained by closely filling the inorganic filler, and a laminated plate having particularly excellent thermal conductivity is obtained. The inorganic component (8) has at least one inorganic particle. It is selected from the group consisting of alumina, magnesia, tantalum, ammonium oxynitride, boron nitride, nitrogen dream, carbonized stone, talc, sintered kaolin, and clay. Jurlei soil guide 26 201008778 Jia is impregnating the woven fiber substrate The same composition of the same composition of the resin composition obtained from the same composition of the resin composition, and the laminated plate has a thermal conductivity of excellent laminated layer, excellent heat resistance, and an excellent laminated plate. The thermosetting properties of the ratios are respectively laminated on the two sheets of the core material layer. According to the above structure, excellent circuitability and flame retardancy can be obtained, and the circuit board made of the above laminated board can be obtained, and heat resistance can be obtained. It is excellent in flame retardancy, and particularly excellent in drilling processability. It is suitable for a circuit board equipped with an electronic component requiring heat dissipation as a light-emitting diode. Industrial Applicability According to the present invention, heat conductivity and heat resistance can be obtained. A laminated board or a circuit board excellent in properties, drilling processability, and flame retardancy. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a composite laminated board according to an embodiment of the present invention. Fig. 2 is a schematic diagram showing the structure of a light-emitting diode backlight. [Description of main component symbols] 1~ core material layer; la~non-woven fiber substrate; 2~surface layer; 2a~woven fiber substrate; 27 201008778 2b~resin composition; 3 ~·•metal box; 10~ Composite laminated board; 20~ light-emitting diode backlight device; 21 ~ printed circuit board; 22~ light-emitting diode; 23~ light-emitting diode module.
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