TWI294441B - - Google Patents

Description

1294441 A7 __B7__ 五、發明説明（彳） 技術領域 (請先聞讀背面之注意事項再填寫本頁) 本發明爲關於電器、電子機器等所使用之絕緣材料， 特別爲關於熱傳導性優良之熱硬化性樹脂硬化物。 背技技術 由馬達和發電機至印刷電路板爲止之幾乎所有的電器 、電子機器爲由用以通電之導體，和絕緣材料所構成。 近年，隨著此些電器機器小型化的急速發展，使得對 於絕緣材料所要求之特性亦頗爲提高。其中，由小型化而 高密度化之導體中所發生的發熱量爲變大，故如何令熱放 射乃爲重要之課題。 相對地，於各種電器機器之絕緣材料中，由絕緣性能 之高度、成型之容易度、耐熱性等之觀點而言，乃廣泛使 用熱硬化性樹脂。 但是，一般而言，熱硬化性樹脂之熱傳導率低，成爲 妨礙前述熱放散之大要因。因此，具有高熱傳導率之絕緣 材料的必要性爲非常高。 經濟部智慧財產局員工消費合作社印製 具有高熱傳導性之材料，已知爲將高熱傳導性之塡料 粉末混合至熱硬化性樹脂之複合材料。所使用之塡料粉末 亦已檢討許多銀和鋁等之金屬粉末、二氧化矽、氧化錨、 氧化鎂、氧化鈹、氮化硼、氮化鋁 '氮化矽、碳化矽、氟 化鋁、氟化鈣等之無機陶瓷粉末等。 但是，若於熱硬化性樹脂中混合此類塡料粉末，則成 形前之樹脂粘度顯著增大，故難以製造微細構造物，又， 本紙張尺度適用中國國家標準（CNS)A4規格（210X 297公釐）^ " ------ -4 - 1294441 A7 B7 五、發明説明（2) 其作業性亦極差。 (請先閱讀背面之注意事項再填寫本頁) 又，熱硬化性樹脂之熱傳導率極低，混合少量之塡料 粉末之材料並不能提高其熱傳導率，必須混合大量的塡料 粉末。但是，實際上難令大量之塡料粉末於樹脂中均勻分 散。 更且，有機物之熱硬化性樹脂和塡料粉末之親和性亦 多發生問題，非常容易引起界面之剝離，於長期使用時其 絕緣性大爲降低之可能性亦大。 由此類觀點而言，達成有機材料爲高熱傳導率之課題 爲極重要。 有機材料達成高熱傳導率之方法，於特開昭6 Ιέ 9 6 0 6 8 號公報中 揭示充 塡以超高度定向聚合物纖維 之具有高熱傳導性之塑膠化合物。其爲利用POLYMER， v〇l. 19，155頁（1978年）所記載之超高度定向 聚合物纖維，於其纖維軸方向提高熱傳導率之性質。 經濟部智慧財產局員工消費合作社印製 但是，超高度定向之聚合物纖維爲其纖維軸之垂直方 向上之熱傳導率降低，故即使令聚合物纖維於有機絕緣組 成物中無規分散，亦幾乎無法提高熱傳導率。 經由令聚合物纖維於有機絕緣組成物中以單一方向排 列，則可取得排列方向上之熱傳導率優良之有機絕緣材料 ，但於此方向以外則熱傳導率有反而降低之問題。 又，於 ADVANCED MATERIALS，Vol. 5，1 0 7 頁（ 1 9 9 3年），及，德國專利第4 2 2 6 9 9 4號中，記 載令具有液晶原之二丙烯酸酯等單體，於某一方向定向後 本纸張尺度適用中國國家標準（CNS ) A4規格（210Χ 297公釐） -5- 1294441 A7 __B7 _ 五、發明説明（3) (請先閲讀背面之注意事項再填寫本頁) 進行交聯反應，爲分子鏈並列之薄膜面內方向之熱傳導率 高之各向異性材料。但是，其他以外之方向，特別於薄膜 厚度方向之熱傳導率變低。 一般，薄膜材料之熱移動方向爲於厚度方向之情況爲 壓倒性變多，且此類材料爲效果小。 關於厚度方向中分子鏈並列之手法亦有檢討。於特開 平1 一 149303號公報，特開平2 — 5307號公報 ，特開平2 - 2 8 3 5 2號公報，特開平2 — 1 2 7 4 3 8號公報中，記載外加靜電壓狀態下之聚氧亞 甲基和聚醯亞胺般有機材料之製法。 又，於特開昭6 3 — 2 6 4 8 2 8號公報中，記載令 聚丙烯和聚乙烯等之分子鏈排列之薄片，以排列方向重疊 層合後，將固粘之層合物以定向方向之垂直方向進行薄切 ，分子鏈於垂直方向排列之材料。 此些手法確實爲薄膜厚度方向之熱傳導率高之材料， 但其成形爲非常煩雜，所使用之材料受到限制。 經濟部智慧財產局員工消費合作社印製 於特開平1 1 — 3 2 3 1 6 2號公報中，記載令具有 液晶原之單體聚合之熱傳導率爲〇.4W/m·K以上之 絕緣組成物。1294441 A7 __B7__ V. INSTRUCTIONS (彳) TECHNICAL FIELD (Please read the notice on the back and fill out this page.) The present invention relates to an insulating material used in electrical appliances, electronic equipment, and the like, particularly for thermal hardening excellent in thermal conductivity. Hardened resin. Back Technology Nearly all electrical and electronic equipment from motors and generators to printed circuit boards are made up of conductors for energization and insulation. In recent years, with the rapid development of miniaturization of such electrical appliances, the characteristics required for insulating materials have also been greatly improved. Among them, the amount of heat generated in a conductor which is reduced in size and density is increased, so how to make heat radiation is an important issue. In contrast, in the insulating materials of various electrical appliances, thermosetting resins are widely used from the viewpoints of the high insulation performance, ease of molding, heat resistance, and the like. However, in general, the thermosetting resin has a low thermal conductivity and is a major factor that hinders the heat dissipation. Therefore, the necessity of an insulating material having a high thermal conductivity is very high. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperative, a material with high thermal conductivity, known as a composite material that mixes high thermal conductivity powder into a thermosetting resin. The used powders have also been reviewed for many metal powders such as silver and aluminum, cerium oxide, oxidized anchors, magnesium oxide, cerium oxide, boron nitride, aluminum nitride, tantalum nitride, tantalum carbide, aluminum fluoride, An inorganic ceramic powder such as calcium fluoride. However, if such a pigment powder is mixed in a thermosetting resin, the viscosity of the resin before molding is remarkably increased, so that it is difficult to manufacture a fine structure, and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297). ^) quot; ------ -4 - 1294441 A7 B7 V. Description of invention (2) Its workability is also extremely poor. (Please read the precautions on the back and fill out this page.) Also, the thermal conductivity of the thermosetting resin is extremely low. Mixing a small amount of the material of the powder does not improve the thermal conductivity. It is necessary to mix a large amount of the powder. However, it is actually difficult to evenly disperse a large amount of the powder in the resin. Further, the affinity between the thermosetting resin of the organic material and the pigment powder is also problematic, and the peeling of the interface is very likely to occur, and the possibility of greatly reducing the insulation property in long-term use is also large. From this point of view, it is extremely important to achieve the problem of high thermal conductivity of organic materials. A method of achieving a high thermal conductivity of an organic material is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 6,096, the disclosure of which is incorporated herein by reference. It is a super-highly oriented polymer fiber described in POLYMER, v.l. 19, 155 (1978), which improves the thermal conductivity in the fiber axis direction. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the consumer cooperatives, but the highly highly oriented polymer fibers have a lower thermal conductivity in the vertical direction of the fiber axis, so even if the polymer fibers are randomly dispersed in the organic insulating composition, almost Unable to increase thermal conductivity. By arranging the polymer fibers in a single direction in the organic insulating composition, an organic insulating material having excellent thermal conductivity in the alignment direction can be obtained. However, in addition to this, the thermal conductivity is inversely lowered. Further, in ADVANCED MATERIALS, Vol. 5, 1 0 7 (1939), and German Patent No. 4 2 2 6 9 9 4, a monomer such as a diacrylate having a liquid crystal source is described. After orientation in a certain direction, the paper size is applicable to China National Standard (CNS) A4 specification (210Χ 297 mm) -5-1294441 A7 __B7 _ V. Invention description (3) (Please read the notes on the back and fill in the form) Page) An anisotropic material having a high thermal conductivity in the in-plane direction of the film in which the molecular chain is juxtaposed. However, in other directions, the thermal conductivity particularly in the thickness direction of the film is lowered. In general, the thermal movement direction of the film material is such that the overwhelming property is increased in the thickness direction, and such materials have a small effect. There is also a review of the method of juxtaposition of molecular chains in the thickness direction. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A method for preparing polyoxymethylene and polyimine-like organic materials. Further, in Japanese Laid-Open Patent Publication No. SHO-63-269-82, a sheet in which molecular chains such as polypropylene and polyethylene are arranged is laminated, and the laminate is laminated in the direction of arrangement, and the cured laminate is A material in which the orientation direction is thinly cut and the molecular chains are arranged in the vertical direction. These methods are indeed materials having a high thermal conductivity in the thickness direction of the film, but they are very complicated to form and the materials used are limited. The Ministry of Economic Affairs, the Intellectual Property Office, and the Employees' Cooperatives Co., Ltd., published in the Unexamined Japanese Patent Publication No. 1 1 - 3 2 3 1 6 2, describes the insulation composition of the thermal conductivity of the monomer having a liquid crystal original of 〇.4 W/m·K or more. Things.

此絕緣組成物於空間性大約爲各向同性且其熱傳導率 高，不需採用煩雜之成形法，且可提高厚度方向之熱傳導 率。但是，此熱傳導率之値爲0 _ 4〜0 · 5W/m.K 左右。 於特開平9 一 1 1 8 6 7 3號公報中，記載具有有2 本纸張尺度適用中國國家標準（CNS ) A4規格（2】〇Χ 297公釐） -6 - 1294441 A7 _._B7 _ 五、發明説明（4) (請先閲讀背面之注意事項再填寫本頁) 個液晶原之液晶熱硬化性單體，及，由此單體所製造之具 有近晶性構造之液晶熱硬化性單體。此液晶熱硬化性聚合 物可形成高度排列之近晶性構造。但是，關於此聚合物之 熱傳導率之一切並未記載。 本發明爲鑑於上述情事，以提供可繼續於空間性大約 保持於各向同性，且大爲提高熱傳導率之高熱傳導性之熱 硬化性樹脂硬化物爲其目的。 發明之揭示 達成上述目的之本發明要旨爲如下。 〔1〕 一種熱硬化性樹脂硬化物.，其特徵爲於熱硬化性 樹脂硬化物之樹脂成分中存在各向異性構造，且構成該各 向異性構造之各向異性構造單位爲具有共價鍵部分，該各 向異性構造單位直徑之最大値爲4 0 0 n m以上，且樹脂 成分中所含之各向異性構造之比例爲2 5體積％以上。 經濟部智慧財產局員工消費合作社印製 〔2〕 如上述〔1〕記載之熱硬化性樹脂硬化物，其中 該熱硬化性樹脂硬化物中之樹脂成分爲具有液晶原之環氧 樹脂單體和含有環氧樹脂用硬化劑之環氧樹脂硬化物。 〔3〕 如上述〔2〕記載之熱硬化性樹脂硬化物，其中 該環氧樹脂單體爲下述一般式（1 ) E - M— S— M~~E ".(I) (但，E爲環氧基，Μ爲液晶原，S爲表示間隔部）所示 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇Χ：297公釐） 1294441 A7 ___B7_ 五、發明説明（」 〇 之環氧樹脂單體。 (讀先閱讀背面之注意事項再填寫本頁) 本發明所謂之熱硬化性樹脂硬化物，爲表示經由其中 樹脂成分加熱形成交聯構造物之樹脂硬化物。 具體的樹脂成分爲列舉不飽和聚酯樹脂、環氧樹脂、 丙烯酸樹脂、苯酚樹脂、蜜胺樹脂、脲樹脂、胺基甲酸酯 樹脂等之硬化物。特別，可列舉絕緣性、耐熱性優良之環 氧樹脂。此些樹脂成分可包含單體、交聯劑、可動化劑、 稀釋劑、改質劑等。 此熱硬化性樹脂硬化物爲以上述之樹脂成分做爲主成 分，且其他亦可含有金屬、無機陶瓷、有機物之粉末、織 造織物、非織造織物、短纖維、長纖維等。此時，彼等爲 不影響樹脂成分之熱傳導率，令樹脂成分之高熱傳導率爲 出現其原來之效果。 經濟部智慧財產局員工消費合作社印製 本發明所謂之各向異性構造，爲指進行微細排列之構 造物。例如，相當於結晶相和液^相等。於樹脂中是否存 在此類構造物，可經由偏光顯微鏡觀察而輕易判別。即， 於直列尼科耳（Nicol)狀態之觀察中，可經由察見偏光解 除現象所造成之干涉條紋進行判別。 此各向異性構造通常於樹脂中以島狀存在，本發明所 謂之各向異性構造單位爲指其中一個島。於本發明中，此 各向異性構造單位必須爲具有共價鍵部分。 本發明中之各向異性構造單位直徑之最大値及各向異 性構造之比例，可經由穿透型電子顯微鏡（T E Μ )直接 觀察而算出。具體的算出方法爲記載於後述之實施例中。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X29*7公釐） -8- 1294441 A7 _B7_The insulating composition is approximately isotropic in space and has high thermal conductivity, and does not require a complicated molding method, and can improve the thermal conductivity in the thickness direction. However, the thermal conductivity is about 0 _ 4 to 0 · 5 W/m.K. In Japanese Patent Publication No. 9 1 1 8 6 7 3, there are two paper sizes applicable to the Chinese National Standard (CNS) A4 specification (2) 297 297 mm) -6 - 1294441 A7 _._B7 _ V. INSTRUCTIONS (4) (Please read the precautions on the back and fill in this page) Liquid crystal thermosetting monomers of liquid crystal, and liquid crystal thermosetting properties of smectic structure manufactured by the monomer monomer. The liquid crystal thermosetting polymer can form a highly aligned smectic structure. However, nothing about the thermal conductivity of this polymer is described. In view of the above, the present invention has an object of providing a thermosetting resin cured product which can continue to be approximately isotropy in space and has high thermal conductivity and high thermal conductivity. Disclosure of the Invention The gist of the present invention for achieving the above object is as follows. [1] A thermosetting resin cured product, characterized in that an anisotropic structure exists in a resin component of a thermosetting resin cured product, and an anisotropic structural unit constituting the anisotropic structure has a covalent bond In part, the maximum enthalpy of the unit diameter of the anisotropic structure is 4,000 nm or more, and the ratio of the anisotropic structure contained in the resin component is 25 vol% or more. [2] The thermosetting resin cured product according to the above [1], wherein the resin component in the thermosetting resin cured product is an epoxy resin monomer having a liquid crystal source and An epoxy resin cured product containing a hardener for epoxy resin. [3] The thermosetting resin cured product according to the above [2], wherein the epoxy resin monomer is the following general formula (1) E - M - S - M~~E " (I) (but , E is an epoxy group, Μ is a liquid crystal original, and S is a spacer. The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (21〇Χ: 297 mm) 1294441 A7 ___B7_ V. Invention Description ( The epoxy resin monomer of the ruthenium. (Read the first note on the back side and fill in the page.) The heat-curable resin cured product of the present invention is a cured product of a resin which is formed by heating a resin component to form a crosslinked structure. The resin component is a cured product such as an unsaturated polyester resin, an epoxy resin, an acrylic resin, a phenol resin, a melamine resin, a urea resin, or a urethane resin. In particular, it is excellent in insulation and heat resistance. The resin component may include a monomer, a crosslinking agent, a mobilizing agent, a diluent, a modifier, etc. The thermosetting resin cured product is mainly composed of the above-mentioned resin component, and other May contain metals, inorganic ceramics, Powder, woven fabric, non-woven fabric, short fiber, long fiber, etc. of the machine. At this time, they do not affect the thermal conductivity of the resin component, so that the high thermal conductivity of the resin component has its original effect. The property bureau employee consumption cooperative prints the so-called anisotropic structure of the present invention, and refers to a structure in which fine alignment is performed. For example, it corresponds to a crystal phase and a liquid phase. Whether or not such a structure exists in the resin can be passed through a polarizing microscope. Observable and easy to discriminate. That is, in the observation of the Niñol state, it can be discriminated by the interference fringes caused by the phenomenon of polarization release. This anisotropic structure usually exists as an island in the resin. The so-called anisotropic structural unit refers to one of the islands. In the present invention, the anisotropic structural unit must have a covalent bond portion. The maximum enthalpy and anisotropy of the unit diameter of the anisotropic structure in the present invention The ratio of the structure can be calculated directly by a transmission electron microscope (TE Μ ). The specific calculation method is described later. The embodiment of this paper is suitable China National Standard Scale (CNS) Α4 Specification (210X29 * 7 mm) -8- 1294441 A7 _B7_

五、發明説明（J 6/ (請先閱讀背面之注意事項再填寫本頁) 本發明所謂之液晶原（mes〇Sen)爲表示具有表現液晶 性可能性之官能基。具體而言，可列舉二乙烯基、苯甲酸 苯酯、偶氮苯、芪等和其衍生物。 又本發明所謂之環氧樹脂單體，爲表示具有至少一個 環氧基之單體。更且，此環氧樹脂單體較佳具有液晶原。 具體而言，可列舉二乙烯基、苯甲酸苯酯基、芪基、偶氮 苯基等之分子內具有至少一個液晶原之環氧樹脂單體，和 分子內具有二個以上之雙液晶原型之環氧樹脂單體。 特別，下述一般式（1 )所示之雙液晶原型之環氧樹 脂單體，於提高各向異性構造單位直徑之最大値及各向異 性構造之比例上爲最佳。 E — M— S— Μ— E ---(1) (但，E爲環氧基，Μ爲液晶原，S爲表示間隔部） 經濟部智慧財產局員工消費合作社印製 本發明所謂之環氧樹脂用硬化劑，爲指令環氧樹脂硬 化所用之硬化劑。具體而言，可列舉酸酐系硬化劑、聚胺 系硬化劑、聚苯酚系硬化劑、聚硫醇系硬化劑等之重加成 型硬化劑、離子聚合型之觸媒型硬化劑、潛在性硬化劑等 〇 如上述處理之高熱傳導性之熱硬化性樹脂硬化物，爲 繼續於空間性大約保持各向同性，且大爲提高熱傳導率之 高熱傳導性之熱硬化性樹脂硬化物。此熱硬化性樹脂本身 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -9- 1294441 A7 B7 五、發明説明（7) 之熱傳導率高，例如，混合同量之高熱傳導性塡料粉末作 成樹脂材料，則比先前之樹脂材料爲具有更高熱傳導率之 樹脂材料。 因此，於相同熱傳導率之情況中，可減低必須混合之 塡料粉末之份量，且因降低硬化前的樹脂粘度，故提高成 形性。 因此，本發明之高熱傳導性之熱硬化性樹脂硬化物之 效果爲非常大，可適於發電機和馬達、變壓器等之絕緣層 、半導體包裝用之材料、多層印刷基板層間絕緣膜、基板 元件、接粘元件、塗佈型接粘劑、樹脂塡料、粘合樹脂、 放熱板等。 圖面之簡單說明 圖1爲示出本發明高熱傳導性之熱硬化性樹脂硬化物 以TEM觀察之結果之一例圖示。 圖2爲示出本發明高熱傳導性之熱硬化性樹脂硬化物 之各向異性構造單位直徑之最大値，和熱傳導率之關係圖 〇 圖3爲示出本發明高熱傳導性之熱硬化性樹脂硬化物 之各向異性構造之比例，和熱傳導率之關係圖。 用以實施發明之最佳型態 以下，示出本發明之實施例並且具體說明。尙，實施 例中記載之環氧樹脂單體、環氧樹脂用硬化劑、丙烯酸樹 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ----------«裝-- (請先閲讀背面之注意事項再填寫本頁) 钉 經濟部智慧財產局員工消費合作社印製 -10- 1294441 A7 B7 五、發明説明（8) 脂單體之種類及其縮寫示於下。 〔環氧樹脂單體〕 (請先閲讀背面之注意事項再填寫本頁)5. Description of the Invention (J 6/ (Please read the precautions on the back side and fill in the page again.) The so-called liquid crystal precursor (mes〇Sen) of the present invention is a functional group indicating the possibility of exhibiting liquid crystallinity. Divinyl, phenyl benzoate, azobenzene, anthracene, etc. and derivatives thereof. The so-called epoxy resin monomer of the present invention is a monomer having at least one epoxy group. Moreover, the epoxy resin The monomer preferably has a liquid crystal original. Specifically, an epoxy resin monomer having at least one liquid crystal element in a molecule such as a divinyl group, a phenyl benzoate group, a fluorenyl group or an azophenyl group, and an intramolecular group are exemplified. An epoxy resin monomer having two or more double liquid crystal prototypes. In particular, the epoxy resin monomer of the double liquid crystal prototype shown in the following general formula (1) is used to increase the maximum diameter of the unit diameter of the anisotropic structure and each The ratio of the structure to the opposite sex is optimal. E — M— S — Μ — E --- (1) (However, E is an epoxy group, Μ is a liquid crystal original, and S is a spacer.) Ministry of Economic Affairs Intellectual Property Bureau The employee consumption cooperative prints the so-called hardener for epoxy resin of the present invention. In addition, it is a hardening agent used for hardening of an epoxy resin. Specifically, the hardening-hardening agent and ion of an acid-acid hardening agent, a polyamine-type hardening|curing agent, a poly- The polymer type catalyst hardener, latent curing agent, etc., such as the above-mentioned high thermal conductivity thermosetting resin cured product, which maintains isotropy in space and greatly improves thermal conductivity. The thermosetting resin is cured. The thermosetting resin itself is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) -9-1294441 A7 B7 5. The invention (7) has high thermal conductivity. For example, mixing the same amount of high thermal conductivity tantalum powder as a resin material is a resin material having a higher thermal conductivity than the prior resin material. Therefore, in the case of the same thermal conductivity, the dip powder which must be mixed can be reduced. Since the amount of the resin is lowered, the viscosity of the resin before curing is lowered, so that the moldability is improved. Therefore, the heat-curable resin cured product of the present invention has high heat conductivity. It is very large and can be used for insulating layers of generators, motors, transformers, etc., materials for semiconductor packaging, interlayer printed circuit interlayer insulating films, substrate components, bonding components, coating adhesives, resin coatings, and adhesives. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of the results of TEM observation of a cured product of a thermosetting resin having high thermal conductivity according to the present invention. Fig. 2 is a view showing the high thermal conductivity of the present invention. FIG. 3 is a graph showing the relationship between the anisotropy structure of the thermosetting resin cured product and the thermal conductivity of the cured product of the thermosetting resin of the present invention, and FIG. The relationship between the thermal conductivity and the best mode for carrying out the invention. Hereinafter, an embodiment of the present invention will be described and specifically described. 环氧树脂, the epoxy resin monomer, the epoxy resin hardener, and the acrylic tree described in the examples This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) ---------- «Installation -- (Please read the note on the back and fill out this page) fiscal Office workers consumer cooperative printed -10- 1294441 A7 B7 V. Description of the Invention (8) of the type aliphatic monomers and their abbreviations shown below. [Epoxy resin monomer] (Please read the notes on the back and fill out this page)

Tw8 : 4 -（環氧乙烷甲氧基）苯甲酸一4 ，4 / 一〔 1，8 —辛烷二基雙（氧，基）〕雙酚酯 Tw6 : 4 - （環氧乙烷甲氧基）苯甲酸一4 ，4 / —〔 1，6 -己烷二基雙（氧基）〕雙酚酯 Tw4 : 4 -（環氧乙烷甲氧基）苯甲酸一 4 ，4>一〔 1，4 一丁烷二基雙（氧基）〕雙酚酯 BzE ·· 4 -（4 —環氧乙烷丁氧基）苯甲酸一1 ， -伸苯酯 B i E : 4，4 / —雙酚二縮水甘油醚 TME : 3 ，3 / ，5 ，5 四甲基一4 ，4 一一雙酚 二縮水甘油醚 BAE:雙酚A二縮水甘油醚 〔環氧樹脂用硬化劑〕 經濟部智慧財產局員工消費合作社印製 DDM: 4，4 > 一二胺基二苯基甲烷 DDE:4，4> —二胺基二苯醚 DDS:4，4/ —二胺基二苯硕 DDB : 4，4，_二胺基一 3，-二甲氧基聯苯 DSt : 4，4——二胺基—甲基芪 DBz : 4，4 > —二胺基苯基苯甲酸酯 〔丙烯酸樹脂單體〕 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -11 - 1294441 A7 B7 五、發明説明（9)Tw8 : 4 -(oxirane methoxy)benzoic acid - 4 , 4 / 1 [1,8-octanediylbis(oxy)yl]bisphenolate Tw6 : 4 - (ethylene oxide A Oxy)benzoic acid-4,4/-[1,6-hexanediylbis(oxy)]bisphenolate Tw4: 4-(ethylene oxide methoxy)benzoic acid-4,4> [1,4-butanediylbis(oxy)]bisphenolate BzE ··4 -(4-oxiranylbutoxy)benzoic acid-1,-phenylene ester B i E : 4,4 / — Bisphenol diglycidyl ether TME : 3 , 3 / , 5 , 5 Tetramethyl - 4 , 4 - bisphenol diglycidyl ether BAE : bisphenol A diglycidyl ether [hardener for epoxy resin ] Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed DDM: 4,4 > Monoaminodiphenylmethane DDE: 4,4>-Diaminodiphenyl Ether DDS: 4,4/-Diaminodiphenyl DDB: 4,4,-diamino-3,-dimethoxybiphenyl DSt: 4,4-diamino-methylindole DBz: 4,4 >-diaminophenylbenzene Acid ester [acrylic resin monomer] This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) PCT) -11 - 1294441 A7 B7 V. Description of invention (9)

BzA : 4 -（6 -丙烯醯己氧基）苯甲酸—1 ，4 / 一 伸苯酯 (請先閱讀背面之注意事項再填寫本頁) 〔丙烯酸樹脂用硬化劑〕 BPO:過氧化苯甲醯 DPA : w，w —二甲氧基一 w —苯基乙醯苯 〔實施例〕 將T w 8和D D Μ預先以1 6 0 °C熔融混合，流入已 脫模處理完畢之模具中，並加熱硬化作成厚度5mm之高 熱傳導性之熱硬化性樹脂硬化物所構成的樹脂板。尙，環 氧樹脂單體與硬化劑之配合比爲以化學計量比，且硬化溫 度爲1 6 0 °C，硬化時間爲1 0小時。此些條件整理示於 表1 〇 將此樹脂板***以直角尼科耳狀態配置之二枚偏光板 之間，且以顯微鏡觀察時，察見解除偏光所引起的干涉條 紋。因此，可知此樹脂板爲具有各向異性構造。 經濟部智慧財產局員工消費合作社印製 此樹脂板之各向異性構造單位爲以T E Μ觀察。觀察 爲使用Ru〇4染色劑，並以倍率30，0 0 0倍進行觀察 。各向異性構造單位直徑之最大値爲1 6 0 0 n m，各向 異性構造之比例爲4 0體積％。尙，各向異性構造之部分 邊界爲經由調整照相相片之對比度之畫像處理予以決定。 圖1示出由照片決定各向異性構造部分的觀察結果。 各向異性構造於深度方向亦爲同#分布，故各向異性構造 本紙張尺度適用中國國家標準（CNS ) A4規格（2〗〇父297公釐） -12- 1294441 A7 B7___ 五、發明説明（^ 之比例，爲以各向異性構造部之面積相對於圖（照片）全 體面積之比例而算出。各向異性構造單位直徑之最大値， 爲各個各向異性構造單位之最長部分的測定値。 測定此樹脂板之熱傳導率時，顯示出0 . 8 3 w/m • K之非常高的熱傳導率。尙，熱傳導率爲根據平板比較 法之試料厚度方向値，測定時之試料平均溫度爲約8 0 °C 。尙，標準試料爲使用硼矽酸玻璃。以上之結果整理示於 表2。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本纸張尺度適用中國國家標準（CNS ) A4規袼（210X 297公釐） -13 - 1294441BzA : 4 -(6 -Acetylhexyloxy)benzoic acid - 1 ,4 / phenylene ester (please read the notes on the back and fill out this page) [hardener for acrylic resin] BPO: Benzoyl peroxide DPA: w, w - dimethoxy-w-phenyl acetophenone benzene [Examples] T w 8 and DD 熔融 were previously melt-mixed at 160 ° C, and flowed into a mold which had been subjected to mold release treatment, and A resin plate composed of a heat-curable resin cured product having a high thermal conductivity of 5 mm in thickness was heat-hardened.尙, the ratio of the epoxy resin monomer to the hardener is stoichiometric, and the hardening temperature is 160 ° C, and the hardening time is 10 hours. These conditions are shown in Table 1. 将此 The resin plate was inserted between two polarizing plates arranged in a right-angled Nicols state, and when observed under a microscope, the interference pattern caused by the removal of the polarized light was observed. Therefore, it is understood that the resin sheet has an anisotropic structure. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperatives. The anisotropic structural unit of this resin plate is observed by T E Μ. It was observed to use Ru〇4 staining agent and observed at a magnification of 30,0 0. The maximum enthalpy of the anisotropic structure unit diameter is 1 600 nm, and the ratio of the anisotropic structure is 40% by volume.尙, part of the anisotropic structure The boundary is determined by the image processing of adjusting the contrast of the photographic print. Fig. 1 shows an observation result of determining an anisotropic structure portion from a photograph. The anisotropic structure is also the same as the # distribution in the depth direction, so the anisotropic structure of this paper scale applies to the Chinese National Standard (CNS) A4 specification (2〗 〇 297 mm) -12- 1294441 A7 B7___ V. Description of invention ( The ratio of ^ is calculated as the ratio of the area of the anisotropic structure to the total area of the figure (photograph). The maximum 値 of the anisotropic structure unit diameter is the measurement of the longest part of each anisotropic structure unit. When the thermal conductivity of the resin sheet was measured, it showed a very high thermal conductivity of 0.83 w/m • K. 热, the thermal conductivity was the thickness direction of the sample according to the flat plate comparison method, and the average temperature of the sample at the time of measurement was about 80 ° C. 尙, the standard sample is the use of borosilicate glass. The above results are shown in Table 2. (Please read the note on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed this paper The scale applies to the Chinese National Standard (CNS) A4 Regulation (210X 297 mm) -13 - 1294441

A B7 五、發明説明（j 表] No. 單體 硬化劑 硬化劑之配合量 硬化溫度（°C) 實施例1 Tw8 DDM 化學計量 150 實施例2 Tw6 DDE 化學計量 180 實施例3 Tw4 DDS 化學計量 200 實施例4 BAE DSt 化學計量 180 實施例5 BzE DBz 化學計量 180 實施例6 BzA BPO 0.5wt% 80 比較例1 BzE DBz 化學計量 230 比較例2 BiE DDM 化學計量 180 比較例3 B正 DBi 化學計量 180 比較例4 BzA DPA 0.5wt% 50* 比較例5 TME DBi 化學計量 180 比較例6 TME DDM 化學計量 150 比較例7 BAE DDM 化學計量 150 ——·—,—---— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 *uv照射所引起之反應（1小時） 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -14- 1294441 經濟部智慧財產局員工消費合作社印製 五、發明説明（^表2A B7 V. INSTRUCTIONS (j Table) No. Compound hardening agent hardening temperature (°C) Example 1 Tw8 DDM stoichiometry 150 Example 2 Tw6 DDE stoichiometry 180 Example 3 Tw4 DDS Chemometrics 200 Example 4 BAE DSt stoichiometry 180 Example 5 BzE DBz stoichiometry 180 Example 6 BzA BPO 0.5 wt% 80 Comparative Example 1 BzE DBz stoichiometry 230 Comparative Example 2 BiE DDM stoichiometry 180 Comparative Example 3 B-DBMI Chemometrics 180 Comparative Example 4 BzA DPA 0.5 wt% 50* Comparative Example 5 TME DBi stoichiometry 180 Comparative Example 6 TME DDM stoichiometry 150 Comparative Example 7 BAE DDM stoichiometry 150 ——·—, —---— (Please read the back first Note: Please fill out this page again) The Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative printed *uv radiation reaction (1 hour) This paper scale applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -14 - 1294441 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Inventions (^ Table 2

No. 各向異性構造 各向異性構造單位直 徑之最大値 (nm) 各向異性構告之比 例 (vol%) 熱傳導率 (W/m-K) 實施例1 〇 1600 40 0.83 實施例2 〇 1700 43 0.88 實施例3 〇 1800 45 1.05 實施例4 〇 910 35 0.78 實施例5 〇 520 38 0.69 實施例6 〇 760 26 0.68 比較例1 〇 320 37 0.44 比較例2 〇 170 29 0.30 比較例3 〇 760 22 0.33 比較例4 〇 1000 15 0.38 比較例5 〇 280 20 0.29 比較例6 〇 130 14 0.26 比較例7 X 一 0.19 ------------ (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -15- 1294441 A7 _ B7__ 五、發明説明（^ 〔實施例2〜6〕 (請先閱讀背面之注意事項再填寫本頁) 將組合表1所示單體和硬化劑並硬化之高熱傳導性之 熱硬化性樹脂硬化物之樹脂板爲同實施例1作成。尙，硬 化劑之配合量爲以表1所示之份量，且硬化條件爲以表1 之硬化溫度進行，硬化時間爲以1 〇小時。 此樹脂板之各向異性構造之有無、熱傳導率、各向異 性構造單體直徑之最大値、各向異性構造之比例爲同實施 例1測定，且其結果合倂示於表1。 任何樹脂板均確認爲各向異性構造，且各向異性構造 單位直徑之最大値爲4 0 0 n m以上，各向異性構造之比 例爲2 5體積％。 此些樹脂板之熱傳導率爲非常高至0 · 6 8〜 1 · 0 5 W/ m · K。其中，使用實施例1〜3之雙液晶 原型環氧樹脂單體之樹脂板，於各向異性構造單位直徑之 最大値，各向異性構造之比例均大於實施例4〜6，且熱 傳導率爲極高至〇 · 83〜1 · 05W/m*K。 經濟部智慧財產局員工消費合作社印製 由以上之結果，可知雙液晶辱型之環氧樹脂單體爲適 於令各向異性構造單位直徑之最大値、各向異性構造之比 例均變大，可達成更高的熱傳導率。 〔比較例1〜7〕 組合表1所示單體和硬化劑並硬化之熱硬化性樹脂硬 化物之樹脂板爲同實施例1作成。尙，硬化劑之配合量爲 以表1所示之份量，且硬化條件爲以表1之硬化溫度進行 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -16- 1294441 B7_ 五、發明説明（^ ，硬化時間爲以1 0小時。 (請先閱讀背面之注意事項再填寫本頁) 但，比較例4爲一邊照射U V —邊進行硬化反應，且 其硬化時間爲以1小時。 此樹脂板之各向異性構造之有無、熱傳導率、各向異 性構造單體直徑之最大値、各向異性構造之比例爲同實施 例1測定，且其結果合倂示於表2。 各向異性構造單位直徑之最大値爲未滿4 0 0 n m之 比較例1、2之樹脂的熱傳導率爲低至0 · 4 4、 0 · 3 0 W/m · K。又，各向異性構造之比例爲未滿 2 5體積％之比較例3、4之樹脂的熱傳導率爲低至 0.33、0.38W/m，K。 又，各向異性構造單位直徑之平均値爲未滿7 0 0 n m、且，各向異性構造之比例爲未滿2 5體積％之比較 例5、6之樹脂的熱傳導率爲更低至0 . 2 9、0 . 2 6 W/m · K。尙，不具有各向異性構造之比較例7之樹脂 的熱傳導率爲非常低至〇 . 1 9 W/m · K。 經濟部智慧財產局員工消費合作社印製 將以上之實施例1〜6及比較例1〜7之樹脂之熱傳 導率，相對於此各向異性構造單位直徑最大値所描繪之圖 示於圖1 ，而相對於各向異性構造比例所描繪之圖示於圖 2 ° 由圖2可知，各向異性構造之比例爲4 0體積％之情 況中，各向異性構造單位直徑之最大値爲4 0 0 n m以上 ，且熱傳導率爲急劇上升。但，於各向異性構造之比例爲 未滿2 5體積％之情況中，則幾乎未察見其效果。 本紙張尺度適用中國國家標準（CNS) A4規格（2〗〇Χ297公釐） -17- 1294441 A8 B8 C8 D8 六、申請專利範圍15 又，由圖3可知，各向異性構造單位直徑之最大値爲 4 0 0 n m以上之情況中，各向異性構造之比例爲2 5體 積％，且熱傳導率爲急劇上升。但各向異性構造單位直徑 之最大値爲未滿4 0 0 n m之情況中’則幾乎未察見其效 果。 產業上之可利用性 若根據本發明，則可取得繼續於空間性大約保持各向 異性，並可令熱傳導率大爲提局之局熱傳導性之熱硬化性 樹脂硬化物，將其使用於電器、電子機器等之絕緣材料’ 則可取得放熱性良好之電器、電子機器。 (請先閲讀背面之注意事項再填寫本頁) _I---I---Λ- I —· I I —裝—-----訂----- Jlmr 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18-No. Anisotropic structure Anisotropic structure Maximum diameter per unit diameter (nm) Proportion of anisotropic structure (vol%) Thermal conductivity (W/mK) Example 1 〇1600 40 0.83 Example 2 〇1700 43 0.88 Example 3 〇 1800 45 1.05 Example 4 〇 910 35 0.78 Example 5 〇 520 38 0.69 Example 6 〇 760 26 0.68 Comparative Example 1 〇 320 37 0.44 Comparative Example 2 〇 170 29 0.30 Comparative Example 3 〇 760 22 0.33 Comparison Example 4 〇1000 15 0.38 Comparative Example 5 〇280 20 0.29 Comparative Example 6 〇130 14 0.26 Comparative Example 7 X A 0.19 ------------ (Please read the back note first and then fill out this page This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) -15- 1294441 A7 _ B7__ V. Invention description (^ [Examples 2 to 6] (Please read the notes on the back and fill in the form) The resin sheet of the thermosetting resin cured product of the high thermal conductivity which is cured by combining the monomer shown in Table 1 and the hardener is prepared in the same manner as in Example 1. The amount of the hardener is shown in Table 1. The amount and the hardening conditions are carried out at the hardening temperature of Table 1, when hardened The amount of the anisotropic structure of the resin sheet, the thermal conductivity, the maximum diameter of the anisotropic structure monomer, and the ratio of the anisotropic structure were measured in the same manner as in Example 1, and the results were combined. In Table 1. Any resin plate was confirmed to be an anisotropic structure, and the maximum enthalpy of the anisotropic structure unit diameter was 400 nm or more, and the ratio of the anisotropic structure was 25 vol%. The rate is very high to 0 · 6 8 〜 1 · 0 5 W / m · K. Among them, the resin sheets of the double liquid crystal prototype epoxy resin of Examples 1 to 3 are used, and the unit diameter of the anisotropic structure is the largest.値, the ratio of the anisotropic structure is larger than that of the examples 4 to 6, and the thermal conductivity is extremely high to 83·83~1 · 05W/m*K. The Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints the above results. It is understood that the epoxy resin monomer of the double liquid crystal-inducing type is suitable for increasing the ratio of the maximum enthalpy of the anisotropic structural unit diameter and the anisotropic structure, and a higher thermal conductivity can be achieved. [Comparative Examples 1 to 7] Combine the monomer and hardener shown in Table 1 The resin plate of the cured thermosetting resin is prepared in the same manner as in Example 1. The amount of the hardener is the amount shown in Table 1, and the hardening conditions are the hardening temperature of Table 1. National Standard (CNS) A4 Specification (210 X 297 mm) -16-1294441 B7_ V. Description of Invention (^, hardening time is 10 hours. (Please read the precautions on the back side and fill out this page.) However, in Comparative Example 4, the curing reaction was carried out while irradiating U V, and the curing time was 1 hour. The presence or absence of the anisotropic structure of the resin sheet, the thermal conductivity, the maximum diameter of the anisotropic structure monomer, and the ratio of the anisotropic structure were measured in the same manner as in Example 1, and the results are shown in Table 2. The maximum enthalpy of the unit diameter of the anisotropic structure is less than 4 0 0 n m The thermal conductivity of the resins of Comparative Examples 1 and 2 is as low as 0 · 4 4, 0 · 3 0 W/m · K. Further, the resins of Comparative Examples 3 and 4 in which the ratio of the anisotropic structure was less than 25 vol% were as low as 0.33 and 0.38 W/m, K. Further, the average enthalpy of the unit diameter of the anisotropic structure is less than 700 nm, and the ratio of the anisotropic structure is less than 25 vol%. The thermal conductivity of the resins of Comparative Examples 5 and 6 is lower to 0. . 2 9,0 . 2 6 W/m · K. The thermal conductivity of the resin of Comparative Example 7 which does not have an anisotropic structure is very low to 0.19 W/m · K. The thermal conductivity of the resins of Examples 1 to 6 and Comparative Examples 1 to 7 printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs is shown in Figure 1 with respect to the maximum thermal conductivity of the anisotropic structural unit diameter. The graph depicted with respect to the anisotropic structure ratio is shown in Fig. 2 °. As can be seen from Fig. 2, in the case where the ratio of the anisotropic structure is 40% by volume, the maximum 値 of the anisotropic structure unit diameter is 4 0 0 Above nm, and the thermal conductivity rises sharply. However, in the case where the ratio of the anisotropic structure is less than 25 vol%, the effect is hardly observed. This paper scale applies to China National Standard (CNS) A4 specification (2〗 〇Χ 297 mm) -17- 1294441 A8 B8 C8 D8 VI. Patent application scope 15 Also, as shown in Figure 3, the maximum diameter of the anisotropic structure unit is 値In the case of 400 nm or more, the ratio of the anisotropic structure is 25 vol%, and the thermal conductivity sharply rises. However, in the case where the maximum diameter of the unit diameter of the anisotropic structure is less than 4 0 0 n m, the effect is hardly observed. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a thermosetting resin cured product which continues to maintain anisotropy in space and maintains thermal conductivity as a result of thermal conductivity, and is used in an electric appliance. Insulation materials such as electronic equipment can provide electrical and electronic equipment with good heat dissipation. (Please read the notes on the back and fill out this page) _I---I---Λ- I —· II —装—-----订----- Jlmr Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperative The printed paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -18-

Claims (1)

12944411294441 六、申請專利範圍1 …一 第90 1 1 3 08 5號專利申請案 ， - ,[ 4；-中文申請專利範圍修正本 ί—_—— · (請先聞·«背面之注意事項再填寫本頁) ~ 民國96年4月24日修正 1 . 一種高熱傳導性之熱硬化性樹脂硬化物，其特徵 爲於熱硬化性樹脂硬化物之樹脂成分中存在各向異性構造 ，且硬化物全體保持爲空間上之各向同性，構成該各向異 性構造之各向異性構造單位爲具有共價鍵部分，該各向異 性構造單位直徑之最大値爲4 0 0 n m以上，且樹脂成分 中所含各向異性構造比例爲2 5體積％以上，熱傳導率爲 0.68w/m*K以上， 該高熱傳導性之熱硬化性樹脂硬化物中之樹脂成分爲 含有，具有液晶原（mesogen )之環氧樹脂單體和環氧樹脂 用硬化劑之環氧樹脂硬化物。 2 .如申請專利範圍第1項之高熱傳導性之熱硬化性 樹脂硬化物，其中該環氧樹脂單體爲下述一般式（1 ) 經濟部智慧財產局員工消費合作社印製 (1 E— M— S— Μ— E (但，E爲環氧基，Μ爲液晶原基，S爲間隔部）所示之 環氧樹脂單體。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）Sixth, the scope of application for patents 1 ... a patent application No. 90 1 1 3 08 5, -, [4; - Chinese patent application scope revision ί__ - · (Please read the first note on the back) Page 1 of the Republic of China, April 24, 1996. 1. A thermosetting resin cured product having high thermal conductivity, characterized in that an anisotropic structure exists in the resin component of the thermosetting resin cured product, and the cured product is entirely Maintaining the isotropy in space, the anisotropic structural unit constituting the anisotropic structure has a covalent bond portion, and the maximum enthalpy of the unit diameter of the anisotropic structure is 400 nm or more, and the resin component The ratio of the anisotropic structure is 25 vol% or more, and the thermal conductivity is 0.68 w/m*K or more. The resin component of the thermosetting resin cured product having high thermal conductivity is contained, and has a ring of mesogens. An epoxy resin cured product of an oxygen resin monomer and a hardener for an epoxy resin. 2. The thermosetting resin hardened material with high thermal conductivity as claimed in item 1 of the patent scope, wherein the epoxy resin monomer is the following general formula (1) printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative (1 E- M—S— Μ—E (but E is an epoxy group, Μ is a liquid crystal priming group, and S is a spacer). The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210X297). MM)