201022390 六、發明說明： 【發明所屬之技術領域】 本發明關於以具有導熱性同時對被壓黏物施加均勻壓 力爲目的而使用之熱壓黏用聚矽氧橡膠薄片，尤其關於耐 熱性良好，即使在300°C以上重複進行壓黏，永久變形所 致的劣化也小，對於機械破壞的耐久性也良好，斷裂時的 延伸度係適度地小，而且具有適度硬度及適度導熱率，用 0 於液晶顯示器等的電極之連接的各向異性導電膜之壓黏所 使用的熱壓黏用聚矽氧橡膠薄片，以及可適應於層合板或 撓性印刷基板之成形，可高精度壓黏的熱壓黏用聚矽氧橡 膠薄片。 【先前技術】 近年來，作爲行動電話、攜帶用電腦、電腦用監視器 、攝影機、數位照相機、導航系統、薄型電視等的顯示器 # ，液晶面板、電漿顯示器面板或有機EL面板係廣泛普及 。又’最近作爲可重寫的媒體，電子紙係開始普及，惟於 此等顯示面板中，爲了驅動影像，經由各向異性導電性黏 著劑，對面板側之引線電極與搭載有驅動用LSI的撓性印 刷基板之引線電極作熱壓黏，而進行電氣及機械的連接。 近年來’尤其以液晶面板爲中心，隨著局精細化顯示 技術的發展，前述引線電極的窄間距化係成爲必要。然而 ，於用各向異性導電性黏著劑的引線電極彼此之連接步驟 中，除了各自的引線電極成形時之尺寸公差，由於亦發生 -5- 201022390 引線電極彼此之對位誤差，撓性印刷基板與面板的熱膨脹 率不同，及壓黏時引線電極彼此的位置偏差，故窄間距的 連接係不容易。 作爲熱壓黏用聚矽氧橡膠薄片，例如已知有在聚矽氧 橡膠中摻合氮化硼同時以玻璃布補強者（專利文獻1)， 在聚矽氧橡膠中摻合氮化硼與導電性物質同時以玻璃布補 強，亦賦予抗靜電性者（專利文獻2)，在聚矽氧橡膠中 摻合有陶瓷或金屬等的良導熱性物質者（專利文獻3)等 9 。然而此等熱壓黏用聚矽氧橡膠薄片，由於基本要求的耐 熱性或緩衝性等未最合適化，故在將此等聚矽氧橡膠薄片 使用於窄間距連接時，無法得到良好的結果。 [專利文獻1]特開平5- 1 98344號公報 [專利文獻2]特開平6-3 6 8 5 3號公報 [專利文獻3]特開平6-2 8 93 52號公報 又，已知有於聚矽氧橡膠中摻合水分以外的揮發分爲 0-5%以下的碳黑而改良耐熱性者（專利文獻4)，藉由摻 © 合BET比表面積爲l〇〇m2/g以上的碳黑而進一步改良耐熱 性的熱壓黏用聚矽氧橡膠薄片（專利文獻5)。然而，此 熱壓黏用聚矽氧橡膠薄片，雖然耐熱性及耐久性極優異， 但是作爲對應於窄間距連接的薄片，係有斷裂時的延伸度 、硬度及導熱率等未最合適化的缺點。如此地，尙未得到 可對應於引線電極之窄間距化，耐熱性及耐久性優異的熱 壓黏用聚矽氧橡膠薄片。 [專利文獻4]特開平7-1 1010號公報 -6- 201022390 [專利文獻5]特開2003-261769號公報 因此，本發明者等，對於不僅耐熱性及耐久性優異， 而且也可對應於引線電極的窄間距化之熱壓黏用聚矽氧橡 膠薄片’進行專心致力的檢討。結果查明爲了對應於引線 電極的窄間距化’聚矽氧橡膠薄片之（1)室溫的硬度、 (2)斷裂時的延伸度及（3)導熱率等3個特性係極爲重 要’而且較佳爲使用金屬砂粉末及/或結晶性二氧化砂粉 φ 末當作導熱性粉末’當使用此等粉未時，由於可減小聚砂 氧橡膠薄片的壓縮永久變形，故容易減小由於重複壓黏而 來的永久變形所致的劣化。再者，由於上述的兩種粉末皆 爲低比重，故亦可減輕薄片的比重，聚矽氧橡膠薄片的操 作性也變良好。 尙且，已知作爲摻合有金屬矽粉末的聚矽氧，共塡充 氮化鋁與金屬矽粉末而成的導熱性有機聚矽氧烷組成物（ 專利文獻6)，將金屬矽當作導熱性塡充劑，摻合於聚矽 φ 氧橡膠中的導熱性聚矽氧組成物及其成形體（專利文獻7 )’慘合平均粒·徑爲以下的金屬砂粉末，而使高導 熱率與低壓縮永久變形並存的高導熱性聚矽氧橡膠組成物 (專利文獻8)，摻合有平均粒徑爲ΙΟΟμηι以下的金屬矽 粉末之高導熱性熱固定輥或固定帶用聚矽氧橡膠組成物， 及熱固定輥或固定帶（專利文獻9)，惟此等皆未考慮對 於熱壓黏用聚矽氧橡膠薄片的應用，對於熱壓黏用聚矽氧 橡膠薄片的用途’硬度、延伸度及導熱率係未最合適化。 [專利文獻6]特開平3 - 1 4 87 3號公報 201022390 [專利文獻7]特開2000-63670號公報 [專利文獻8]特開2007- 1 3 8 1 00號公報 [專利文獻9]特開2007-1 71 946號公報 再者，作爲考慮熱壓黏用途，摻合有金屬矽粉末的聚 矽氧薄片，已知摻合有金屬矽粉末當作導熱性電絕緣劑的 導熱性彈性薄片（專利文獻10)。然而，此薄片由於對於 熱壓黏用途的硬度、延伸度及導熱率係未最合適化，故作 爲熱壓黏薄片使用時有問題，尤其在作爲窄間距連接用的 @ 薄片使用時係耐不住。 [專利文獻10]特開2007-3 1 1 628號公報 【發明內容】 [發明所欲解決的問題] 即，本發明之第1目的爲提供適合於高精度熱壓黏的 熱壓黏用聚矽氧橡膠薄片，其在3 00°C以上的高溫下之熱 壓黏耐久性優異，而且使用於在液晶顯示器等中經由各向 @ 異性導電膜來壓黏窄間距的引線電極彼此之際。 本發明之第2目的爲提供可實現高精度成形的熱壓黏 用聚矽氧橡膠薄片，其適合作爲層合板或撓性印刷基板成 形時所用的緩衝薄片。 本發明者等爲了達成上述諸目的，進行專心致力的檢 討’結果發現對於基礎聚合物，即聚合度高之所謂混煉系 的有機聚矽氧烷，以一定比例配合導熱性粉末、碳黑粉末 及硬化劑’同時以23°C下斷裂時延伸度爲成爲50〜120% -8 - 201022390 ，以A型硬度計所測定的23 °C之硬度成爲65〜75 ,導熱 率成爲 0.5〜1 .OW/Mk的方式，按照需要配合一定量的 BET比表面積爲50m2/g以上的微粉末補強性矽石，則在 使所得到的組成物成形爲薄片狀後並使其硬化時，可得到 良好的結果，而達成本發明。 [解決問題的手段] φ 即，本發明係熱壓黏用聚矽氧橡膠薄片，其特徵爲該 聚矽氧橡膠薄片係使由（A)〜（E)所構成的聚矽氧橡膠 組成物成形爲薄片狀並使其硬化而成， (A) 平均聚合度爲3000以上的有機聚矽氧烷：100 質量份 (B) 由金屬、金屬氧化物、金屬氮化物及金屬碳化 物所選出的至少1種之導熱性粉末：50〜250質量份 (C) 碳黑粉末：5〜60質量份 # ( D ) 0〜40質量份的BET比表面積爲50m2/g以上的 微粉末補強性矽石，其中使成分（C)與成分（D)的合計 量爲10〜60質量份之量，及 (E )硬化劑，而 23 °C之斷裂時延伸度爲50〜120%，以A型硬度計所 測定的 23°C之硬度爲 65〜75，而且導熱率爲 0.5〜 1 .OW/mK。 於本發明中，較佳爲：（A)成分之平均聚合度爲 3 0 00以上的有機聚矽氧烷，係由下述平均組成式（1)所 201022390 示的一分子中至少具有平均2個烯基的有機聚矽氧烷所成 的一種以上之有機聚矽氧烷分子所構成，（A)成分之有 機聚矽氧烷分子所含有的全部R之0.10〜0.30莫耳％係乙 烯基’以此（A)成分的有機聚矽氧烷分子之全部乙烯基 量？（莫耳％)上，加上使（D)成分的補強性矽石粉末的 質量份除以100之數値Q後的合計（P + Q)之値爲0.20〜 〇.5〇的方式，調整前述（A)成分與（D)成分的使用量 ’同時（E)成分的硬化劑係由一分子中至少具有2個與 _ 矽原子鍵結的氫原子之有機氫聚矽氧烷及舶系觸媒所成。[Technical Field] The present invention relates to a thermocompression-bonded polyoxyethylene rubber sheet which is used for the purpose of imparting uniform heat to a pressure-sensitive adhesive while having thermal conductivity, and particularly relates to heat resistance. Even if it is repeatedly pressed at 300 ° C or higher, the deterioration due to permanent deformation is small, the durability against mechanical damage is good, the elongation at break is moderately small, and it has moderate hardness and moderate thermal conductivity. A thermocompression adhesive polyoxyethylene rubber sheet used for pressure bonding of an anisotropic conductive film connected to an electrode of a liquid crystal display or the like, and can be adapted to formation of a laminate or a flexible printed substrate, and can be highly pressure-bonded. Thermocompression bonding of polyoxyethylene rubber sheets. [Prior Art] In recent years, as a mobile phone, a portable computer, a computer monitor, a video camera, a digital camera, a navigation system, a thin television, etc., a liquid crystal panel, a plasma display panel, or an organic EL panel has been widely used. In addition, the electronic paper system has been widely used as a rewritable medium, and in the display panel, in order to drive the image, the lead electrode on the panel side and the driving LSI are mounted via an anisotropic conductive adhesive. The lead electrodes of the flexible printed circuit board are thermally bonded and electrically and mechanically connected. In recent years, especially in the case of liquid crystal panels, with the development of fine display technology, the narrow pitch of the lead electrodes has become necessary. However, in the step of connecting the lead electrodes of the anisotropic conductive adhesive to each other, in addition to the dimensional tolerances of the respective lead electrodes, the alignment error of the lead electrodes of the -5 - 201022390 is also caused, the flexible printed circuit board Unlike the thermal expansion coefficient of the panel, and the positional deviation of the lead electrodes at the time of pressure bonding, the connection of the narrow pitch is not easy. As a hot-pressing adhesive polyoxyethylene rubber sheet, for example, it is known to blend boron nitride with a glass cloth while reinforcing it with a glass cloth (Patent Document 1), and to mix boron nitride with polyoxymethylene rubber. In the case where the conductive material is reinforced with a glass cloth and the antistatic property is also imparted (Patent Document 2), a good thermal conductive material such as ceramic or metal is blended in the polyoxyxene rubber (Patent Document 3). However, such thermocompression-bonded polyoxyethylene rubber sheets are not optimally optimized because of the heat resistance or cushioning properties which are basically required, and therefore, when these polyoxyethylene rubber sheets are used for narrow-pitch connection, good results are not obtained. . [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. In the polyoxyxene rubber, carbon black having a volatilization amount other than water of 0 to 5% or less is added to improve heat resistance (Patent Document 4), and carbon having a BET specific surface area of l〇〇m 2 /g or more is incorporated. A thermocompression-bonded polyoxyethylene rubber sheet which is further improved in heat resistance by black (Patent Document 5). However, this thermocompression-bonded polyoxyethylene rubber sheet is excellent in heat resistance and durability, but is not optimally suited for elongation, hardness, and thermal conductivity at break when used as a sheet corresponding to a narrow pitch. Disadvantages. In this way, a hot-pressed polyoxyethylene rubber sheet which is excellent in heat resistance and durability is obtained in accordance with the narrow pitch of the lead electrode. In the inventors of the present invention, the inventors of the present invention are excellent in heat resistance and durability, and can also be used in accordance with the above-mentioned Japanese Patent Application Publication No. 2003-261769. The narrow-pitched hot-pressed polysilicon rubber sheet of the lead electrode was carefully reviewed. As a result, it was found that three characteristics such as (1) room temperature hardness, (2) elongation at break, and (3) thermal conductivity of the narrow-pitch 'polyoxyethylene rubber sheet corresponding to the lead electrode are extremely important'. Preferably, the metal sand powder and/or the crystalline silica sand powder φ is used as the thermal conductive powder. When the powder is used, since the compression set of the sand oxide rubber sheet can be reduced, it is easy to reduce. Deterioration due to permanent deformation due to repeated pressure bonding. Further, since both of the above powders have a low specific gravity, the specific gravity of the sheet can be alleviated, and the workability of the silicone rubber sheet is also improved. Further, a thermally conductive organopolyoxane composition obtained by mixing aluminum nitride and a metal ruthenium powder as a polyruthenium oxide doped with a metal ruthenium powder is known (Patent Document 6) The thermally conductive enthalpy, the thermally conductive polyfluorene oxide composition blended in the polyfluorene φ oxy rubber and the molded body thereof (Patent Document 7), which has a high thermal conductivity with a metal granule powder having an average particle diameter and the following A highly thermally conductive polyoxymethylene rubber composition having a ratio of low compression set and a low compression set (Patent Document 8), a high thermal conductivity heat-fixing roll or a polyether containing a metal tantalum powder having an average particle diameter of ΙΟΟμηι or less Rubber composition, and heat-fixing roll or fixing tape (Patent Document 9), but these are not considered for the application of hot-pressing adhesive silicone rubber sheets, and for the use of hot-pressed polyoxyethylene rubber sheets. The elongation and thermal conductivity are not optimal. [Patent Document 6] Japanese Laid-Open Patent Publication No. JP-A No. 2000-63670 (Patent Document No. JP-A No. 2000-63670) Japanese Patent Publication No. 2007-1 71 946. Further, as a polyfluorene oxide sheet in which metal cerium powder is blended for thermal compression bonding, a thermally conductive elastic sheet in which metal cerium powder is blended as a thermally conductive electrically insulating agent is known. (Patent Document 10). However, since the sheet is not most suitable for the hardness, elongation, and thermal conductivity of the thermocompression bonding application, it is problematic when used as a thermocompression bonding sheet, especially when used as a thin sheet for a narrow pitch connection. live. [Patent Document 10] JP-A-2007-3 1 628 SUMMARY OF INVENTION [Problem to be Solved by the Invention] That is, the first object of the present invention is to provide a thermocompression adhesive which is suitable for high-precision hot press bonding The silicone rubber sheet is excellent in thermal pressure-bonding durability at a high temperature of 300 ° C or higher, and is used for press-bonding narrow-pitch lead electrodes to each other via a respective anisotropic conductive film in a liquid crystal display or the like. A second object of the present invention is to provide a thermocompression adhesive polyoxyethylene rubber sheet which can be molded with high precision, which is suitable as a buffer sheet for forming a laminate or a flexible printed circuit board. In order to achieve the above-mentioned objects, the inventors of the present invention conducted an intensive review. As a result, it has been found that a thermal conductive powder or a carbon black powder is blended in a certain ratio with respect to a base polymer, that is, an organic polyoxane of a so-called kneading system having a high degree of polymerization. And the hardener 'at the same time, the elongation at break at 23 ° C is 50 to 120% -8 - 201022390 , the hardness at 23 ° C measured by the type A durometer is 65 to 75 , and the thermal conductivity is 0.5 to 1 . In the OW/Mk method, if a certain amount of fine powder-reinforcing vermiculite having a BET specific surface area of 50 m 2 /g or more is blended as needed, the obtained composition can be formed into a sheet shape and then cured. As a result, the invention is achieved. [Means for Solving the Problem] φ That is, the present invention is a thermosetting adhesive polyoxyethylene rubber sheet characterized in that the polyoxyethylene rubber sheet is a polyoxyethylene rubber composition composed of (A) to (E). It is formed into a sheet and hardened. (A) Organic polyoxyalkylene having an average degree of polymerization of 3,000 or more: 100 parts by mass (B) selected from metals, metal oxides, metal nitrides and metal carbides At least one kind of thermal conductive powder: 50 to 250 parts by mass (C) Carbon black powder: 5 to 60 parts by mass # (D) 0 to 40 parts by mass of fine powder reinforced vermiculite having a BET specific surface area of 50 m 2 /g or more Wherein the total amount of the component (C) and the component (D) is 10 to 60 parts by mass, and (E) the hardener, and the elongation at break of 23 ° C is 50 to 120%, and the hardness is A type. The hardness measured at 23 ° C was 65 to 75, and the thermal conductivity was 0.5 to 1 OW / mK. In the present invention, it is preferred that the organopolysiloxane having an average degree of polymerization of the component (A) of 300 or more is at least an average of 2 molecules represented by the following average composition formula (1) 201022390. One or more organic polyoxyalkylene molecules formed by an alkenyl group of an organic polyoxane, and the organic polyoxyalkylene molecules of the component (A) contain 0.10 to 0.30 mol% of the total R of the vinyl group. 'The total amount of vinyl of the organopolyoxane molecule of this (A) component? (mole %), the total amount (P + Q) after dividing the mass fraction of the reinforcing vermiculite powder of the component (D) by the number of 値Q is 0.20 to 〇.5〇, The amount of the component (A) and the component (D) to be used is adjusted. The hardener of the component (E) is an organohydrogenpolyoxane having at least two hydrogen atoms bonded to the _ 矽 atom in one molecule. It is made by the catalyst.
RnSiO(4 — n)/2.··· (1) 惟，式（1)中，η表示1.9〜2.4的正數，R表示取代 或非取代的一價烴基，各分子中的R之0.0001〜10莫耳％ 爲乙烯基，而且80莫耳。/。以上爲甲基。 於本發明中，（B)成分之導熱性粉末較佳爲金屬矽 粉末，特佳爲平均粒徑1〜20 μπι。其形狀較佳爲以粉碎法 所製造之不定形的所謂粉碎粉或以霧化法等所製造的球狀 G 粉。於上述金屬矽粉末的表面上，亦可形成強制氧化膜。 再者，本發明中的（Β)成分之導熱性粉末爲平均粒徑1 〜20μιη的結晶性二氧化矽粉末之情況，亦爲本發明的較 佳態樣。又，本發明的熱壓黏用聚矽氧橡膠薄片之厚度較 佳爲0.05〜1mm的範圍。 [發明的效果] 本發明的聚矽氧橡膠薄片，由於不僅熱壓黏耐久性優 -10- 201022390 異，而且斷裂時的延伸度亦比較小，具有適度硬度與適度 導熱率，故適合作爲熱壓黏用聚矽氧橡膠薄片，其係使用 於經由各向異性導電膜來高精度地熱壓黏窄間距的引線電 極彼此。又，當使用本發明的聚矽氧橡膠薄片作爲層合板 或撓性印刷基板成形時所用的緩衝薄片時，高精度的成形 係成爲可能。 Φ 【實施方式】 [實施發明的最佳形態] 首先，說明本說明書中所使用的「平均粒徑」及「平 均聚合度」之用語的定義。 「平均粒徑」： 碳黑的平均粒徑係指由使用電子顯微鏡所拍攝的照片 ，測定一次粒徑，將所求得的粒徑作算術平均，所謂之電 φ 子顯微鏡法的平均粒徑。再者，通常碳黑係凝聚一次粒子 而形成二次粒子，但是此處所言的平均粒徑不是指其二次 粒子的平均粒徑，而是指一次粒子的平均粒徑。 導熱性粉末的平均粒徑係指藉由光繞射/散射法測定 粒度分布，當由其小粒徑側累計的質量積分値成爲50%時 的粒徑。具體的測定例如可藉由日機裝株式會社製的粒度 分析計Microtrack等來進行。 「平均聚合度 -11 - 201022390 指有機聚矽氧烷等中構成當作骨架的矽氧烷鍵結之矽 原子數的平均値。 接著，說明本發明所用的組成物。 [組成物] 隨著液晶面板等的顯示面板之高精細化，對應於面板 側的引線電極與搭載有用於驅動影像的驅動用LS I的撓性 印刷基板之外引線電極的窄間距，在窄間距引線電極彼此 之經由各向異性導電膜的高精度熱壓黏連接中，重要的是 抑制壓黏時引線電極彼此的位置偏差。 爲了抑制上述熱壓黏時引線電極的位置偏差，本發明 的熱壓黏用聚矽氧薄片具有以下所示的（1)〜（3)之特 徴。 (1 ) 23 °C的室溫之斷裂時延伸度必須爲50〜120 %之 比較小’特佳爲60〜1 1 0%。基本上，從引線電極的位置 偏差之觀點，延伸度係愈小愈佳。然而，由於延伸度低於 5 0%則薄片欠缺柔軟性，故在被壓黏部有凹凸或高低差時 ’由於無法分散局部應力而容易斷裂，當對於薄片施加彎 曲方向的力時，發生薄片斷裂的問題。 (2 )以A型硬度計所測定的2 3 °C之室溫的硬度必須 爲65〜75’特佳爲67〜73。此硬度係防止引線電極的位 置偏差，同時使修正被壓黏物的平面度、平坦度或平行度 的公差而傳達均勻壓力的緩衝性並存。 (3 ) 23°C的室溫之導熱率必須爲0.5〜l.〇W/mK，特 201022390 佳爲0.6〜0.9 W/mK。爲了將來自熱壓黏裝置的加熱工具 之熱傳給各向異性導電膜，導熱率愈高愈佳，但若導熱率 比l.〇W/mK還大，則對各向異性導電膜急劇地過度傳熱 。於此情況下，硬化前的各向異性導電膜之黏度係急劇地 過度降低，而由連接電極之間流出，電極的電連接會變不 充分。 另一方面，若比〇.5W/mK還低，則由於難以將熱傳 φ 給各向異性導電膜，而必須提高加熱工具的溫度。由於提 高加熱工具的溫度，對熱壓黏裝置的負擔變重。又，由於 更高溫的加熱工具接觸熱壓黏用聚矽氧薄片，而促進聚矽 氧薄片的熱降解。再者，由於高溫的加熱工具將輻射熱給 予不耐熱的液晶面板之彩色濾光片等，而亦造成問題。 接著，說明本發明所用的組成物之必要成分（A )成 分〜（E )成分。 Φ ( A)成分： 本發明所使用的（A)成分之平均聚合度3000以上的 有機聚矽氧烷，例如係由以下的平均組成式（1)所示， RnSl〇 (4 -η) /2* · · ·⑴ 惟，式（1)中的η表示ι·95〜2.4的正數，R表示取 代或非取代的一價烴基。 作爲R所示的取代或非取代的一價烴基之具體例，可 例示甲基、乙基、丙基等的烷基，環戊基、環己基等的環 烷基，乙烯基、烯丙基等的烯基，苯基、甲苯基等的芳基 -13- 201022390 ，或此等基的氫原子部分地經氯原子、氟原子等的齒素原 子取代的鹵化烴基等。 作爲（A)成分的有機聚矽氧烷，較佳爲主鏈由甲基 矽氧烷單位所構成者，或於此等的有機聚矽氧院之主鏈導 入有甲基、乙烯基、苯基、三氟丙基等的有機基者。特別 地，較佳爲前述有機基的0.0001〜10莫耳％係乙烯基，而 且80莫耳％以上係甲基。又，較佳爲分子鏈末端被有機矽 烷基或羥基所封端者。作爲此有機矽烷基，可例示三甲基 矽烷基、二甲基乙烯基矽烷基' 三乙烯基矽烷基等。 作爲（A)成分的有機聚砂氧院，可僅使用一種，也 可混合複數種來使用，較佳爲前述式（1)所示的（A)成 分之有機聚矽氧烷分子全體所具有的全部R之0.10〜0.30 莫耳％爲乙烯基。又，於本發明中，式（1)所示的（A) 成分之平均聚合度必須爲3000以上。聚合度若低於3 000 ，則硬化後的機械強度差。 (B)成分： (B)成分係由金屬、金屬氧化物、金屬氮化物及金 屬碳化物所選出的至少1種之導熱性粉末，其係將導熱性 賦予本發明的聚矽氧橡膠薄片之塡充劑。此等的具體例之 金屬例如爲銀、銅、鐵、金屬矽、鎳、鋁等，金屬氧化物 例如爲氧化鋅、氧化鋁、氧化鎂、二氧化矽 '氧化鐵等’ 金屬氮化物例如爲氮化硼、氮化鋁、氮化矽等’金屬碳化 物例如爲碳化矽、碳化硼等。 -14- 201022390 於上述導熱性粉末之中，特佳爲金屬矽粉末或結晶性 二氧化矽粉末。藉由使用此等粉末，可減少壓縮成形畸變 ’由於減小因重複壓黏所生成的永久變形所致的劣化，可 實現耐久性優異的熱壓黏用聚矽氧橡膠薄片。又，由於兩 種粉末皆爲低比重，可減輕薄片的比重，熱壓黏用聚矽氧 橡膠薄片的操作性變良好。 此等粉末的形狀可爲球狀、橢圓狀、扁平狀、有稜角 φ 的不定形、帶圓的不定形、針狀等的任何者，並沒有特別 的限定。例如，當爲金屬矽時，可例示球狀、粉碎所致的 不定形等》 又，導熱性粉末的純度係沒有特別的限定，從賦予導 熱性的觀點來看，較佳爲5 0%以上，尤佳爲80%以上，更 佳爲95%以上。純度高的金屬矽粉末係在表面的自然氧化 膜沒有缺陷，而高溫熱安定性良好，特佳爲在金屬矽粉末 的表面設置強制氧化膜。藉由設置強制氧化膜，可消除對 ® 金屬矽粉末表面的活性點，該活性點會對薄片成形時的有 機聚矽氧烷之交聯反應給予不良影響。 本發明所使用的熱性粉末的平均粒徑係沒有特別的限 制，較佳爲0.1〜50μιη，尤其0.5〜20μιη，而且最佳爲1 〜1 0 μιη。平均粒徑若低0.1 μχη，則由於相對地粉末的比表 面積變大，故高塡充變困難，導熱率變不充分，同時硬化 後的橡膠會變過硬。另一方面，平均粒徑若大於50μπι， 則由於硬化後的橡膠變脆，同時表面容易出現凹凸，故不 宜。 -15- 201022390 本發明中的（B)成分之配合量，相對於100質量份 的（A )成分而言必須爲50〜250質量份，特佳爲以70〜 200質量份的範圍來使用。若比250質量份多，則配合變 困難’而且成形加工性變差。又，若比5 0質量份少，貝(I 導熱率變不充分。 (C )成分： 本發明所使用的（C)成分之碳黑，係使聚矽氧橡膠 _ 薄片的機械強度，尤其加熱時的機械強度升高而提高耐熱 性，同時賦予導熱性及導電化所致的抗靜電性。 碳黑係根據其製造方法而分類爲爐黑、槽黑、熱黑、 乙炔黑等’而且通常多含有硫等的雜質。於本發明中，較 佳爲使用水以外的揮發分爲〇 . 5質量％以下者。特佳爲乙 炔黑，因爲雜質少。 上述水以外的揮發分之測定方法係在Π S K 6 2 2 1的“ 橡膠用碳黑試驗方法”中有記載。具體地，於坩堝中置入 參 規定量的碳黑，以950°C加熱7分鐘後，測定揮發減量。 (C)成分之碳黑的平均粒徑較佳爲10〜300nm的範 圍，特佳爲1 5〜1 OOnm的範圍。而且’ BET比表面積較佳 爲 20 〜300m2/g，特佳爲 30 〜20 0m2/g。 本發明中的（C)成分之配合量，相對於1〇〇質量份 的（A)成分而言爲5〜60質量份’特佳爲以1〇〜55質量 份的範圍來使用。若低於5質量份’則導熱性及耐熱壓黏 性的提高變不充分’而若超過60質量份，則均句地配合 -16- 201022390 變困難，而且所得到的組成物之成形加工性係極度變差。 (D) 成分： 本發明所使用的（D)成分之BET比表面積爲50m2/g 以上的微粉末補強性矽石，係使用作爲聚矽氧橡膠的補強 成分。此微粉末矽石係親水性者，也可爲疏水性者，從補 強性效果的方面來看，BET比表面積較佳爲50〜800m2/g _ ’特佳爲100〜500m2/g的微粉末矽石。比表面積若低於 5〇m2/g，則無法得到充分的補強效果。 本發明中的（D)成分之配合量，相對於100質量份 的（A)成分較佳爲0〜40質量份，更佳爲5〜35質量份 ，特佳爲10〜30質量份。若比40質量份多，則聚矽氧橡 膠組成物的可塑度變過高而成形性變差，或硬化後的橡膠 變過硬。 尙且在本發明中，成分（C)與成分（D)的合計量必 〇 須爲10〜60質量份，較佳爲20〜50質量份。若低於10 質量份，則所得到的聚矽氧橡膠之強度變不充分，而若超 過60質量份，則均勻地配合變困難，而且所得到的組成 物之可塑度變過高，故成形加工性變極差。 (E) 成分： 本發明所使用的（E)成分之硬化劑，係可從通常聚 矽氧橡膠之硬化所使用的眾所周知者之中適宜地選擇使用 。作爲如此的硬化劑，例如： -17- 201022390 (a) 自由基反應所使用的二第三丁基過氧化物、2,5-二甲基-2,5-二（第三丁基過氧）己烷、二枯基過氧化物等 的有機過氧化物； (b) 當（A)成分的有機聚矽氧烷具有烯基時，作爲 加成反應硬化劑，可例示1分子中含有2個以上的鍵結於 矽原子之氫原子的有機氫聚矽氧烷與舶、鈀等的鉑族金屬 系觸媒之組合等。於本發明中，基於容易控制反應、反應 殘渣不殘留等的理由，（b )之加成反應硬化劑係較佳， φ 視需要亦可倂用兩者。此等硬化劑的添加量係可與通常的 聚矽氧橡膠之情況同樣，一般係如以下。 關於硬化劑（a)，係每100質量份的（A)成分之有 機聚矽氧烷使用0.1〜20質量份。 關於硬化劑（b)，前述1分子中含有2個以上的鍵 結於矽原子之氫原子的有機氫聚矽氧烷之量，係以每1莫 耳的（A)成分之烯基而言，該有機氫聚矽氧烷所具有的 鍵結於矽原子的氫原子成爲0.5〜5莫耳之量，鉑族金屬 系觸媒的量係相對於（A)成分而言，使金屬部分成爲0.1 〜lOOOppm (質量基準）。 爲了控制本發明的聚矽氧橡膠薄片之硬度及延伸度， 以便可以使用各向異性導電膜，以高精度窄間距地連接引 線電極彼此，必須將聚矽氧分子間的交聯程度以及塡充粉 末與聚矽氧分子之間的相互作用控制在適當範圍。藉由加 成反應的控制，可容易控制聚矽氧分子間的交聯度，特別 地在聚合度高的混煉系聚矽氧橡膠之情況，係可藉由控制 -18- 201022390 參與交聯的乙烯基之含有率來控制。又，當爲聚矽氧橡膠 時’已知作爲聚砂氧分子與塡充粉末之間的相互作用，聚 矽氧分子與補強性矽石的氫鍵之假交聯所致的相互作用係 大。因此’當爲以加成反應的硬化當作主要交聯反應的聚 矽氧橡膠時，藉由將乙烯基的含有率與補強性矽石的配合 量之二個因子控制最合適範圍，可將本發明的聚矽氧橡膠 薄片之硬度及延伸度調整在合適的範圍。 φ 具體地’藉由使（A)成分之有機聚矽氧烷全部分子 的側鏈中所含有的全部R內之〇.1〇〜〇.3〇莫耳％成爲乙烯 基，同時於此（A)成分之有機聚矽氧烷分子全體的側鏈 總量中的乙烯基之莫耳％値（p )上，加上使（D )成分的 微粉末補強性矽石之相對於1 〇〇質量份的（A )成分而言 之質量份除以100之數値（Q)後的合計（P + q)爲〇.20 〜0.50的方式，調整（A)成分與（d)成分後，使加成 反應而使硬化’可將本發明的聚矽氧橡膠薄片之硬度及延 φ 伸度調整在合適的範圍。 前述（P + Q )的合計値若低於〇 · 2 0，則加成反應所致 的交聯點、與微粉末補強性矽石和聚矽氧分子的氫鍵所致 的假交聯點之和係不足，故不僅延伸度變過大，而且硬度 亦不足。相反地，當超過0.50時，由於交聯點與假交聯 點之和變過大，故延伸度變過小而薄片變脆，耐久性差， 而且變過硬而緩衝性不足。 其它成分 -19- 201022390 於本發明的聚矽氧橡膠組成物中，按照需要更可添加 氧化鈽、氧化鐵紅、氧化鈦等的耐熱賦予劑、黏土'碳酸 鈣、矽藻土、二氧化鈦等的塡充劑、低分子矽氧烷酯、矽 烷醇等的分散劑、矽烷偶合劑、鈦偶合劑等的賦黏劑、賦 予難燃性的鉑族金屬系化合物、提高橡膠複合物的生膠強 度之四氟聚乙烯粒子等。 調製•加工 @ 本發明中所用的聚矽氧橡膠組成物係可以使用二輥磨 機、捏合機、班百里混合機等的混合機，將所使用的各成 分混煉，一般可在即將使用之前僅添加硬化劑，較佳爲預 先與混煉其它成分。 作爲本發明的聚矽氧橡膠薄片之成形方法，可舉出將 摻合有到硬化劑爲止的全部成分之聚矽氧橡膠組成物，經 由壓延機或擠壓機分成指定的厚度後，使硬化之方法，將 液狀的聚矽氧橡膠組成物或溶解在甲苯等的溶劑中而液狀 〇 化的聚矽氧橡膠組成物，塗佈在薄膜上後，使硬化之方法 等。 如此所成形、硬化之聚矽氧橡膠薄片的厚度爲0.05〜 1mm，特佳爲0.1〜0_ 8mm的範圍。厚度若低於〇.〇5mm， 則緩衝性不足’均勻的壓力傳達變不可能。另一方面，若 爲超過1 mm的厚度，則導熱性變差。 以下’藉由實施例來更詳述本發明，惟本發明完全不 受此等所限制。 -20- 201022390 於下述之例中’使用以下的材料。 有機聚矽氧烷： (a-l )由99.85莫耳％的 耳％的甲基乙烯基矽氧烷單 8,000的分子鏈兩末端經二甲 甲基乙烯基聚矽氧烷 二甲基矽氧烷單位及0.15莫 位所構成，平均聚合度爲 基乙烯基矽烷氧基所封鎖的RnSiO(4 - n)/2. (1) However, in the formula (1), η represents a positive number of 1.9 to 2.4, and R represents a substituted or unsubstituted monovalent hydrocarbon group, and 0.001 of R in each molecule 10 mole % is vinyl and 80 moles. /. The above is a methyl group. In the present invention, the thermally conductive powder of the component (B) is preferably a metal ruthenium powder, particularly preferably having an average particle diameter of 1 to 20 μm. The shape thereof is preferably an unshaped so-called pulverized powder produced by a pulverization method or a spherical G powder produced by an atomization method or the like. A forced oxide film may be formed on the surface of the above metal cerium powder. Further, the thermally conductive powder of the (Β) component in the present invention is a crystalline ceria powder having an average particle diameter of 1 to 20 μm, which is also a preferred aspect of the present invention. Further, the thickness of the thermocompression-bonding polyoxyethylene rubber sheet of the present invention is preferably in the range of 0.05 to 1 mm. [Effects of the Invention] The polyoxyxene rubber sheet of the present invention is suitable as a heat because it has excellent heat-bonding durability, -10-201022390, and elongation at break, and has moderate hardness and moderate thermal conductivity. A pressure-sensitive adhesive polyoxyethylene rubber sheet is used for thermally pressing a pinch electrode having a high pitch through an anisotropic conductive film with high precision. Further, when the polyoxyethylene rubber sheet of the present invention is used as a buffer sheet for forming a laminate or a flexible printed circuit board, a high-precision molding system is possible. [Embodiment] [Best Mode for Carrying Out the Invention] First, the definitions of the terms "average particle diameter" and "average polymerization degree" used in the present specification will be described. "Average particle diameter": The average particle diameter of carbon black refers to a photograph taken by using an electron microscope, and the primary particle diameter is measured, and the obtained particle diameter is arithmetically averaged. The average particle diameter of the so-called electric φ submicroscope is used. . Further, in general, carbon black aggregates primary particles to form secondary particles, but the average particle diameter as used herein does not mean the average particle diameter of the secondary particles, but refers to the average particle diameter of the primary particles. The average particle diameter of the thermally conductive powder is a particle diameter obtained by measuring the particle size distribution by a light diffraction/scattering method when the mass integral enthalpy accumulated on the small particle diameter side becomes 50%. The specific measurement can be carried out, for example, by a particle size analyzer Microtrack manufactured by Nikkiso Co., Ltd. "Average polymerization degree -11 - 201022390 refers to the average enthalpy of the number of argon atoms constituting the siloxane supporting a skeleton as a skeleton in an organic polysiloxane. Next, the composition used in the present invention will be described. [Composition] The display panel such as a liquid crystal panel has a high definition, and corresponds to a narrow pitch of lead electrodes other than the lead printed electrodes on the panel side and the flexible printed circuit board on which the driving LS I is driven, and the narrow pitch lead electrodes pass through each other. In the high-precision thermocompression bonding of an anisotropic conductive film, it is important to suppress the positional deviation of the lead electrodes when the pressure-adhesive is pressed. In order to suppress the positional deviation of the lead electrodes during the above-mentioned hot-pressing, the hot-pressing adhesive of the present invention The oxygen flakes have the characteristics of (1) to (3) shown below. (1) The elongation at room temperature of 23 ° C must be 50 to 120 %, which is relatively small - particularly preferably 60 to 1 10%. Basically, from the viewpoint of the positional deviation of the lead electrode, the smaller the elongation is, the better. However, since the elongation is less than 50%, the sheet lacks flexibility, so when there is unevenness or height difference in the pressed portion. Due to the inability to disperse local The force is easy to break, and when the force in the bending direction is applied to the sheet, the problem of sheet fracture occurs. (2) The hardness of the room temperature of 23 ° C measured by the type A durometer must be 65 to 75'. 67 to 73. This hardness prevents the positional deviation of the lead electrode, and at the same time corrects the cushioning property of the uniform pressure by correcting the tolerance of the flatness, flatness or parallelism of the pressure-sensitive adhesive. (3) Room temperature of 23 ° C The thermal conductivity must be 0.5~l.〇W/mK, especially 201022390 is preferably 0.6~0.9 W/mK. In order to transfer the heat from the heating tool of the thermocompression bonding device to the anisotropic conductive film, the higher the thermal conductivity Preferably, if the thermal conductivity is larger than l.〇W/mK, the anisotropic conductive film is excessively excessively transferred. In this case, the viscosity of the anisotropic conductive film before curing is drastically excessively lowered. On the other hand, if the connection between the electrodes is out, the electrical connection of the electrodes may become insufficient. On the other hand, if it is lower than 〇5 W/mK, it is difficult to heat the φ to the anisotropic conductive film, and the heating tool must be improved. Temperature. Due to the increased temperature of the heating tool, the thermal pressure bonding device Moreover, the higher temperature heating tool contacts the hot-pressing polysilicon oxide sheet to promote the thermal degradation of the polyfluorene oxide sheet. Furthermore, the high-temperature heating tool gives the radiant heat to the color of the heat-resistant liquid crystal panel. The filter or the like also causes problems. Next, the essential components (A) to (E) of the composition used in the present invention will be described. Φ (A) component: Average polymerization of the component (A) used in the present invention The organopolyoxane having a degree of 3,000 or more is represented by, for example, the following average composition formula (1): RnSl〇(4 -η) /2* · · · (1) However, η in the formula (1) represents ι· A positive number from 95 to 2.4, and R represents a substituted or unsubstituted monovalent hydrocarbon group. Specific examples of the substituted or unsubstituted monovalent hydrocarbon group represented by R may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group, a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a vinyl group or an allyl group. An alkenyl group such as an aryl group, an aryl group such as a phenyl group or a tolyl group, or a halogenated hydrocarbon group in which a hydrogen atom of the group is partially substituted with a dentate atom such as a chlorine atom or a fluorine atom. The organopolyoxane as the component (A) is preferably one in which the main chain is composed of a methyl siloxane unit, or a main chain of the organic polysiloxane is introduced with a methyl group, a vinyl group, or a benzene group. An organic group such as a group or a trifluoropropyl group. In particular, it is preferred that 0.0001 to 10 mol% of the organic group be a vinyl group, and 80 mol% or more is a methyl group. Further, it is preferred that the end of the molecular chain is blocked by an organic decyl group or a hydroxyl group. As such an organic decyl group, a trimethyl decyl group, a dimethyl vinyl decyl group, a trivinyl fluorenyl group, etc. are illustrated. The organic polyxanthine of the component (A) may be used alone or in combination of a plurality of kinds, and it is preferred that all of the organopolyoxane molecules of the component (A) represented by the above formula (1) have All of R's 0.10~0.30 mol% is vinyl. Further, in the present invention, the average polymerization degree of the component (A) represented by the formula (1) must be 3,000 or more. If the degree of polymerization is less than 3,000, the mechanical strength after hardening is poor. (B) Component: The component (B) is at least one type of thermally conductive powder selected from the group consisting of a metal, a metal oxide, a metal nitride, and a metal carbide, and imparts thermal conductivity to the polyoxyethylene rubber sheet of the present invention.塡 剂. Examples of the metal of such a specific example are silver, copper, iron, metal ruthenium, nickel, aluminum, etc., and the metal oxide is, for example, zinc oxide, aluminum oxide, magnesium oxide, ruthenium dioxide, iron oxide or the like. The 'metal carbides such as boron nitride, aluminum nitride, and tantalum nitride are, for example, tantalum carbide, boron carbide, or the like. -14- 201022390 Among the above thermally conductive powders, metal cerium powder or crystalline cerium oxide powder is particularly preferred. By using such a powder, it is possible to reduce the distortion of the compression molding. By reducing the deterioration due to the permanent deformation caused by the repeated pressure-bonding, a thermocompression-bonding polyoxyethylene rubber sheet excellent in durability can be obtained. Further, since both of the powders have a low specific gravity, the specific gravity of the sheet can be alleviated, and the workability of the hot-pressed polyoxyethylene rubber sheet becomes good. The shape of the powder may be any of a spherical shape, an elliptical shape, a flat shape, an amorphous shape with an angular φ, an amorphous shape with a round shape, a needle shape, or the like, and is not particularly limited. For example, in the case of a metal crucible, a spherical shape, an amorphous shape due to pulverization, and the like can be exemplified. The purity of the thermal conductive powder is not particularly limited, and from the viewpoint of imparting thermal conductivity, it is preferably 50% or more. More preferably, it is 80% or more, and more preferably 95% or more. The metal ruthenium powder having a high purity has no defects on the surface of the natural oxide film, and the high temperature heat stability is good, and it is particularly preferable to provide a forced oxide film on the surface of the ruthenium metal powder. By providing a forced oxide film, the active point on the surface of the ® metal tantalum powder can be eliminated, and this active point adversely affects the crosslinking reaction of the organic polyoxane at the time of sheet formation. The average particle diameter of the thermal powder used in the present invention is not particularly limited, and is preferably from 0.1 to 50 μm, particularly from 0.5 to 20 μm, and most preferably from 1 to 10 μm. When the average particle diameter is as low as 0.1 μχη, the relative surface area of the powder is increased, so that the high enthalpy is difficult to be charged, the thermal conductivity is insufficient, and the hardened rubber becomes hard. On the other hand, when the average particle diameter is more than 50 μm, the rubber after curing becomes brittle and the surface tends to have irregularities, which is not preferable. -15-201022390 The amount of the component (B) in the present invention is 50 to 250 parts by mass, and particularly preferably 70 to 200 parts by mass, per 100 parts by mass of the component (A). If it is more than 250 parts by mass, the blending becomes difficult, and the moldability is deteriorated. In addition, when it is less than 50 parts by mass, shell (I thermal conductivity is insufficient. (C) component: The carbon black of the component (C) used in the present invention is a mechanical strength of the polyxene oxide sheet. The mechanical strength during heating is increased to improve the heat resistance, and the antistatic property due to thermal conductivity and electrical conductivity is imparted. The carbon black is classified into furnace black, channel black, hot black, acetylene black, etc. according to the method of production. In the present invention, it is preferable to use a volatile matter other than water, and it is preferably 5% by mass or less, particularly preferably acetylene black, because the amount of impurities is small. It is described in "Testing method for carbon black for rubber" of 6 SK 6 2 2 1. Specifically, a predetermined amount of carbon black is placed in a crucible, and heated at 950 ° C for 7 minutes, and then the amount of volatilization is measured. The average particle diameter of the carbon black of the component C) is preferably in the range of 10 to 300 nm, particularly preferably in the range of 15 to 100 nm, and the 'BET specific surface area is preferably 20 to 300 m 2 /g, particularly preferably 30 to 20 0m2/g. The compounding amount of the component (C) in the present invention is relative to 1 part by mass. The component (A) is 5 to 60 parts by mass, and particularly preferably used in a range of 1 to 55 parts by mass. When the amount is less than 5 parts by mass, the improvement in thermal conductivity and heat-resistant pressure-sensitive property is insufficient. When the amount is more than 60 parts by mass, it is difficult to uniformly blend with -16 to 201022390, and the formability of the obtained composition is extremely deteriorated. (D) Component: BET ratio of the component (D) used in the present invention The fine powder-reinforcing vermiculite having a surface area of 50 m 2 /g or more is used as a reinforcing component of the polyoxyxene rubber. The fine powder of vermiculite is hydrophilic, and may be hydrophobic, from the viewpoint of reinforcing effect. The BET specific surface area is preferably from 50 to 800 m 2 /g _ ', particularly preferably from 100 to 500 m 2 /g. When the specific surface area is less than 5 〇 m 2 /g, a sufficient reinforcing effect cannot be obtained. The amount of the component (D) is preferably from 0 to 40 parts by mass, more preferably from 5 to 35 parts by mass, even more preferably from 10 to 30 parts by mass, per 100 parts by mass of the component (A). If the amount is too large, the plasticity of the composition of the polyoxymethylene rubber becomes too high and the formability deteriorates, or the rubber after hardening changes. Further, in the present invention, the total amount of the component (C) and the component (D) must be 10 to 60 parts by mass, preferably 20 to 50 parts by mass. If less than 10 parts by mass, the result is obtained. The strength of the polyoxyxene rubber is insufficient, and if it exceeds 60 parts by mass, the uniform blending becomes difficult, and the plasticity of the obtained composition becomes too high, so that the formability is extremely poor. (E) Ingredients The hardener of the component (E) used in the present invention can be suitably selected from those well-known as those used in the curing of the conventional polyoxyxene rubber. As such a hardener, for example: -17- 201022390 (a ) organic peroxides such as di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, etc. used in the radical reaction (b) When the organic polyoxyalkylene of the component (A) has an alkenyl group, an organic hydrogen having two or more hydrogen atoms bonded to a halogen atom in one molecule can be exemplified as the addition reaction curing agent. A combination of a polyoxyalkylene oxide and a platinum group metal catalyst such as a ship or a palladium. In the present invention, the addition reaction hardener (b) is preferred because of the ease of controlling the reaction, the residue of the reaction residue, and the like, and φ may be used as needed. The amount of these hardeners added can be the same as in the case of a conventional polyoxyxene rubber, and is generally as follows. The curing agent (a) is used in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the organic polyoxyalkylene of the component (A). In the case of the curing agent (b), the amount of the organic hydrogen polyoxyalkylene which contains two or more hydrogen atoms bonded to a halogen atom in one molecule is in the case of an alkenyl group of the component (A) per 1 mole. The hydrogen atom of the organic hydrogen polyoxyalkylene bonded to the halogen atom is 0.5 to 5 moles, and the amount of the platinum group metal catalyst is based on the component (A), so that the metal portion becomes 0.1 to lOOOppm (quality basis). In order to control the hardness and elongation of the polyoxyethylene rubber sheet of the present invention, an anisotropic conductive film can be used to connect the lead electrodes to each other with high precision and narrow pitch, and the degree of crosslinking between the polyoxymethylene molecules and the charge must be supplemented. The interaction between the powder and the polyoxymolecular molecules is controlled to an appropriate range. By controlling the addition reaction, the degree of crosslinking between the polyoxo molecules can be easily controlled, especially in the case of a highly polymerized kneading system, which can be crosslinked by controlling -18-201022390. The vinyl content is controlled. Moreover, when it is a polyoxyxene rubber, it is known that the interaction between the polysiloxane molecules and the enthalpy powder is large, and the interaction between the polyoxyl molecules and the hydrogen bonds of the reinforcing vermiculite is large. . Therefore, when the polysulfide rubber which is the main cross-linking reaction by the hardening reaction of the addition reaction is controlled, the two factors of the blending ratio of the vinyl group content and the reinforcing vermiculite are controlled to the most suitable range. The hardness and elongation of the polyoxyethylene rubber sheet of the present invention are adjusted to a suitable range. φ Specifically, by making all of R contained in the side chain of all the molecules of the organopolyoxyalkylene of the component (A), 〇.1〇~〇.3〇mol% becomes a vinyl group, and at the same time A) The molar amount of the vinyl group in the total amount of the side chain of the organopolysiloxane molecule of the component A) (p) plus the fine powder of the (D) component reinforced with vermiculite relative to 1 〇〇 After adjusting the (A) component and the (d) component, the mass fraction (A) is divided by the number of 値 (Q) and the total amount (P + q) is 〇.20 to 0.50. The addition reaction and hardening can adjust the hardness and elongation of the polyoxyethylene rubber sheet of the present invention to an appropriate range. When the total amount of the above (P + Q ) is less than 〇·20, the crosslinking point due to the addition reaction and the pseudo-crosslinking point due to hydrogen bonding with the fine powder-reinforcing vermiculite and the polyfluorene oxygen molecule The system is insufficient, so not only the elongation becomes too large, but also the hardness is insufficient. On the other hand, when it exceeds 0.50, since the sum of the cross-linking point and the pseudo-cross-linking point becomes too large, the elongation becomes too small, the sheet becomes brittle, the durability is poor, and it becomes too hard and the cushioning property is insufficient. Other components -19-201022390 In the polyoxyethylene rubber composition of the present invention, a heat-resistant imparting agent such as cerium oxide, iron oxide red or titanium oxide, or clay 'calcium carbonate, diatomaceous earth, titanium dioxide or the like may be further added as needed. A dispersant such as a chelating agent, a low molecular weight oxoxane or a decyl alcohol, a condensing agent such as a decane coupling agent, or a titanium coupling agent, a platinum group metal compound which imparts flame retardancy, and a green rubber strength of the rubber compound Tetrafluoroethylene particles and the like. Modification and processing @ The polyoxyxene rubber composition used in the present invention can be kneaded by using a mixer such as a two-roll mill, a kneader or a Banbury mixer, and is generally ready for use. Only the hardener is added before, and it is preferred to mix and mix the other components in advance. The method for forming the polyoxyethylene rubber sheet of the present invention includes a polyoxyethylene rubber composition in which all the components to the curing agent are blended, and is divided into a predetermined thickness by a calender or an extruder to be hardened. In the method, a liquid polysulfide rubber composition or a polyoxyxylene rubber composition which is dissolved in a solvent such as toluene and is liquid-deuterated is applied onto a film to be cured. The thickness of the thus formed and hardened polyoxyethylene rubber sheet is 0.05 to 1 mm, particularly preferably in the range of 0.1 to 0 to 8 mm. If the thickness is less than 〇.〇5 mm, the cushioning property is insufficient. Uniform pressure transmission becomes impossible. On the other hand, if the thickness is more than 1 mm, the thermal conductivity is deteriorated. The invention is described in more detail below by way of examples, but the invention is not limited at all. -20- 201022390 Use the following materials in the following examples. Organic polyoxyalkylene: (al) from 99.85 mol% of the ear% of methyl vinyl oxime, a single 8,000 molecular chain at both ends via a dimethylmethylvinyl polyoxyalkylene dimethyl oxane unit And 0.15 molar position, the average degree of polymerization is blocked by the vinyl vinyl alkoxy group
(a-2)由99.5莫耳％的二甲基矽氧烷單位及〇.5莫耳 %的甲基乙烯基矽氧烷單位所構成，平均聚合度爲8,〇〇〇 的分子鏈兩末端經二甲基乙烯基矽烷氧基所封鎖的甲基乙 烯基聚矽氧烷 導熱性塡充劑： (b-Ι)平均粒徑爲5μιη的金屬矽粉碎粉末（表面經 強制氧化處理者） Φ ( b-2 )平均粒徑爲4μιη的結晶性二氧化矽粉碎粉末 (b-3)平均粒徑爲4μπι的氧化鋁粉碎粉末 碳黑粉末： (c-1 )平均粒徑爲35nm，水以外的揮發分爲0.10質 量％，BET比表面積爲69m2/g的乙炔黑 微粉末補強性矽石： (d-1) BET比表面積爲3〇〇m2/g的微粉末補強性矽 -21 - 201022390 石（商品名：Aerosil 3 00,日本AEROSIL株式會社製） 硬化劑： (e-Ι)氯舶酸的乙稀基砍氧院錯合物（銷含量丨質 量％ ) (e-2)下述式（1)所示的甲基氫聚矽氧院 C»3 <p{3 (CH 3bsi〇(s Λ) af(Siq) wsi(CH ah (i) & A φ 其它成分： (f-l)二甲基二甲氧基矽烷 (g-1) BET比表面積爲140m2/g的氧化铈粉末 (h-1 )乙炔基環己醇 [實施例1] 用由60質量份的（a-Ι )與40質量份的（a-2 )所構 〇 成的糊1〇〇質量份當作（A )成分，用20質量份的（d_i )當作（D)成分，（D)成分的表面處理劑係用3質量 份的（f-l)及1質量的離子交換水，使用捏合機邊在 1 70 °C加熱2小時邊摻合•混煉而均勻化。 對於1 23質量份的所得之聚矽氧橡膠組成物，添加 130質量份當作（B)成分的（b-Ι) 、10質量份當作 )成分的（c-1 )及0.5質量份當作耐熱改良劑的的（ )，使用加壓捏合機，進行1 5分鐘摻合·混煉而均勻化 -22- 201022390 對於1 00質量份的所得之聚矽氧橡膠組成物’更將 〇.〇5質量份的（e-Ι) 、0.025質量份的鉑觸媒之控制劑的 (h-Ι)以及0.7質量份的（e-2) ’邊依序以二輥磨機混 煉邊依上述順序添加’而製作硬化性聚矽氧橡膠組成物（ I )。 使用壓延成形機將所得之聚矽氧橡膠組成物分成厚度 φ 0.25mm後，轉印到厚度ΙΟΟμιη的聚對苯二甲酸乙二酯（ PET )薄膜上。以PET薄膜的層合品之狀態’照原樣地費 5分鐘通過150 °C的加熱爐中’以使薄片狀的聚矽氧橡膠 組成物硬化。由所得之薄片狀組成物剝離PET薄膜’在 200。(：的乾燥機中熱處理4小時，而製作厚度爲〇.25111111的 熱壓黏用聚矽氧橡膠薄片。 [實施例2] % 使用加壓捏合機摻合1〇〇質量份當作（A)成分的（ a-2) 、140質量份當作（B)成分的（b-2) 、50質量份 當作（C )成分的（c-1 )以及0.5質量份當作耐熱改良劑 的（g- 1 )，混煉1 5分鐘而均勻化。對於1 〇〇質量份的所 得之聚矽氧橡膠組成物，添加0.1質量份的（e-Ι ) > 0.04 質量份的粕觸媒之控制劑的（h-1 )以及1 . 〇質量份的（e-2)，藉由二輥磨機充分混煉而調製硬化性聚矽氧橡膠組 成物（11 ) ’與實施例1之情況同樣地使成形及硬化，而 製作厚度爲〇.25mm的聚矽氧橡膠薄片。 -23- 201022390 [實施例3] 除了代替實施例1所使用的（B)成分，使用220質 量份的（b-3)以外’與實施例1同樣地製作厚度0.25 mm 的聚矽氧橡膠薄片。 比較例1 除了使用100質量份當作（A)成分的（a-2) 、30質 φ 量份當作（D)成分的（d-1) 、0_1質量份的（e-1)、 0.04質量份的（h-1)以及υ質量份的（e_2)以外，與 實施例1同樣地製作厚度0.25mm的聚矽氧橡膠薄片》 比較例2 除了作爲（A )成分，使用（a_i )代替（a_2 )以外 ，與實施例2同樣地製作厚度〇.25mm的聚矽氧橡膠薄片 比較例3 使用由50質量份的（a-l)及50質量份的（a-2)所 構成的糊質量份當作（A)成分，作爲（D)成分的 表面處理劑’使用3質量份的（f-i)及丨質量份的離子交 換水’使用捏合機邊在1 7 0 °C加熱2小時邊摻合·混煉而 均勻化。對於Ϊ 5 3質量份的所得之聚矽氧橡膠組成物，添 加3 20質量份當作（B )成分的（b-i )，使用加壓捏合機 -24- 201022390 ，進行1 5分鐘摻合·混煉而均勻化。除了對於1 00質量 份的所得之聚矽氧橡膠組成物’使用二輥磨機均勻混煉 0.8質量份的（e-3 )，而調製硬化性聚矽氧橡膠組成物（ III )，一次加硫溫度爲170°C以外，與實施例1同樣地成 形、硬化，而製作厚度〇.25mm的聚矽氧橡膠薄片。 [基本物性的評價] φ 依照JIS K6249的規定來測定硬度、拉伸強度及斷裂 時延伸度。但是，關於硬度，使用A型硬度計，對所製作 的薄片，以厚度成爲6mm以上的方式，重複測定。拉伸 強度及斷裂時延伸度係使用啞鈴狀2號型的試驗片來測定 〇 又，導熱率係依照ASTM E 1 530的規定來測定。 [1 〇〇次壓黏後的厚度減少率] • 僅將聚矽氧橡膠薄片固定在壓黏機的支撐工具上，使 用經加熱到400°C的加熱工具，以1 0秒的間隔連續進行 100次以4MPa的按壓壓力直接按壓10秒的動作。 將[(薄片的初期厚度）-（薄片的1〇〇次壓黏後之厚 度）]/薄片的初期厚度以百分率所記載的數字當作1〇〇次 壓黏後的厚度減少率。 [窄間距連接評價] 如第1圖所示地，將以3 2 μιη間距（線寬1 6 μηι、間隔 -25- 201022390 1 6 μιη )設有5 0條銅電極1 a的F P C (撓性印刷電路板）、 與同樣以32μηι間距（線寬16μιη、間隔16μιη)設有50條 ΙΤΟ電極lb的玻璃板2b，以各自的設有銅電極la及ΙΤΟ 電極lb側之面呈互相面對面的方式，在其間夾持厚度 22μιη、寬度1.2mm的ACF (各向異性導電膜）3之狀態下 ，設置在壓黏機的支撐工具4之上。接著，將實施例1〜3 或比較例1〜3所製作的熱壓黏用聚矽氧橡膠薄片5以碰 觸的方式載置在上述FPC 2a之上面。然後’從上述聚矽 氧橡膠薄片5的上方，藉由經加熱到3 50°C的加壓工具6 ，以4MPa的按壓壓力按壓1〇秒。如此地，在FPC 2a與 玻璃板2b間壓黏ACF 3後’評價銅電極la與ITO電極 1 b之間的電氣導通。表1中顯示結果。 -26- 201022390 [表i](a-2) consisting of 99.5 mol% of dimethyloxane units and 5.5 mol% of methylvinyloxirane units, with an average degree of polymerization of 8, and a molecular chain of two Methylvinyl polyoxyalkylene thermal conductive agent blocked by dimethyl vinyl alkoxy group at the end: (b-Ι) metal cerium pulverized powder having an average particle diameter of 5 μm (surface subjected to forced oxidation treatment) Φ ( b-2 ) crystalline cerium oxide pulverized powder having an average particle diameter of 4 μm (b-3) alumina pulverized powder carbon black powder having an average particle diameter of 4 μm: (c-1 ) average particle diameter of 35 nm, water Other acetylene black fine powder reinforced vermiculite having a volatile content of 0.10% by mass and a BET specific surface area of 69 m 2 /g: (d-1) Micropowder reinforcing 矽-21 - BET specific surface area of 3 〇〇 m 2 /g 201022390 Stone (trade name: Aerosil 3 00, manufactured by Japan AEROSIL Co., Ltd.) Hardener: (e-Ι) chloric acid, ethylene-based sputum compound (sale content 丨 mass%) (e-2) Methylhydrogen polyoxo shown in formula (1) C»3 <p{3 (CH 3bsi〇(s Λ) af(Siq) wsi(CH ah (i) & A φ Other components: ( Flu) dimethyldimethoxy Alkane (g-1) cerium oxide powder (h-1) ethynylcyclohexanol having a BET specific surface area of 140 m 2 /g [Example 1] used by 60 parts by mass of (a-Ι) and 40 parts by mass of (a) -2) The mass fraction of the paste formed as the component (A) is 20 parts by mass of (d_i) as the component (D), and the surface treatment agent of the component (D) is used in an amount of 3 parts by mass. (fl) and 1 mass of ion-exchanged water were mixed and kneaded by heating at 1 70 ° C for 2 hours using a kneader to homogenize. For 1 23 parts by mass of the obtained polyxanthene rubber composition, 130 was added. (b-1) and 10 parts by mass of (b-1) and 0.5 parts by mass of the component (b) as a heat-resistant improver, using a pressure kneader, 1 5 minutes blending and kneading to homogenize -22- 201022390 For 100 parts by mass of the obtained polyoxyxene rubber composition 'more 〇. 〇 5 parts by mass of (e-Ι), 0.025 parts by mass of platinum touch (h-Ι) of the control agent of the medium and 0.7 parts by mass of (e-2) 'sequentially added in a two-roll mill while adding in the above order to produce a curable polyxanthene rubber composition (I) Using a calendering machine The obtained polyoxyethylene rubber composition is divided into a thickness of φ 0.25 mm and then transferred onto a polyethylene terephthalate (PET) film having a thickness of ΙΟΟμηη. The state of the laminate of the PET film is taken as it is. The minute passes through a heating furnace at 150 ° C to harden the flaky polyoxyethylene rubber composition. The PET film was peeled off from the obtained sheet-like composition at 200. The heat treatment of the (: dryer was carried out for 4 hours to prepare a hot-pressed polyoxyethylene rubber sheet having a thickness of 〇.25111111. [Example 2] % A pressure kneader was used to blend 1 part by mass as (A) (a-2), 140 parts by mass of (b-2) as component (B), 50 parts by mass of (c-1) as component (C), and 0.5 part by mass as heat-resistant improver (g-1), homogenized for 15 minutes, and 0.1 parts by mass of (e-Ι) > 0.04 parts by mass of rhodium catalyst was added to 1 part by mass of the obtained polyoxyxene rubber composition. (h-1) of the control agent and (e-2) of the mass fraction (e-2), which are sufficiently kneaded by a two-roll mill to prepare the curable polyoxyethylene rubber composition (11)' and the embodiment 1 In the same manner, a polysilicone rubber sheet having a thickness of 〇25 mm was produced by molding and hardening. -23- 201022390 [Example 3] In place of the component (B) used in Example 1, 220 parts by mass ( In the same manner as in Example 1 except that b-3), a polyxene oxide rubber sheet having a thickness of 0.25 mm was produced. Comparative Example 1 (a-2), 30 mass φ was used as the component (A) in addition to 100 parts by mass. In the same manner as in Example 1, except that (d-1) of the component (D), (e-1) of 0 to 1 part by mass, (h-1) of (0-1) by mass, and (e_2) of the mass fraction of (υ). A polyxylene oxide sheet having a thickness of 0.25 mm was produced. Comparative Example 2 A comparative example of a polyoxyxene rubber sheet having a thickness of 2525 mm was produced in the same manner as in Example 2 except that (a) was used instead of (a_2) as the component (A). 3 A paste mass composed of 50 parts by mass of (al) and 50 parts by mass of (a-2) is used as the component (A), and a surface treating agent as the component (D) is used in an amount of 3 parts by mass (fi) And the mass parts of the ion-exchanged water were mixed and kneaded by heating at 170 ° C for 2 hours using a kneader to homogenize. For the obtained polyoxyxene rubber composition of Ϊ 5 3 parts by mass, add 3 20 parts by mass of (b) as the component (B), homogenized by blending and kneading for 15 minutes using a pressure kneader-24-201022390. Except for 100 parts by mass of the obtained polyoxyl The rubber composition was uniformly kneaded with 0.8 parts by mass of (e-3) using a two-roll mill to prepare a hardenable polyoxyethylene rubber composition (III), one The polysulfide rubber sheet having a thickness of 〇25 mm was produced and cured in the same manner as in Example 1 except that the sulfurization temperature was 170 ° C. [Evaluation of basic physical properties] φ Hardness and elongation were measured in accordance with JIS K6249. The strength and the elongation at break. However, the hardness was measured by repeating the measurement of the produced sheet so that the thickness was 6 mm or more using a type A durometer. The tensile strength and the elongation at break were measured using a dumbbell-shaped No. 2 test piece. The thermal conductivity was measured in accordance with ASTM E 1 530. [1 thickness reduction rate after pressure-bonding] • Fix the poly-xylene rubber sheet only on the support tool of the press machine, and continue using the heating tool heated to 400 °C at intervals of 10 seconds. 100 times of direct pressing for 10 seconds with a pressing pressure of 4 MPa. The number of the initial thickness of the sheet (the initial thickness of the sheet) (the thickness of the sheet after the pressure-bonding of the sheet) was measured as a percentage decrease in the thickness after the pressure-bonding. [Evaluation of narrow-pitch connection] As shown in Fig. 1, FPC (flexibility) of 50 copper electrodes 1 a is provided at a pitch of 3 2 μm (line width of 16 μm, interval -25 - 201022390 1 6 μm) The printed circuit board) and the glass plate 2b provided with 50 bismuth electrodes lb at the same distance of 32 μm (line width 16 μm, interval 16 μm) are faced to each other in such a manner that the faces of the copper electrodes 1a and 1b are provided to face each other. In the state in which the ACF (anisotropic conductive film) 3 having a thickness of 22 μm and a width of 1.2 mm is sandwiched therebetween, it is placed on the support tool 4 of the press machine. Next, the thermocompression-bonding polyoxyethylene rubber sheets 5 produced in Examples 1 to 3 or Comparative Examples 1 to 3 were placed on the upper surface of the FPC 2a in a contact manner. Then, from the above-mentioned polyoxyethylene rubber sheet 5, it was pressed at a pressing pressure of 4 MPa for 1 sec by a pressurizing tool 6 heated to 305 °C. Thus, the electrical conduction between the copper electrode 1a and the ITO electrode 1b was evaluated after the ACF 3 was pressure-bonded between the FPC 2a and the glass plate 2b. The results are shown in Table 1. -26- 201022390 [Table i]
實施例 1 實施例 2 實施例 3 比較例 1 比較例 2 比較例 3 配合組成 (質量份） a-1 60 _ 60 100 50 a-2 40 100 40 100 50 b-1 130 • 130 320 b-2 _ 140 _ • 140 _ b-3 _ _ 220 - 一 c-1 10 50 10 10 50 - d-l 20 _ 20 30 — 50 f-1 3 • 3 3 - 3 g-l 0.5 0.5 0.5 0.5 0.5 _ 離子交換水 1 一 1 1 1 相對於100質量份 的上述複合物而言 之配合組成(質量份） e-1 0.05 0.1 0.05 0.1 0.1 e-2 0.7 1 0.7 1 1 • e-3 • _ _ 編 _ 0.8 h-l 0.025 0.04 0.025 0.04 0.04 乙烯基+補強性矽石合計㈤ 0.35 0.25 0.35 0.55 0.08 0.66 成形方法 壓延 壓延 壓延 壓延 壓延 壓延 薄片的厚度 0.25mm 0.25mm 0.25mm 0.25mm 0.25mm 0.25mm 拉伸強度(MPa) 7.8 6.9 6.3 8.3 5.1 9.8 斷裂時延伸度(％) 90 60 110 20 160 30 硬度 70 72 70 77 62 79 導熱率(W/mk) 0.78 0.81 0.76 0.77 0.82 1.43 100次壓黏後的厚度減少率(％) 7 7 15 8 16 11 窄間距連接評價 初期 OK OK OK NG NG NG 100次壓黏後 OK OK NG NG NG NG ※乙烯基+補強性矽石合計 於（A)成分的有機聚矽氧烷分子全體的側鏈中之乙 烯基的莫耳％之數値加上（D )成分的補強性矽石粉末之 相對於1 〇〇質量份的（A )成分而言之質量份除以1 00後 -27- 201022390 的數値之合計値 於實施例1〜3所製作的本發明之熱壓黏用聚矽氧橡 膠薄片的情況中，完成對應於窄間距的連接，但是如比較 例1地，在過硬的情況中，由於緩衝性不足，電極間的導 通係完全沒有。又，比較例1或3所得之薄片係非常脆， 若折疊則薄片發生破裂。另一方面，於比較例2的情況中 ，薄片的延伸度大，由於發生電極的位置偏差，故發生導 通不良。 @ [產業上的利用可能性] 本發明的熱壓黏用聚矽氧橡膠薄片，不僅在300°C以 上的高溫下之熱壓黏耐久性優異，即使在300°C以上重複 進行壓黏，永久變形所致的劣化也小，對於機械破壞的耐 久性也良好，斷裂時的延伸度係適度地小，而且具有適度 硬度及適度導熱率，故適合於高精度撓性印刷基板的成形 ，或液晶顯示器等中的窄間距之引線電極彼此的經由各向 G 異性導電膜之高精度熱壓黏。 【圖式簡單說明】 第1圖係說明使用本發明的熱壓黏用聚矽氧橡膠薄片 ’熱壓黏FPC所夾持的ACF之方法的示意圖。 【主要元件符號說明】 1 a :銅電極 -28- 201022390 1 b : IΤ 0電極 2a :撓性印刷電路版 2b :玻璃板 3 =各向異性導電膜 4:支撐工具（支持台） 5:熱壓黏用聚矽氧橡膠薄片 6 :加熱•加壓工具Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Composition (parts by mass) a-1 60 _ 60 100 50 a-2 40 100 40 100 50 b-1 130 • 130 320 b-2 _ 140 _ • 140 _ b-3 _ _ 220 - one c-1 10 50 10 10 50 - dl 20 _ 20 30 — 50 f-1 3 • 3 3 - 3 gl 0.5 0.5 0.5 0.5 0.5 _ ion exchange water 1 a composition of 1 1 1 relative to 100 parts by mass of the above composite (parts by mass) e-1 0.05 0.1 0.05 0.1 0.1 e-2 0.7 1 0.7 1 1 • e-3 • _ _ _ _ 0.8 hl 0.025 0.04 0.025 0.04 0.04 Vinyl + Reinforcing Vermiculite Total (5) 0.35 0.25 0.35 0.55 0.08 0.66 Forming Method Calendering Calendering Calendering Calendering Calendering Sheet Thickness 0.25mm 0.25mm 0.25mm 0.25mm 0.25mm 0.25mm Tensile Strength (MPa) 7.8 6.9 6.3 8.3 5.1 9.8 Elongation at break (%) 90 60 110 20 160 30 Hardness 70 72 70 77 62 79 Thermal conductivity (W/mk) 0.78 0.81 0.76 0.77 0.82 1.43 Thickness reduction after 100 presses (%) 7 7 15 8 16 11 Initial evaluation of narrow-pitch connection OK OK OK NG NG NG After 100 times of pressure-bonding OK OK NG NG NG NG ※ B The base + reinforcing vermiculite is a total of the mole % of the vinyl group in the side chain of the entire organopolyoxyalkylene molecule of the component (A) plus the reinforcing vermiculite powder of the component (D) relative to the The mass fraction of the (A) component of the mass fraction is divided by the number of 10,000 to -27-201022390, and the hot-pressed polyoxyethylene rubber sheet of the present invention produced in Examples 1 to 3 In the case of the connection corresponding to the narrow pitch, as in the case of the comparative example 1, in the case of an excessively hard, the conduction between the electrodes was completely absent due to insufficient cushioning property. Further, the sheet obtained in Comparative Example 1 or 3 was very brittle, and if it was folded, the sheet was broken. On the other hand, in the case of Comparative Example 2, the elongation of the sheet was large, and the conduction failure occurred due to the positional deviation of the electrode. @ [Industrial Applicability] The hot-press adhesive polysulfide rubber sheet of the present invention is excellent not only at a high temperature of 300 ° C or higher but also at a temperature of 300 ° C or higher. The deterioration due to permanent deformation is also small, the durability against mechanical damage is also good, the elongation at break is moderately small, and the hardness is moderate and the thermal conductivity is moderate, so it is suitable for forming a high-precision flexible printed circuit board, or The lead electrodes of the narrow pitch in the liquid crystal display or the like are pressure-bonded to each other via the high-precision thermal conductive film of the G-transmissive conductive film. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a method of using the hot-pressed polyoxyethylene rubber sheet of the present invention to thermally bond the ACF held by the FPC. [Main component symbol description] 1 a : Copper electrode-28- 201022390 1 b : IΤ 0 electrode 2a: Flexible printed circuit board 2b: Glass plate 3 = Anisotropic conductive film 4: Supporting tool (support table) 5: Heat Pressure-adhesive polyoxyethylene rubber sheet 6 : heating and pressing tools
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