TWI576236B - Thermos viscous use of silicone rubber sheet - Google Patents
Thermos viscous use of silicone rubber sheet Download PDFInfo
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- TWI576236B TWI576236B TW100139760A TW100139760A TWI576236B TW I576236 B TWI576236 B TW I576236B TW 100139760 A TW100139760 A TW 100139760A TW 100139760 A TW100139760 A TW 100139760A TW I576236 B TWI576236 B TW I576236B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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Description
本發明關於在電力‧電子機器零件的配線連接步驟中，以傳熱且均勻地施加壓力為目的而使用之熱壓黏用聚矽氧橡膠薄片。The present invention relates to a thermocompression adhesive polyoxyethylene rubber sheet which is used for the purpose of heat transfer and uniform application of pressure in a wiring connection step of electric power and electronic equipment parts.
於液晶面板的製造時，將驅動液晶用的液晶面板之透明引線電極與搭載有驅動用LSI之撓性印刷基板(COF)的引線電極，隔著異向性導電接著劑(糊狀或薄膜狀)進行熱壓黏，以進行電及機械的連接。此時，以施加熱而且均勻的壓力為目的，一般在加壓‧加熱金屬工具與COF之間夾住聚矽氧橡膠薄片。In the production of the liquid crystal panel, the transparent lead electrode for driving the liquid crystal panel for liquid crystal and the lead electrode of the flexible printed circuit board (COF) on which the driving LSI is mounted are interposed with an anisotropic conductive adhesive (paste or film). ) Perform thermocompression bonding for electrical and mechanical connections. At this time, for the purpose of applying heat and uniform pressure, the polyoxyethylene rubber sheet is generally sandwiched between the pressurized metal tool and the COF.
作為熱壓黏用聚矽氧橡膠薄片，例如已知在聚矽氧橡膠中摻合氮化硼與導電性物質及經玻璃布補強者(專利文獻1：特開平5-198344號公報)，或在聚矽氧橡膠中摻合氮化硼與導電性物質及經玻璃布補強，賦予抗靜電性者(專利文獻2：特開平6-36853號公報)，在聚矽氧橡膠中摻合有陶瓷、金屬等的良導熱性物質者(專利文獻3：特開平6-289352號公報)，在聚矽氧橡膠中摻合已去除水分而揮發份為0.5%以下的碳黑之改良耐熱性者(專利文獻4：特開平7-11010號公報)等。然而，此等者係未改善薄片表面的黏著性。For example, it is known that a polyfluorene oxide rubber sheet is a pressure-sensitive adhesive, and it is known that a boron nitride, a conductive material, and a glass cloth are reinforced by a polyphthalide rubber (Patent Document 1: Japanese Patent Laid-Open No. Hei 5-198344), or In the polyoxyxene rubber, a boron nitride, a conductive material, and a glass cloth are reinforced to impart antistatic properties (Patent Document 2: JP-A-6-36853), and ceramics are blended in the polyoxyxene rubber. And a heat-resistant material of a carbon black having a volatile content of 0.5% or less in a polyoxyxene rubber (Japanese Patent Publication No. 6-289352). Patent Document 4: JP-A-7-11010, and the like. However, these have not improved the adhesion of the surface of the sheet.
因此，有提案藉由將在聚矽氧橡膠中摻合有碳黑的薄片與耐熱性樹脂薄膜複合化，使薄片表面沒有黏著性，而且強度亦優異之熱壓黏用聚矽氧橡膠複合薄片(專利文獻5：特開平8-174765號公報)。然而，此薄片由於聚矽氧橡膠係與耐熱性樹脂薄膜接著，故柔軟性比橡膠單體低。此傾向係在薄片的兩面設置耐熱性樹脂薄膜時特別強。因此，於加壓時均勻地施加壓力變困難，故需要增大加壓力，但此加壓力係在與被壓黏體的強度之關係上有限度。Therefore, there has been proposed a hot-pressed polyoxyethylene rubber composite sheet which is obtained by combining a sheet in which a carbon black is blended in a polyoxyethylene rubber with a heat-resistant resin film, so that the surface of the sheet is not adhesive, and the strength is excellent. (Patent Document 5: Japanese Laid-Open Patent Publication No. Hei 8-174765). However, since this sheet is followed by a heat-resistant resin film, the flexibility is lower than that of the rubber monomer. This tendency is particularly strong when a heat resistant resin film is provided on both sides of the sheet. Therefore, it is difficult to apply pressure uniformly during pressurization, so it is necessary to increase the pressing force, but this pressing force is limited in the relationship with the strength of the pressed body.
又，有提案層合玻璃布或玻璃布處理氟樹脂薄片與導熱性聚矽氧橡膠(專利文獻6：日本發明專利第3244187號公報，專利文獻7：日本發明專利第4301468號公報，專利文獻8：特開2001-315248號公報，專利文獻9：特開2004-168025號公報)。In addition, it is proposed to laminate a fluororesin sheet and a heat conductive polyoxymethylene rubber by a glass cloth or a glass cloth (Patent Document 6: Japanese Patent No. 3244187, Patent Document 7: Japanese Patent No. 4301468, Patent Document 8) JP-A-2001-315248, JP-A-2004-168025.
然而，近年來更進行液晶面板的高精細化，起因於習知品所使用的玻璃布之織目所造成的凹凸，而妨礙均勻的壓黏，或發生面板電極與COF電極的位置偏移，故要求新穎高精細對應薄片之開發。However, in recent years, the high definition of the liquid crystal panel has been caused, which is caused by the unevenness caused by the woven fabric of the glass cloth used in the conventional product, which hinders the uniform pressure sticking or the positional shift of the panel electrode and the COF electrode. Development of novel high-definition counterpart sheets.
[專利文獻1]特開平5-198344號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 5-198344
[專利文獻2]特開平6-36853號公報[Patent Document 2] Japanese Patent Publication No. 6-36853
[專利文獻3]特開平6-289352號公報[Patent Document 3] JP-A-6-289352
[專利文獻4]特開平7-11010號公報[Patent Document 4] Japanese Patent Publication No. 7-11010
[專利文獻5]特開平8-174765號公報[Patent Document 5] Japanese Patent Laid-Open No. Hei 8-174765
[專利文獻6]日本發明專利第3244187號公報[Patent Document 6] Japanese Invention Patent No. 3244187
[專利文獻7]日本發明專利第4301468號公報 [Patent Document 7] Japanese Invention Patent No. 4301468
[專利文獻8]特開2001-315248號公報 [Patent Document 8] JP-A-2001-315248
[專利文獻9]特開2004-168025號公報 [Patent Document 9] JP-A-2004-168025
本發明係鑒於如此的情事而完成者，目的在於提供適合於高精細液晶面板之製造的熱壓黏用聚矽氧橡膠薄片。 The present invention has been made in view of such circumstances, and an object thereof is to provide a thermocompression adhesive polyoxyethylene rubber sheet suitable for the manufacture of a high-definition liquid crystal panel.
本發明之上述目的係藉由將經扁平或開放加工的玻璃布與導熱性聚矽氧橡膠層層合而成之熱壓黏用聚矽氧橡膠薄片來達成。 The above object of the present invention is achieved by a thermocompression bonding polyoxyethylene rubber sheet obtained by laminating a flat or open processed glass cloth and a thermally conductive polyoxyethylene rubber layer.
即，本發明者進行各種的檢討，結果發現與以往之熱壓黏用聚矽氧橡膠薄片所使用之未經扁平或開纖加工的玻璃布比較下，藉由使用經扁平或開纖加工的凹凸少之玻璃布當作基材，而使壓黏時的壓力分布更均勻，可抑制COF的變形或偏移，終於完成本發明。 That is, the present inventors conducted various reviews, and as a result, it was found that by using a flattened or fiber-opened glass cloth which is not flattened or opened by a conventional hot-press adhesive polyoxyethylene rubber sheet. The glass cloth having less unevenness is used as a substrate, and the pressure distribution at the time of pressure bonding is more uniform, and deformation or offset of COF can be suppressed, and the present invention has finally been completed.
因此，本發明提供下述熱壓黏用聚矽氧橡膠薄片。 Accordingly, the present invention provides the following thermocompression adhesive polyoxyethylene rubber sheet.
申請專利範圍第1項：一種熱壓黏用聚矽氧橡膠薄片，其特徵為在導熱性聚矽氧橡膠層上，層合一體化有經扁平或開纖加工的玻璃布。 Patent Application No. 1: A hot-pressed adhesive polyoxyethylene rubber sheet characterized in that a flat or fiber-opened glass cloth is laminated on a thermally conductive polyoxysulfide rubber layer.
申請專利範圍第2項： 如申請專利範圍第1項之熱壓黏用聚矽氧橡膠薄片，其中上述經扁平或開纖加工的玻璃布，以下述式(I)所示的空隙率計為10%以下，空隙率=[(b1×b2)/(a1×a2)]×100 (I) Patent Application No. 2: The hot-pressed polyoxyethylene rubber sheet according to claim 1, wherein the flat or fiber-opened glass cloth is determined by a void ratio represented by the following formula (I) 10% or less, void ratio = [(b 1 × b 2 ) / (a 1 × a 2 )] × 100 (I)
(式中，a1表示鄰接的經紗之中心間長度的平均值(μm)，a2表示鄰接的緯紗之中心間長度的平均值(μm)，b1表示鄰接的經紗之間隙的平均值(μm)，b2表示鄰接的緯紗之間隙的平均值(μm))。 (wherein a 1 represents an average value (μm) of the lengths between centers of adjacent warp yarns, a 2 represents an average value (μm) of the lengths between centers of adjacent weft yarns, and b 1 represents an average value of gaps between adjacent warp yarns ( Μm), b 2 represents the average value (μm) of the gap of the adjacent weft yarns.
申請專利範圍3：如申請專利範圍第1或2項之熱壓黏用聚矽氧橡膠薄片，其中上述玻璃布係被聚矽氧樹脂所填縫處理，更且至少在其一面上層合有導熱性聚矽氧橡膠層。 Patent Application No. 3: The hot-press adhesive polyoxyethylene rubber sheet according to claim 1 or 2, wherein the glass cloth is filled with a polyoxyn resin, and at least one side is laminated with heat conduction. Polysilicon rubber layer.
申請專利範圍4：如申請專利範圍第1至3項中任一項之熱壓黏用聚矽氧橡膠薄片，其中上述經扁平或開纖加工的玻璃布之厚度為0.02mm以上0.1mm以下。 The hot-press adhesive polyoxyethylene rubber sheet according to any one of claims 1 to 3, wherein the flat or fiber-opened glass cloth has a thickness of 0.02 mm or more and 0.1 mm or less.
申請專利範圍5：如申請專利範圍第1至4項中任一項之熱壓黏用聚矽氧橡膠薄片，其中上述導熱性聚矽氧橡膠層係導熱率0.3W/mK以上5W/mK以下，硬度30以上90以下。 The hot-press adhesive polyoxyethylene rubber sheet according to any one of claims 1 to 4, wherein the thermal conductive polysulfide rubber layer has a thermal conductivity of 0.3 W/mK or more and 5 W/mK or less. The hardness is 30 or more and 90 or less.
於以往的玻璃布中，熱壓黏時經紗與緯紗的交點係特別強地對撓性印刷基板推壓。因此，於窄間距的電極接合 中會發生位置偏移。又，不含有玻璃布的單層導熱性橡膠薄片，由於與含玻璃布品比較下容易變形，故特別在撓性印刷基板的端部有容易發生位置偏移之傾向。 In the conventional glass cloth, the intersection of the warp yarn and the weft yarn during hot press bonding is particularly strong against the flexible printed circuit board. Therefore, electrode bonding at narrow pitch A positional offset occurs in the middle. Further, since the single-layer thermally conductive rubber sheet which does not contain the glass cloth is easily deformed as compared with the glass-containing cloth, there is a tendency that the end portion of the flexible printed circuit board is likely to be displaced.
相對於此，本發明的熱壓黏用聚矽氧橡膠薄片，係藉由將經扁平或開纖加工的玻璃布層合，而與COF接觸的薄片表面之凹凸係比習知品還大幅減輕，即使在窄間距的電極接合中也可大幅抑制位置偏移。 On the other hand, in the hot-pressed polyoxyethylene rubber sheet of the present invention, by laminating the flattened or opened fiber-optic glass cloth, the unevenness of the surface of the sheet which is in contact with the COF is greatly reduced, even if it is a conventional product. Positional offset can also be greatly suppressed in the electrode bonding of narrow pitches.
本發明的熱壓黏用聚矽氧橡膠薄片，係對於經扁平或開纖加工的玻璃布以聚矽氧樹脂填縫處理之基材布，至少在其一面上層合導熱性聚矽氧橡膠層而製作。 The hot-pressing adhesive polyoxynitride rubber sheet of the present invention is a base material cloth which is filled with a polyoxyxylene resin for a flat or opened fiber glass cloth, and a thermal conductive polyoxysulfide rubber layer is laminated on at least one side thereof. And making.
圖1顯示其一例，在基材布11的一面上層合導熱性聚矽氧橡膠層12所成。再者，圖中11a表示玻璃纖維，11b表示聚矽氧樹脂。 Fig. 1 shows an example in which a thermally conductive polyoxyxene rubber layer 12 is laminated on one surface of a base fabric 11. Further, in the figure, 11a denotes glass fiber, and 11b denotes a polysiloxane resin.
此處，作為本發明所使用的玻璃布，構成經紗及緯紗的紗線之平均單纖維直徑為4μm以上8μm以下，厚度為0.03mm以上0.20mm以下，特佳為0.10mm以下，經紗及緯紗的密度各自較佳為50條/25mm以上。單纖維直徑及厚度若小於此，則強度不足，相反地若變大，則薄片表面的凹凸變大，而妨礙均勻的壓力傳達。又，即使經紗及緯紗的密度變小，薄片表面的凹凸也變大。 Here, as the glass cloth used in the present invention, the yarn constituting the warp yarn and the weft yarn has an average single fiber diameter of 4 μm or more and 8 μm or less, a thickness of 0.03 mm or more and 0.20 mm or less, particularly preferably 0.10 mm or less, and warp and weft. The density is preferably 50 strips/25 mm or more. If the diameter and thickness of the single fiber are smaller than this, the strength is insufficient, and conversely, if the diameter becomes large, the unevenness on the surface of the sheet becomes large, and uniform pressure transmission is hindered. Further, even if the density of the warp yarn and the weft yarn becomes small, the unevenness on the surface of the sheet becomes large.
此玻璃布係被扁平或開纖加工者，作為開纖處理方法 ，可採用使玻璃布在經超音波振動的水中內開織之超音波法、將玻璃布在溫水中藉由上下旋轉筒體來加壓而使開纖之旋轉筒體的推壓法、對玻璃布噴射柱狀流高壓水而使開纖之柱狀流高壓水噴射開纖法、振動洗滌法、稜線法等。 This glass cloth is processed by a flat or open fiber processor as a method of opening the fiber. The ultrasonic method of spinning the glass cloth in water subjected to ultrasonic vibration, the method of pressing the glass cloth in the warm water by rotating the cylinder up and down to pressurize the rotating cylinder, and The glass cloth sprays a columnar flow of high-pressure water to open the columnar flow of high-pressure water, a vibrating method, a vibration washing method, a ridge line method, and the like.
此時，上述經扁平或開纖加工的玻璃布，以下述式(I)所示的空隙率較佳為10%以下，特佳為0~5%。 In this case, the flat or opened fiber glass cloth preferably has a void ratio represented by the following formula (I) of 10% or less, particularly preferably 0 to 5%.
空隙率=[(b1×b2)/(a1×a2)]×100 (I) Void ratio = [(b 1 × b 2 ) / (a 1 × a 2 )] × 100 (I)
(式中，a1表示鄰接的經紗之中心間長度的平均值(μm)，a2表示鄰接的緯紗之中心間長度的平均值(μm)，b1表示鄰接的經紗之間隙的平均值(μm)，b2表示鄰接的緯紗之間隙的平均值(μm))。 (wherein a 1 represents an average value (μm) of the lengths between centers of adjacent warp yarns, a 2 represents an average value (μm) of the lengths between centers of adjacent weft yarns, and b 1 represents an average value of gaps between adjacent warp yarns ( Μm), b 2 represents the average value (μm) of the gap of the adjacent weft yarns.
上述經扁平或開纖加工的玻璃布較佳為被聚矽氧樹脂所填縫處理。此時，較佳為對玻璃布進行矽烷偶合劑處理，以使聚矽氧樹脂強固地接著於玻璃纖維。作為矽烷偶合劑的種類，有乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等之含乙烯基的矽烷偶合劑、3-環氧丙氧基丙基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷等之含環氧基的矽烷偶合劑、N-2(胺基乙基)3-胺基丙基三甲氧基矽烷、N-2(胺基乙基)3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基三乙氧基矽烷等之含胺基的矽烷偶合劑、3-甲基丙烯醯氧基丙基三甲氧基矽烷等之含(甲基)丙烯醯基的矽烷偶合劑等，尤其在使用含乙烯基的矽烷偶合劑時，玻璃布與聚矽氧樹脂的接著力係升高。 Preferably, the flat or fiber-opened glass cloth is filled with a polyoxyn resin. At this time, it is preferred to subject the glass cloth to a decane coupling agent so that the polyoxymethylene resin is strongly adhered to the glass fiber. Examples of the type of the decane coupling agent include vinyl-containing decane coupling agents such as vinyl trimethoxy decane and vinyl triethoxy decane, 3-glycidoxypropyltrimethoxy decane, and 2-(3). An epoxy group-containing decane coupling agent such as 4-epoxycyclohexyl)ethyltrimethoxydecane, N-2 (aminoethyl) 3-aminopropyltrimethoxydecane, N-2 ( Amino group-containing decane coupling agent such as aminoethyl) 3-aminopropylmethyldimethoxydecane, 3-aminopropyltriethoxydecane, etc., 3-methylpropenyloxypropyl The (meth)acrylonitrile-containing decane coupling agent such as trimethoxydecane, and the like, particularly when a vinyl group-containing decane coupling agent is used, the adhesion force between the glass cloth and the polyoxymethylene resin is increased.
再者，基材布所使用的玻璃布之厚度較佳為0.02mm以上0.1mm以下。若比0.02mm薄，則機械強度不足，熱壓黏時或導熱性聚矽氧橡膠層層合時有變形之虞。又，若比0.1mm厚，則熱壓黏用聚矽氧橡膠薄片中所佔有的玻璃布層之比例變多，薄片全體的導熱率會降低。Further, the thickness of the glass cloth used for the base fabric is preferably 0.02 mm or more and 0.1 mm or less. If it is thinner than 0.02 mm, the mechanical strength is insufficient, and there is deformation when the thermocompression bonding or the thermal conductive polyoxymethylene rubber layer is laminated. Moreover, when it is thicker than 0.1 mm, the ratio of the glass cloth layer which is contained in the thermocompression-bonded polyoxyethylene rubber sheet is increased, and the thermal conductivity of the entire sheet is lowered.
作為對玻璃布含浸聚矽氧樹脂方法，可舉出浸塗法、刀塗法、噴塗法等，特別地若使用浸塗法，則可良好地形成薄的塗層。Examples of the method for impregnating the glass cloth with the polyoxynoxy resin include a dip coating method, a knife coating method, a spray coating method, and the like. Particularly, if a dip coating method is used, a thin coating layer can be favorably formed.
作為玻璃布所含浸的樹脂，較佳為摻合有補強性矽石的聚矽氧橡膠組成物。與其它合成橡膠比較下，摻合有補強性矽石的聚矽氧橡膠組成物之聚合物成分的有機聚矽氧烷係強度非常弱，其本身單獨係無法使用的水準。藉由在有機聚矽氧烷中添加填充劑，尤其補強性矽石，可發揮能使用的強度。As the resin impregnated with the glass cloth, a polyoxyethylene rubber composition in which reinforced vermiculite is blended is preferable. Compared with other synthetic rubbers, the organopolyoxymethane of the polymer component of the polyoxyxene rubber composition in which the reinforced vermiculite is blended is very weak, and is itself unusable at a level which is unusable. By adding a filler to the organopolyoxane, especially reinforcing vermiculite, the strength that can be used can be exhibited.
有機聚矽氧烷係以下述平均組成式(II)所表示者，The organopolyoxyalkylene is represented by the following average composition formula (II).
RaSiO(4-a)/2 (II)R a SiO (4-a)/2 (II)
(式中，a係1.95～2.05之正數)，(where a is a positive number of 1.95 to 2.05),
R表示非取代或取代的一價烴基，具體可例示甲基、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、或此等基的氫原子經氯原子、氟原子等所部分或全部取代之鹵化烴基等，但一般較佳為有機聚矽氧烷的主鏈係由二甲基矽氧烷單位所構成者，或在此有機聚矽氧烷的主鏈導入有乙烯基、苯基、三氟丙基等者。又，可為分子鏈末端經三有機矽烷基或羥基所封鎖者，作為此三有機矽烷基，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。再者，此成分的GPC所測定的聚苯乙烯換算之平均聚合度較佳為200以上，藉由旋轉黏度計所測定的在25℃的黏度較佳為0.3Pa‧s以上，平均聚合度若末達200，則硬化後的機械強度差，有變脆弱之虞。再者，平均聚合度的上限係沒有特別的限制，但較佳為10,000以下。R represents an unsubstituted or substituted monovalent hydrocarbon group, and specifically, 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; an alkenyl group such as a vinyl group or an allyl 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 or wholly substituted with a chlorine atom or a fluorine atom, etc., but it is generally preferred that the main chain system of the organopolyoxane is two A vinyl group, a phenyl group, a trifluoropropyl group or the like is introduced into the main chain of the organopolyoxane. Further, the terminal of the molecular chain may be blocked by a triorganoalkylene group or a hydroxyl group, and examples of the triorganoalkylene group include a trimethyldecyl group, a dimethylvinyl fluorenyl group, a trivinyl fluorenyl group and the like. Further, the average degree of polymerization in terms of polystyrene measured by GPC of the component is preferably 200 or more, and the viscosity at 25 ° C measured by a rotational viscometer is preferably 0.3 Pa ‧ or more, and the average degree of polymerization is At the end of 200, the mechanical strength after hardening is poor, and it becomes fragile. Further, the upper limit of the average degree of polymerization is not particularly limited, but is preferably 10,000 or less.
又，此有機聚矽氧烷較佳為在1分子中具有鍵結於至少2個矽原子的烯基，R中較佳含有0.001～5莫耳%的乙烯基，特佳為0.01～1莫耳%的乙烯基。Further, the organopolyoxane preferably has an alkenyl group bonded to at least two deuterium atoms in one molecule, and R preferably contains 0.001 to 5 mol% of a vinyl group, particularly preferably 0.01 to 1 mol. Ears of vinyl.
補強性矽石係為了得到機械強度優異的聚矽氧橡膠而摻合者，BET法的比表面積較佳為50m2/g以上，特佳為100～400m2/g。作為此補強性矽石，可例示煙霧質矽石(乾式矽石)、沈降矽石(濕式矽石)等。又，可用有機聚矽氧烷、有機矽氮烷、氯矽烷、烷氧基矽烷等，對補強性矽石的表面進行疏水化處理。The reinforcing vermiculite is blended in order to obtain a polyoxyxene rubber having excellent mechanical strength, and the specific surface area of the BET method is preferably 50 m 2 /g or more, and particularly preferably 100 to 400 m 2 /g. Examples of the reinforcing vermiculite include smoky vermiculite (dry vermiculite) and sedimentary vermiculite (wet vermiculite). Further, the surface of the reinforced vermiculite may be hydrophobized by using an organic polyoxane, an organic decane, a chlorodecane or an alkoxy decane.
此補強性矽石的添加量係沒有特別的限制，相對於有機聚矽氧烷100質量份而言，若未達5質量份，則有得不到充分的補強效果之虞，若多於100質量份，則成形加工性會變差，故為5～100質量份的範圍，較佳為20～80質量份的範圍。The amount of the reinforcing vermiculite to be added is not particularly limited, and if it is less than 5 parts by mass based on 100 parts by mass of the organopolysiloxane, a sufficient reinforcing effect cannot be obtained, and if it is more than 100 In the case of the mass portion, the moldability is deteriorated, so the range is from 5 to 100 parts by mass, preferably from 20 to 80 parts by mass.
再者按照需要，亦可添加導熱性填料、著色顏料、耐熱性改良劑、難燃性改良劑、受酸劑等的各種添加劑、或作為補強性矽石分散劑的各種烷氧基矽烷、二苯基矽烷二醇、碳官能矽烷、含矽烷醇基的矽氧烷等。Further, if necessary, various additives such as a thermally conductive filler, a coloring pigment, a heat resistance improver, a flame retardant improver, and an acid acceptor, or various alkoxydecanes as a reinforcing vermiculite dispersant may be added. Phenylnonanediol, carbon functional decane, decyl alcohol-containing decane, and the like.
摻合有補強性矽石的聚矽氧橡膠組成物，係可藉由使用二輥、班百里混合機、捏合機、行星式混合機等的混煉機，將上述成分均勻混合，視需要以100℃以上的溫度進行熱處理而得。The polyxanthene rubber composition blended with the reinforcing vermiculite can be uniformly mixed by using a kneader such as a two-roller, a Banbury mixer, a kneader or a planetary mixer, as needed. It is obtained by heat-treating at a temperature of 100 ° C or higher.
作為使摻合有補強性矽石的聚矽氧橡膠組成物硬化而成為橡膠彈性體之硬化劑，可為通常聚矽氧橡膠之硬化所使用的習知者，此可例示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、二異丙苯基過氧化物等之有機過氧化物，作為加成反應硬化劑，當有機聚矽氧烷具有烯基時，為由在1分子中含有2個以上鍵結於矽原子的氫原子之有機氫聚矽氧烷與鉑族金屬系觸媒所構成者，作為縮合反應硬化劑，當有機聚矽氧烷含有矽烷醇基時，為具有2個以上的烷氧基、乙醯氧基、酮肟基、丙烯氧基等的水解性基之有機矽化合物等，其添加量係可與通常的聚矽氧橡膠同樣。The curing agent for curing the polyoxyxene rubber composition in which the reinforcing vermiculite is blended to form a rubber elastomer may be a conventional one used for curing the polyoxyxene rubber, and this may be exemplified by a radical reaction. Organic peroxides such as di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, etc. The addition reaction hardener is an organohydrogen polyoxyalkylene and a platinum group metal catalyst containing two or more hydrogen atoms bonded to a halogen atom in one molecule when the organic polyoxyalkylene has an alkenyl group. In the case of a condensation reaction hardener, when the organopolyoxane contains a stanol group, it is an organic group having two or more hydrolyzable groups such as an alkoxy group, an ethyloxy group, a ketoximino group, or a propyleneoxy group. The hydrazine compound or the like may be added in the same amount as the usual polyoxyxene rubber.
作為摻合有補強性矽石的聚矽氧橡膠組成物，可使用混煉型聚矽氧橡膠組成物及液狀型聚矽氧橡膠組成物中的任一者。從作業性、成形加工性之點來看，較佳為有機過氧化物硬化型或加成反應硬化型之摻合有補強性矽石的聚矽氧橡膠組成物。As the polyoxyxene rubber composition in which the reinforcing vermiculite is blended, any of the kneaded polyoxyxene rubber composition and the liquid polyoxyxylene rubber composition can be used. From the viewpoint of workability and moldability, a polyoxyxylene rubber composition in which an organic peroxide hardening type or an addition reaction hardening type is blended with reinforcing vermiculite is preferred.
玻璃布所含浸的聚矽氧樹脂，較佳為選擇可在玻璃布上薄且安定地塗佈之樹脂。亦可選擇導熱率高的材料，但全體的導熱率係依賴於玻璃布更勝於聚矽氧樹脂，而且若增多導熱性粉末，則有玻璃布發生網眼堵塞而塗佈面皸裂，或硬度上升而阻礙均勻的壓力傳達之虞。The polyoxyxylene resin impregnated with the glass cloth is preferably a resin which is thin and stable coated on the glass cloth. It is also possible to select a material with a high thermal conductivity, but the overall thermal conductivity depends on the glass cloth to be better than the polyoxynoxy resin, and if the thermal conductive powder is increased, the glass cloth is clogged with the mesh and the coated surface is cleaved, or the hardness is Rise and hinder even pressure transmission.
基材布層上所層合的導熱性聚矽氧橡膠層，較佳為導熱率0.3W/mK以上5W/mK以下(ASTM E 1530)，特佳為0.5～3W/mK。導熱率若小於0.3W/mK，則必須升高熱壓黏溫度或加長壓黏時間，在效率方面會發生不利的情況。即使超過3W/mK，由於基材布層的導熱率係受到限制，而無法期待特別有利的效果。The thermally conductive polyoxyxene rubber layer laminated on the base fabric layer preferably has a thermal conductivity of 0.3 W/mK or more and 5 W/mK or less (ASTM E 1530), particularly preferably 0.5 to 3 W/mK. If the thermal conductivity is less than 0.3 W/mK, the hot press bonding temperature or the long pressurization time must be increased, and an unfavorable situation may occur in terms of efficiency. Even if it exceeds 3 W/mK, since the thermal conductivity of the base fabric layer is limited, a particularly advantageous effect cannot be expected.
形成上述導熱性聚矽氧橡膠層用的導熱性聚矽氧橡膠組成物，較佳為藉由對與玻璃布含浸的樹脂同樣的有機聚矽氧烷100質量份，添加10～1,600質量份的由碳、金屬、金屬氧化物、金屬氮化物、金屬碳化物中選出的至少1種。作為此等的具體例，於金屬中可例示銀粉、銅粉、鐵粉、鎳粉、鋁粉等，於金屬氧化物中可例示鋅、鎂、鋁、矽、鐵等的氧化物，於金屬氮化物中可例示硼、鋁、矽等的氮化物，於金屬碳化物中可例示矽、硼等的碳化物等。The thermally conductive polyoxyxene rubber composition for forming the thermally conductive polyoxyxene rubber layer is preferably added in an amount of 10 to 1,600 parts by mass based on 100 parts by mass of the same organic polyoxane as the resin impregnated with the glass cloth. At least one selected from the group consisting of carbon, a metal, a metal oxide, a metal nitride, and a metal carbide. Specific examples of the metal include silver powder, copper powder, iron powder, nickel powder, and aluminum powder. Examples of the metal oxide include oxides of zinc, magnesium, aluminum, barium, and iron. A nitride such as boron, aluminum or ruthenium may be exemplified as the nitride, and a carbide such as ruthenium or boron may be exemplified as the metal carbide.
按照需要，亦可添加著色顏料、耐熱性改良劑、難燃性改良劑、受酸劑等的各種添加劑、或作為分散劑的各種烷氧基矽烷、二苯基矽烷二醇、碳官能矽烷、含矽烷醇基的矽氧烷等。Various additives such as a coloring pigment, a heat resistance improver, a flame retardant improver, and an acid acceptor, or various alkoxydecane, diphenyldecanediol, and carbon functional decane as a dispersing agent may be added as needed. a decyl alcohol-containing oxime or the like.
導熱性聚矽氧橡膠組成物，係可藉由使用二輥、班百里混合機、捏合機、行星式混合機等的混煉機，將上述成分均勻混合，視需要以100℃以上的溫度進行熱處理而得。The thermally conductive polyoxymethylene rubber composition can be uniformly mixed by using a kneader such as a two-roller, a Banbury mixer, a kneader, or a planetary mixer, and if necessary, at a temperature of 100 ° C or higher. It is obtained by heat treatment.
作為使導熱性聚矽氧橡膠組成物硬化而成為橡膠彈性體之硬化劑，可為通常聚矽氧橡膠之硬化所使用的習知者，此可例示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、二異丙苯基過氧化物等之有機過氧化物，作為加成反應硬化劑，當有機聚矽氧烷具有烯基時，為由在1分子中含有2個以上鍵結於矽原子的氫原子之有機氫聚矽氧烷與鉑族金屬系觸媒所構成者，作為縮合反應硬化劑，當有機聚矽氧烷含有矽烷醇基時，為具有2個以上的烷氧基、乙醯氧基、酮肟基、丙烯氧基等的水解性基之有機矽化合物等，其添加量係可與通常的聚矽氧橡膠同樣。As a curing agent for curing the thermally conductive polyoxyethylene rubber composition to be a rubber elastic body, it can be a conventional one used for curing of a polyoxyxene rubber, and the di-tert-butyl group used for the radical reaction can be exemplified. An organic peroxide such as a peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane or dicumyl peroxide, as an addition reaction hardener, When the organopolyoxane has an alkenyl group, it is a condensation reaction of an organohydrogen polyoxyalkylene containing two or more hydrogen atoms bonded to a halogen atom in one molecule and a platinum group metal catalyst. When the organic polyoxyalkylene contains a stanol group, the curing agent is an organic ruthenium compound having two or more hydrolyzable groups such as an alkoxy group, an etecyloxy group, a ketoximino group or a propyleneoxy group. The amount can be the same as that of the usual polyoxymethylene rubber.
作為導熱性聚矽氧橡膠組成物，可使用混煉型聚矽氧橡膠組成物及液狀型聚矽氧橡膠組成物中的任一者。從作業性、成形加工性之點來看，較佳為有機過氧化物硬化型或加成反應硬化型之導熱性聚矽氧橡膠組成物。As the thermally conductive polyoxyethylene rubber composition, any of a kneaded polyoxymethylene rubber composition and a liquid polyoxyethylene rubber composition can be used. From the viewpoint of workability and moldability, a thermally conductive polyoxymethylene rubber composition of an organic peroxide curing type or an addition reaction curing type is preferred.
關於導熱性聚矽氧橡膠的硬度，較佳為30以上90以下(JIS K 6253中規定的型A硬度計)。再者，當硬度為40以上60以下時，可減低COF的位置偏移，特別適合作為高精細液晶面板用途。The hardness of the thermally conductive polyoxyxene rubber is preferably 30 or more and 90 or less (the type A durometer specified in JIS K 6253). Further, when the hardness is 40 or more and 60 or less, the positional shift of the COF can be reduced, and it is particularly suitable for use as a high-definition liquid crystal panel.
作為對基材布層合導熱聚矽氧樹脂之方法，可舉出刀塗法、柯馬(comma)塗佈法、輥壓塗佈法等，連續地進行塗佈與烘焙。尤其在輥壓塗佈法後，可為無溶劑塗佈，可削減有機溶劑的使用量。As a method of laminating a thermally conductive polyoxymethylene resin to a base material, a coating method, a comma coating method, a roll coating method, etc. are mentioned, and coating and baking are continuously performed. In particular, after the roll coating method, solvent-free coating can be used, and the amount of the organic solvent used can be reduced.
熱壓黏用聚矽氧橡膠薄片全體之厚度較佳為0.1mm以上1mm以下。製作構造上未達0.1mm者係困難。又，若超過1mm，則由於全體的導熱率降低，故必須提高壓黏機的設定溫度，而且由於每單位長度的質量變重，故作業性亦變差。The thickness of the entire hot-pressed polyoxyethylene rubber sheet is preferably 0.1 mm or more and 1 mm or less. It is difficult to make a structure that is less than 0.1 mm. Moreover, when it exceeds 1 mm, since the whole thermal conductivity falls, it is necessary to raise the setting temperature of a press machine, and since the mass per unit length becomes heavy, workability also worsens.
再者，作為均勻地傳達壓力之手段，亦考慮在耐熱薄膜(例如聚醯亞胺薄膜)上層合導熱性聚矽氧橡膠層，但可舉出缺點為需要底塗漆塗佈，因少的熱壓黏次數而薄膜容易變形，由於是以聚矽氧樹脂填縫處理玻璃布之基材布，而凹凸吸收能力差。Further, as a means for uniformly transmitting the pressure, it is also considered to laminate a thermally conductive polyoxyxene rubber layer on a heat-resistant film (for example, a polyimide film), but a disadvantage is that a primer coating is required, and since The film is easily pressed due to the number of times of hot pressing, and the base cloth of the glass cloth is treated by caulking with a polyoxyn resin, and the unevenness absorption ability is poor.
以下顯示實施例及比較例來具體說明本發明，惟本發明不受下述的實施例所限制。The invention is specifically illustrated by the following examples and comparative examples, but the invention is not limited by the following examples.
如表1及2中所示，準備各種的經由柱狀流高壓水噴射開纖法所開纖處理的玻璃布及未處理平織玻璃布，聚矽氧填縫處理係藉由以下的程序來實施。As shown in Tables 1 and 2, various glass cloths and untreated plain woven glass cloths which were opened by the columnar high-pressure water jet opening method were prepared, and the polyoxygen caulking treatment was carried out by the following procedure. .
於捏合機中，在180℃加熱混合1小時的聚甲基乙烯基矽氧烷(相對於二甲基矽氧烷單位100莫耳，在側鏈具有0.15莫耳的乙烯基者，平均聚合度約5,000)100質量份、二甲氧基二甲基矽烷3質量份、鹽酸水(pH3.5)1質量份、Nipsil VN3(日本矽石工業公司製濕式矽石商品名)40質量份。使所得之橡膠複合物100質量份充分溶解於二甲苯300質量份中後，依順序添加1-乙炔基-1-環己醇0.2質量份、氯鉑酸的乙烯基矽氧烷錯合物(鉑含量0.5質量%)0.2質量份、下述式(III)所示的具有直接鍵結於矽原子的氫原子之二甲基聚矽氧烷1.0質量份，而得到塗佈液。 In a kneader, the polymethylvinyloxirane (100 mols relative to dimethyloxane unit and 0.15 mol of vinyl in the side chain) was heated and mixed at 180 ° C for 1 hour, and the average degree of polymerization was obtained. About 5,000) 100 parts by mass, 3 parts by mass of dimethoxy dimethyl decane, 1 part by mass of hydrochloric acid water (pH 3.5), and 40 parts by mass of Nipsil VN3 (trade name of wet vermiculite manufactured by Nippon Kasei Kogyo Co., Ltd.). After 100 parts by mass of the obtained rubber composite was sufficiently dissolved in 300 parts by mass of xylene, 0.2 parts by mass of 1-ethynyl-1-cyclohexanol and a vinyl siloxane derivative of chloroplatinic acid were added in this order ( The platinum content is 0.5% by mass), and 0.2 parts by mass of a dimethylpolysiloxane having a hydrogen atom directly bonded to a ruthenium atom represented by the following formula (III) is 1.0 part by mass to obtain a coating liquid.
連續地將此塗佈液浸塗於乙烯基三甲氧基矽烷處理玻璃布，通過150℃的加熱爐中5分鐘而使硬化，得到基材布。 This coating liquid was continuously dip-coated on a vinyltrimethoxydecane-treated glass cloth, and hardened in a heating furnace at 150 ° C for 5 minutes to obtain a base fabric.
藉由二輥來摻合3種類的聚甲基乙烯基矽氧烷(相對於二甲基矽氧烷單位100莫耳，在末端具有0.025莫耳的乙烯基者，在側鏈具有0.15莫耳的乙烯基者，在側鏈具有0.5莫耳的乙烯基者，平均聚合度皆約5,000)、乙炔黑(平均粒徑35nm，BET比表面積130m2/g)、疏水性矽石(BET比表面積120m2/g)、氧化鈰(BET比表面積140m2/g)，進行混煉而得到橡膠複合物。各成分的摻合量係調整成使得加工硬度成為50，導熱率皆成為 0.5W/mK。 Three types of polymethylvinyloxiranes (100 mils per dimethyl methoxyne unit, 0.025 mil vinyl at the end, and 0.15 mils in the side chain) were blended by two rolls. Vinyl, having a molar of 0.5 moles in the side chain, an average degree of polymerization of about 5,000), acetylene black (average particle size 35 nm, BET specific surface area 130 m 2 /g), hydrophobic vermiculite (BET specific surface area) 120 m 2 /g), cerium oxide (BET specific surface area: 140 m 2 /g), and kneaded to obtain a rubber composite. The blending amount of each component was adjusted so that the processing hardness became 50, and the thermal conductivity was 0.5 W/mK.
於所得之複合物100質量份中，添加甲苯300質量份，均勻混煉後，依順序添加1-乙炔基-1-環己醇0.2質量份、氯鉑酸的乙烯基矽氧烷錯合物(鉑含量0.5質量%)0.2質量份、上述式(III)所示的具有直接鍵結於矽原子的氫原子之二甲基聚矽氧烷1.0質量份。 To 100 parts by mass of the obtained composite, 300 parts by mass of toluene was added, and after uniformly kneading, 0.2 parts by mass of 1-ethynyl-1-cyclohexanol and a vinyl siloxane derivative of chloroplatinic acid were sequentially added. (Platinum content: 0.5% by mass) 0.2 parts by mass of 1.0 part by mass of dimethylpolysiloxane having a hydrogen atom directly bonded to a ruthenium atom represented by the above formula (III).
接著，使用刀塗器，以基材布與導熱性聚矽氧橡膠層的合計厚度成為0.25mm的方式，在基材布上塗佈上述導熱性聚矽氧橡膠組成物，通過160℃的加熱爐中5分鐘而使硬化(表1及2中記載為橡膠層合)。 Then, the thermally conductive polyoxyethylene rubber composition was applied onto the base fabric by a knife coater so that the total thickness of the base fabric and the thermally conductive polyoxysulfide layer was 0.25 mm, and the mixture was heated at 160 ° C. The furnace was hardened for 5 minutes in the furnace (described as rubber lamination in Tables 1 and 2).
又，與基材布重疊使用的單層聚矽氧橡膠薄片，係使用相同的輥壓成形機，以加工厚度成為0.15mm的方式，將上述導熱性聚矽氧橡膠組成物轉印至PET上，通過160℃的加熱爐中5分鐘而使硬化後，剝離PET而得。在基材布上不黏著而重疊此(表1及2中記載使用2片)。 Further, the single-layer polyoxyethylene rubber sheet used in the same manner as the base fabric was transferred to the PET by using the same roll forming machine so that the thickness was 0.15 mm. It was obtained by peeling PET after hardening in a heating furnace of 160 ° C for 5 minutes. This is superimposed on the base fabric without being adhered (two sheets are used in Tables 1 and 2).
為了評價加壓時是否均等地施加壓力，在平坦的玻璃基板上放置感壓紙(富士軟片公司製品名Prescale中壓用)，於其上以玻璃布面朝下的方式重疊所製作的熱壓黏用聚矽氧橡膠薄片，自其上方用常溫的加壓工具(截面3mm×200mm)以5MPa加壓10秒。藉由目視來評價感壓紙的變色狀態。表1及2中顯示結果。In order to evaluate whether pressure is applied evenly during pressurization, a pressure sensitive paper (for Fujifilm Co., Ltd. product name Prescale medium pressure) is placed on a flat glass substrate, and the hot press is superposed on the glass cloth surface downward. The polysilicone rubber sheet was adhered and pressurized with a normal temperature pressing tool (section 3 mm × 200 mm) at 5 MPa for 10 seconds. The discoloration state of the pressure sensitive paper was evaluated by visual observation. The results are shown in Tables 1 and 2.
以設有25μm間距的銅電極之玻璃基板與厚度35μm的COF來夾住厚度22μm的異向性導電接著薄膜，於其上以玻璃布面朝下的方式重疊所製作的熱壓黏用聚矽氧橡膠薄片，更自其上方用經加熱的加壓工具(調整成使異向性導電接著薄膜的到達溫度成為180℃)以5MPa壓黏15秒，藉由顯微鏡來觀察COF末端的電極在壓黏前後有怎樣程度的偏移。以A(未達5μm)、B(5μm以上且未達10μm)、C(10μm以上)來評價壓黏所伴隨的電極偏移之程度。The glass substrate having a copper electrode with a pitch of 25 μm and the COF having a thickness of 35 μm were used to sandwich an anisotropic conductive adhesive film having a thickness of 22 μm, and the thermocompression adhesive polycondensate was formed by overlapping the glass cloth face down. The oxy-rubber sheet was further pressed with a heated press tool (adjusted so that the temperature of the anisotropic conductive film to reach 180 ° C) was pressed at 5 MPa for 15 seconds, and the electrode at the end of the COF was observed by a microscope. How much offset before and after sticking. The degree of electrode offset accompanying the pressure-bonding was evaluated by A (less than 5 μm), B (5 μm or more and less than 10 μm), and C (10 μm or more).
將厚度50μm、35μm的玻璃布層當作基材時，藉由將玻璃布開纖處理，而改善COF壓黏試驗的位置偏移，表示在高精細對應上有效。表1及2中顯示結果。When a glass cloth layer having a thickness of 50 μm or 35 μm was used as a substrate, the positional shift of the COF pressure-bonding test was improved by opening the glass cloth, indicating that it was effective in high-definition correspondence. The results are shown in Tables 1 and 2.
11．．．基材布11. . . Substrate cloth
11a．．．玻璃纖維11a. . . glass fiber
11b．．．聚矽氧樹脂11b. . . Polyoxyl resin
12．．．導熱性聚矽氧橡膠層12. . . Thermal conductive polyoxyethylene rubber layer
圖1係本發明的實施例1之熱壓黏用聚矽氧橡膠薄片的截面圖。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a thermocompression adhesive polyoxyethylene rubber sheet of Example 1 of the present invention.
11．．．基材布11. . . Substrate cloth
11a．．．玻璃纖維11a. . . glass fiber
11b．．．聚矽氧樹脂11b. . . Polyoxyl resin
12．．．導熱性聚矽氧橡膠層12. . . Thermal conductive polyoxyethylene rubber layer
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| CN103113846B (en) * | 2013-03-12 | 2014-12-31 | 深圳市博恩实业有限公司 | Heat-conducting silica gel sheet and manufacturing method thereof |
| CN104947349B (en) * | 2015-06-09 | 2017-01-18 | 铜陵华洋特种线材有限责任公司 | Manufacturing method for high-strength electronic grade glass fiber cloth |
| JP6780289B2 (en) * | 2016-05-09 | 2020-11-04 | 信越化学工業株式会社 | How to repair a box culvert |
| JP6539234B2 (en) * | 2016-07-25 | 2019-07-03 | 富士高分子工業株式会社 | Composite sheet and method for manufacturing the same |
| EP3530709B1 (en) * | 2016-10-14 | 2022-11-02 | Shin-Etsu Chemical Co., Ltd. | Thermally conductive composite silicone rubber sheet and method for manufacturing same |
| JP6448736B2 (en) * | 2017-09-28 | 2019-01-09 | 信越化学工業株式会社 | Thermally conductive sheet |
| JP7149229B2 (en) * | 2019-06-19 | 2022-10-06 | 信越化学工業株式会社 | Thermal conductive composite silicone rubber sheet |
| JP6866916B2 (en) * | 2019-11-13 | 2021-04-28 | 信越化学工業株式会社 | Box culvert construction method and protective sheet |
| KR102380624B1 (en) * | 2020-02-14 | 2022-03-31 | 실리콘밸리(주) | silicone pad for hot press |
| CN112992722B (en) * | 2020-07-27 | 2023-04-25 | 重庆康佳光电技术研究院有限公司 | Adapter plate, mass transfer method and Micro-LED display |
| CN115195230B (en) * | 2022-07-12 | 2023-05-05 | 航天特种材料及工艺技术研究所 | Broadband wave-absorbing and high-heat-conductivity flexible electromagnetic loss material and preparation method thereof |
| CN117757271A (en) * | 2023-12-31 | 2024-03-26 | 东莞市朗晟材料科技有限公司 | Flame-retardant fireproof silicon tape and preparation method thereof |
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| TW200420701A (en) * | 2003-03-07 | 2004-10-16 | Shinetsu Chemical Co | Silicone rubber sheet for thermo compression bonding |
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| CN102414831B (en) * | 2009-03-11 | 2015-09-30 | 信越化学工业株式会社 | The connection sheet of electrode of solar battery, the manufacture method of solar module and solar module |
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| JPH05198344A (en) * | 1992-01-20 | 1993-08-06 | Denki Kagaku Kogyo Kk | Auxiliary sheet for thermocompression bonding |
| TW263595B (en) * | 1994-04-12 | 1995-11-21 | Toshiba Co Ltd | |
| JP2002249984A (en) * | 2001-02-23 | 2002-09-06 | Mitsubishi Rayon Co Ltd | Rolled material of reinforcing fiber cloth, method and apparatus for producing the same |
| TW200420701A (en) * | 2003-03-07 | 2004-10-16 | Shinetsu Chemical Co | Silicone rubber sheet for thermo compression bonding |
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