TWI294904B - Adhesive film, lead frame with adhesive film, and semiconductor device using same - Google Patents
Adhesive film, lead frame with adhesive film, and semiconductor device using same Download PDFInfo
- Publication number
- TWI294904B TWI294904B TW94113639A TW94113639A TWI294904B TW I294904 B TWI294904 B TW I294904B TW 94113639 A TW94113639 A TW 94113639A TW 94113639 A TW94113639 A TW 94113639A TW I294904 B TWI294904 B TW I294904B
- Authority
- TW
- Taiwan
- Prior art keywords
- resin
- adhesive film
- adhesive
- lead frame
- acid
- Prior art date
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 75
- 239000004065 semiconductor Substances 0.000 title claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 145
- 239000011347 resin Substances 0.000 claims abstract description 145
- 239000012790 adhesive layer Substances 0.000 claims abstract description 42
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- -1 polylith Polymers 0.000 claims description 41
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 239000000853 adhesive Substances 0.000 claims description 29
- 230000001070 adhesive effect Effects 0.000 claims description 29
- 150000001412 amines Chemical class 0.000 claims description 23
- 229920000768 polyamine Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 15
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- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 7
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- 229920000728 polyester Polymers 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 21
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 238000006482 condensation reaction Methods 0.000 description 3
- 229930004069 diterpene Natural products 0.000 description 3
- 150000004141 diterpene derivatives Chemical class 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 3
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Classifications
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
- H01L23/49503—Lead-frames or other flat leads characterised by the die pad
- H01L23/4951—Chip-on-leads or leads-on-chip techniques, i.e. inner lead fingers being used as die pad
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
- H01L23/49503—Lead-frames or other flat leads characterised by the die pad
- H01L23/49513—Lead-frames or other flat leads characterised by the die pad having bonding material between chip and die pad
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2477/00—Presence of polyamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2481/00—Presence of sulfur containing polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45144—Gold (Au) as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- Die Bonding (AREA)
Description
129魏。, 九、發明說明: 【發明所屬之技術領域】 推用t發明是有關於—種黏著膜、具黏著膜的導線架以及 使用此導線架的半導體裝置。久 【先技術】 近年來’半導體晶片已進展至多功能大容量的大 °因此’容納晶片之封I结構的尺寸亦須縮小; 刷電路基板(PCB)設計上的限制及電子裝置小 專而求:為配合此趨勢,一些適用於半導體晶片之高度隹 和化及尚密度封賴式的㈣方法已被提出。例如,記二 ,兀件所用的將引腳(Lead)黏著在晶片上而形成的引卿在 晶片上(LQC)結構、以㈣或有機基板取代導線架的㈣ 格陣列〇BGA)、細密球格陣列(FBGA)及銲球在晶片上 (BOC)等以級封裝(csp)結構,以及制晶片堆疊結 堆疊式封裝科。如善用這純術,即可使晶片内配線或 打線配置最佳化,使配線縮短而提高訊號的傳送速率,迷 使封衣結構的尺寸縮小。 在上述各種新型封裝結構中,半導體晶片與導線架之 間皆存在異質材料的黏著介質,其黏著品質對半導體封裝 的可罪性有很大的影響。此黏著介質除了要有可耐受封裝 製程溫度的可靠性以及作業方便性之外,其能使半導體^ 片與導線架穩定地打線連接也是很重要的評估項目。 習知的黏著作業係使用軟膏狀的黏著劑或塗布在耐熱 基材上的黏著劑’例如是使用聚亞醯胺樹脂的熱熔膠型黏 I294m,doc 著劑薄膜,如日本專利公開案平5_105850號、平5_ii276o 號或平5-112761號所述者。然而’由於熱炼膠 ?上作為㈣劑之樹脂的破璃轉換溫度(Tg)甚高 著時所需溫度也很高。因此,將熱_型 二 高度集積化的半導體晶片或銅料線架;被= 月豆上%,後者可能會受熱損壞。 為因應低溫黏著性的需求,一些含破璃轉換溫度較低 的黏著劑曾被使用。然而,由於在打線溫度下此種 树月曰曹變軟,所以在半導體封裝製程的打線步驟中,可能 會有半導體晶片與導線㈣無法f性連接的問題。 【發明内容】 目的之—即是提供—縣具低溫㈣性及打線 穩疋性的黏著膜。 本發明另-目的是提供—種具黏著膜的導線架。 本發明再一目的則是提供一種半導體裝置,其係以本 ㈣之黏者膜黏合導線架與半導體元件而得者。 t明之發明人在研究如何使黏著膜兼具低溫黏著性 性之後發現’如果黏著膜使用在成膜狀態下呈 相1’的特定關係的兩種樹脂,即可解決上述問題。 ㈣’本發明之黏著膜係用以將半導體元件黏著至 包括’熱膜及形成在其單面或兩面上的黏 =八=,黏著劑層含有樹脂Α與樹脂Β,且具有連 ^目:構’其中樹脂Α的玻璃轉換溫度低於樹脂 B’· A為連續相’且樹脂β為分散相。 1294侧 if. doc 在上述黏著膜中,樹脂A與樹脂β二者之一可 =二、聚醯胺、芳香族聚醋餐聚_,或是「 达2或更多種聚合物的混合樹脂。 斤另外^樹脂Α與樹脂Β亦可各自為聚醯胺亞醯胺、聚 0邊、方香族聚酯、聚砜、聚醚砜,或是前述2或更多種 聚合物的混合樹脂。 k > ίΐ’樹脂Α與樹脂Β中可至少有-者為聚醯胺亞醯 胺、屬胺,或是《胺亞_與輯胺的混合樹脂。 此夕^樹月旨A與樹脂B二者中亦可僅有樹脂A為聚 月女亞Si&胺、_胺’或是二者的混合樹脂。 外二在上述黏著膜中,樹脂人例如是由—單體組成 her而得者’此單體組成物含有1〇树%〜⑽的具有石夕 口,的單,。此時樹脂B可由另-單體組成物聚合而得 ’/、另一早體組成物不含具矽酮結構的單體,或是含有 Wt。以上l〇Wt%以下的具有矽酮結構的單體。 =外,樹脂A的Tg可大於等於30°C且小於200°c, 夕B的Tg可為2〇〇〇C〜4〇〇°C。此時樹脂A與樹脂B 曰的Ts差異較佳為20°C〜300QC。 =外,上述黏著膜中的黏著劑層在150°C或更高溫下 勺早性儲存模數可為3MPa〜lOGPa。 甘/if Ϊ,上述黏著膜中的黏著劑層更可含有一耦合劑, 其例如包括矽烷耦合劑。 本叙明之具黏著膜的導線架包括一導線架以及 貼附於其上的前述黏著膜。 129 気。c 架與==構則具有以上一 ^上所4,本發之黏著膜係在㈤無的單或兩面上形 ’其含有連續相的樹脂A與分散相的樹脂B, 二、^^ A的1低於_ B。因此,本發明之黏著膜可 孝方::::’且其在打線穩定性、可靠性、黏著性及作 業方便性#方面的表現皆良好。 亦^外柄明之黏著膜上簡脂如使料定的種類, 亦可進一步提高黏著膜的黏著性。 W 本發明之黏著膜上的樹脂如為聚酿胺或聚醯胺 亞基樹脂,即可進—步提高料性及可靠性。 以J ί 1树明之._莫上各種樹脂的Tg可善加調整, 兼顧低溫黏著性及打線穩定性。 ::,如Ϊ用上述黏著膜’則可得到低溫黏著性、打 且::靠性、黏著性及作業方便性等各方面皆表現 k良的具黏著膜的導線架。 =’如使用上述黏著膜或具黏著膜的導線架,即可 侍到可罪性高的半導體裝置。 【實施方式】 =明之㈣膜制⑽半導體元件歸在被黏著體 _占著二Γ為圖1⑻或1(b)所示之結構,包括财熱膜1 限制二:Λ。半導體兀件所黏著之被黏著體種類無特別 線架、軟膜、有機基板或另一半導體元件等等。 在本發明中,於财熱膜單面或兩面形成之黏著劑層含 if.doc I2949A4 有樹脂A與樹脂b,且且古 脂A的Tgfe於樹脂B Γ ^目^散相之結構,其中樹 散相。以下將為連她,且樹脂β為分 在本:=:7Γ詳― Α及分散相之;^ R *,黏著劑層具有由連續相之樹脂 B所構成的連續相 於,即連續相-分散^ 此’本發明之黏著_具低溫黏著性 在本發明中,樹脂A與樹脂B較佳選自耐孰型的 性樹脂’其例包括聚亞酿胺、㈣亞_、聚醋亞酿胺、 聚醯胺、聚醯胺亞醯胺、芳香族聚酯(聚 及聚醚颯等工程用塑夥。 J來石風 在未施加於黏著膜上時,上述樹脂Α與樹脂β可 分離狀態,而樹脂Α或樹脂Β例如可為含2或更多種、 聚合物的混合樹脂。另外,考慮到黏著性與溶解性,= A與樹脂B較佳使用聚醯胺亞醯胺、聚酿胺、芳夭a取曰 (聚芳香酸酯)、聚颯及聚_颯等樹脂,其效優於妓〜q 在本电明一實施例中,如考慮到黏著性,樹脂A鱼 脂B中較佳有一者是選自由聚醯胺亞醯胺、聚隨胺、二对 族聚酯(聚芳香酸酯)、聚砜及聚醚颯所組成之族君"芳香 脂,或是含有2或更多種上述聚合物的混合樹脂。的才对 於本發明其他實施例中,同樣考慮到黏著性,樹腊A 脂B自^一者較佳皆是選自由聚酿胺亞酿胺、聚醉^ 族聚酯(聚芳香酸酯)、聚砜及聚醚砜所組成之族^中 12949猶 fdoc 脂,或是含有這些聚合物巾的2或更錄的混合樹脂。此 外,於本發明其他實施例中,如考慮黏著性與封妒可靠性, 則樹脂A與_ B二者愤紅少有—者為輯胺㈣ 胺、?《胺或其混合樹脂等含_基的樹脂。這是因為酿 胺基的極性大,故該樹脂與被黏著體間的黏著力會因極 基的交互作用而增強,同時樹脂A與樹脂B之界二的黏著 力也會增強。再者,由於醯胺基具反應性,其可藉由耦合 劑引發微交鏈(crosslinking)反應,以產生強化樹脂的作用。 士匕因此,在本發明中,為進一步提高黏著力,樹脂A與 樹脂B二者中較佳至少有—者為聚醯胺亞酿胺、聚酸胺或 其混合樹脂等含醯胺基的樹脂。另外,當樹脂A盥 中僅有一者為含醯胺基的樹脂時,如以黏著性為考'量,曰則 較佳是連續相的樹脂A為含醯胺基的翻旨,原因在^酿胺 基的極性甚高。再者,更佳情形是樹脂Α與樹脂Β二者皆 為含醯胺基樹脂’如此樹脂Α與樹脂Β的交互作用即可增 強,而不易產生界面剝離的現象。 曰 本發明所用的樹脂Α與樹脂Β較佳為3()。如_〇^ :耐熱型樹脂’更佳為5跑Tg<35〇〇c的耐熱型二旨。1 I ^ 30〇^Tg<200〇C , Β ^
Tg犯圍較佳是2〇〇tTgg〇〇〇c。再者, ,態黏彈性測定法測得之_A的彈 ‘$ 0-Pa ,,, β f〇Mpl ^者看,樹脂A與樹脂B二者中較佳至 有者為基的樹脂。另外,本發明所謂的打線溫 1294m^ 度通常在150°C或以上。 降低當Γΐ…在200°c或以上時,低溫黏著性即會
用,同時也备使打線drp有黏者性’故不易取 的强卜"Ιϊ 線性與可靠性降低。另外,樹脂A 3性=模數如低於_a,則打線胁 樹脂MTg更佳為6〇儀,再佳為二 =曰。A的彈性儲存模數更佳為3〜雇购,再佳為5〜3_ 時,二Γ二Τ§:於2〇〇。°或彈性儲存模數低於10MPa
3U tr卩會降低。再者,樹脂B的1更佳為勝 0 c再佳為25〇〜·。c。樹脂B 為20〜3_MPa,再佳為5〇〜3〇〇〇胳。玲數更仏 樹脂A與_ B的Tg差異較佳為2Q〜3〇〇〇C。 二’低溫黏著性與打線穩定性即難以兼 、^ ^ 時’打線穩定性與可靠度即會降低。
另外,含有本發明所使用之樹脂A與樹脂b的-層,其在室溫以上的最低了 | #者W
性測定法測得之黏著劑層的彈性儲存; 二T ㈣3〜3_MPa,再佳為5〜3_Mpf =〜 發明中含樹脂A與樹脂B之黏著 =本 彈性測定法測得黏著劑層本二‘彈性:= 數曲線’再求出分別位於此曲線的兩個彎㈣ 、 線的交點,此點對應之溫度即為T。 、“1木刀 g 12949觀版 在成膜狀您下’會形成通士 結構的黏著劍組成物,係/事^樹腊A-分散相樹脂3之 擇標準為:樹脂A輿樹的試驗結果來選擇,其選 因相分離而產生混濁,或是農各在自^清漆(讎f)混合時會 離結構而得到不透明_著:耐熱㈣會產生相分 八與黏者劑組合物層。另外,連續相_ ::ΐ及的大小,可以樹脂A與樹脂B各自 ”月之碗濃度或軸條件的調整來控制。 倾細旨A和與其相分離之分散減脂_組合 k擇方面,一般可選用含有化學性 組合。此種組合例如是極性;、細生:) 二非極絲(或非錄結構)之岭κ縣基(或親水妹 構)與疏水基(或疏水結構)之組合。例如,烧基、芳煙基、 貺代烷基減僻絲我代轉 =性成一基、幾基、_基、二= 疋為極性、親水性成分。因此,選擇由該些化學性質祕 構相異的單體各自製得之樹脂的組合,即可得到合適_ 脂A與樹脂B組合。 例如,多含矽S同結構的聚合物與不含石夕酮結構的聚合 ,之間即今易產生相分離。多含石夕_結構的聚合物例如 是:由具⑪晴構之單體在全部單體中佔1Gwt%s以上(較 佳10wt%〜80wt%)的單體組成物聚合而得之聚合物。此處 不含賴結構的聚合物例如是:完全不切赌構的聚合 物,或是雖含矽酮結構,但具矽酮結構之單體在全部單體 中佔不到1_% (較佳不到5wt%)的單餘成物聚^而^ 1294904>ifd〇c 之聚合物,此種聚合物中亦可含有許多高極性的颯基或醚 基。另外,為得樹脂A所用之具矽酮結構單體在全部單體 中的比例較佳為l〇wt%〜80wt% ;如在80wt%以上,則黏著 力會降低。然而,即使所用的兩種聚合物皆是以非極性、 疏水性成分為主,當其結構差異甚大時,其間仍可能產生
相分離。例如,多含矽酮結構之聚合物與含大體積(bulky) h基取代基之聚合物的組合,即易產生相分離。由此可見, 本發明之樹脂組合不限於極性-非極性或親水性_疏水性之 組合,而,可使用各種結構相異之樹脂A與樹脂B的組合。 在選擇樹脂A與樹脂B的組合時,為使樹脂A的丁 低於樹脂B,由含上述結構之單體製得之樹脂的剛 g 素對Tg的影響也必須考慮。 又在本發明中,如以樹脂A與樹脂B 樹脂A含量佔测秦樹脂B佔5〜5_%:丰: 是樹脂A佔50〜90wt%、樹脂B佔1〇〜5〇w “二 脂A佔50〜85wt0/〇、樹脂B佔15〜50wt〇/〇。 土疋对 长钻著劑層中的樹脂B (分散相)的平均 5辦或以下,更佳為!〜〇 寸車U土在 勻,散相的尺寸愈小愈好,且較=二均 二,彳目·分散減構的確認與分散相尺寸;处。另 =田式電顯(SEM)觀察黏著劑層的研磨剖面,二可以 ^尺寸。另外,在以動態师性測定法所 π出平均 :存模數曲線上,也可看出分別來自樹脂A 的彈性 點’故連續相-分散相的結構得以和。’ B的管 13 129,‘ 上述樹脂A與樹脂B較佳使用的聚醯胺亞醯胺或聚醯 联’基本上是由二胺(A)與/或二異氰酸酯(A’)以及酸成分合 成而得者。酸成分可為(B)三叛酸、四綾酸或其反應性衍生 物,以及(C)二羧酸或其反應性衍生物等等,而其中多種併 用亦可。本發明係組合這些反應成分,並調整其反應比例、 反應條件、分子量、黏著劑中添加劑之有無及種類,以及 環氣樹脂等添加樹脂等,以得到上文提及的各種特性。 I 上述二胺例如是:六亞曱二胺、八亞曱二胺、十二亞 甲一^女專亞烧二胺,對苯二胺、間苯二胺、間曱苯二胺等 方知一胺,4,4,-二胺基二苯鱗(DDE)、4,4’-二胺基二苯乙 垸、4,4,-二胺基二苯砜、3,3,-二胺基二苯砜(DDS)、4,4,-二胺基二苯酮、3,3’-二胺基二苯酮、4,4,-二胺基苯甲醯苯 胺等二胺基二苯基衍生物;1,4-二(4-胺基異苯丙基)苯 (f AP)、1,3-二(心胺基異苯丙基)苯、胺基苯氧基) 苯(APB)、1,4_二(3_胺基苯氧基)苯、M^(4_胺基苯氧基) 苯、2,2_二[4-(4-胺基苯氧基)苯基]丙烷(BApp)、2,2_二[4_(3_ φ 胺基苯氧基)笨基]丙烷、二[4-(3-胺基苯氧基)苯基μ風 (m-APPS)、二[4-(4-胺基苯氧基)苯基]颯、2,2_二[4_(4•胺基 苯氧基)苯基]六氟丙烷、以下通式(1)所示之二胺,以及以 下通式(2)所不之矽氧烷二胺等等。這些二胺可以單獨使 用,也可以多種併用。
I2949Q4d0C 在式(1)中,Z表胺基。R!、R2、R3、R4各自為氫或碳 數1〜4之烷基或烷氧基,但四者中至少有2者為烷基或烷 氧基。X 表-CH2-、-C(CH3)2-、-〇-、-s02-、—CO-或-NHCΟ-等官能基。 符合通式⑴的二胺例如是4_4’_二胺基_3,3,,5,5,-四曱 基二苯曱烷、4-4’-二胺基-3,3’,5,5’_四乙基二苯曱烷、4-4,-二胺基-3,3’,5,5’-四正丙基二苯曱烷、4,4’-二胺基-3,3,,5,5,-四異丙基二苯曱烷(IPDDM)、4,4’·二胺基-3,3,,5,5,-四丁基 二苯曱烷、4,4’-二胺基-3,3’-二甲基_5,5’_二乙基二苯甲 烷、4,4’-二胺基-3,3’-二曱基-5,5’-二異丙基二苯曱烷、4,4’-二胺基-3,3’_二乙基-5,5’-二異丙基二苯曱烷、4,4’-二胺基 _3,5_二甲基_3’,5’_二乙基二苯曱烷、4,4’-二胺基-3,5-二曱基 -3’,5’-二異丙基二苯曱烷、4,4’-二胺基-3,5-二乙基_3’,5’_二 異丙基二苯甲烷、4,4’_二胺基_3,5_二乙基-3’,5’-二丁基二 苯曱烷、4,4’-二胺基_3,5_二異丙基_3’,5’-二丁基二苯曱 烷、4,4’-二胺基-3,3’_二異丙基_5,5’_二丁基二苯曱烷、4,4’_ 二胺基-3,3,-二甲基-5,5、二丁基二苯甲烷、4,4’-二胺基 -3,3’-二乙基-5,5’-二丁基二苯曱烷、4-4’-二胺基_3,3’_二曱 基二苯曱烷、4,4’-二胺基-3,3,_二乙基二苯曱烷、4,4’-二胺 基-3,3’_二正丙基二苯曱烷、4,4,-二胺基-3,3,_二異丙基二 苯曱烷、4,4,-二胺基-3,3,-二丁基二苯甲烷、4,4’-二胺基 -3,3,,5-三曱基二苯曱烷、4,4,-二胺基-3,3,,5-三乙基二苯曱 烷、4,4,_二胺基-3,3,,5-三正丙基二苯曱烷、二胺基 -3,3’,5-三異丙基二苯曱烧、4,4,_二胺基-3,3’,5_三丁基二苯 15 I294_ifdoc 甲烷、4,4,_二胺基-3_甲基-3,_乙基二苯曱烷、4,4、二胺基I 甲基-3,-異丙基二苯曱烷、4,4’-二胺基-3-乙基-3’-異丙基二 苯曱烷、4,4,-二胺基-3-乙基-3’-丁基二苯甲烷、4,4’-二胺 基-3-異丙基-3,-丁基二苯曱烷、2,2-二(4-胺基-3,5-二甲苯基) 丙烷、2,2-二(4-胺基-3,5_二乙苯基)丙烷、2,2-二(4-胺基-3,5-二正丙基苯基)丙烷、2,2-二(4-胺基-3,5-二異丙基苯基)丙 烷、2,2_二(4_胺基-3,5-二丁苯基)丙烷、4,4、二胺基 _3,3’,5,5’-四曱基二苯醚、4,4’_二胺基-3,3,,5,5,-四乙基二苯 釀醚、4,4’-二胺基-3,3,,5,5,-四正丙基二苯醚、4,4,_二胺基 -3,3’,5,5,_四異丙基二苯醚、4,4,-二胺基·3,3,,5,5,_四 丁基二 苯醚、4,4’-二胺基_3,3’,5,5,-四曱基二苯颯、4,4,-二胺基 -3,3’,5,5,_四乙基二苯颯、4,4,_二胺基_3,3,,5,5,_四正丙基二 苯颯、4,4’-二胺基-3,3’,5,5’-四異丙基二苯砜、4,4,-二胺基 -3,3’,5,5’_四丁基二苯颯、4,4,-二胺基_3,3,,5,5,-四曱基二苯 酮、4,4’-二胺基_3,3’,5,5’-四乙基二苯酮、4,4,-二胺基 -3,3’,5,5’-四正丙基二苯酮、4,4,-二胺基_3,3,,5,5,_四異丙基 φ 二苯酮、4,4’_二胺基_3,3’,5,5’-四丁基二苯酮、4,4,_二胺基 -3,3’,5,5’-四甲基苯曱醯苯胺、4,4'二胺基-3,3,,5,5、四乙基 苯曱醯苯胺、4,4’-二胺基-3,3,,5,5,-四正丙基苯曱醯苯胺、 4,4’-二胺基-3,3’,5,5’-四異丙基苯曱醯苯胺及4,4、二胺基 -3,3’,5,5’_四丁基苯曱醯苯胺等等。
(2) 16 ⑧ 12949^4咖〇。 式(2)中^與汉8各自為二價有機官能基、心與^為 一價有機官此基,且m1ώ 1 五m為1〜100之整數。尺5與r8各自可 為三亞甲基:四亞甲基、苯撐基、甲苯樓基等。心與r7 各自可為甲土、乙基、苯基等,其中各個&可為同 同的官能基,汉7亦同。 對式(2),石夕氧垸二胺而言,當r5與R8皆為三亞曱基 且〜與為甲基日夺,m等於1及m平均值分別為1〇、 20、30 5G 1GQ左右的化合物,分別例如是市場上販售 的 LP-7100、H161AS、X-22-161A、X-22-161B 二 X_22-161CH161E (皆信越化學工業公司的商品名 上述一異氰酸酯(A,)例如是將以上例示之二胺的胺基 以異氰酸酯基取代而得者,其可單獨使用或多種併用。如 有必要,更可使用前述二胺與二異紐酯的混合物。 聚醯胺亞醯胺或聚醯胺合成用的酸成分可為三羧 酸、四羧酸或其反應性衍生物,或是(c)二羧酸或其反應性 衍生物。成分(B)較佳為芳族三羧酸、芳族四羧酸或其反應 性衍生物’例如是偏苯三甲酸(trimeiiitic acid)軒等單環芳 族三羧酸酐、偏苯三曱酸酐醯氯等偏苯三曱酸酐的反應性 衍生物、苯均四酸(Pyr〇meUitic扣⑹二酐等單環芳族四敌 酉义一酐、—求酮四叛酸二酐、氧聯二鄰苯二曱酸二酐,以 及雙紛A二偏苯三曱酸酯二酐等多環芳族四羧酸二軒等 等。另外,成分(C)較佳為芳族二羧酸或其反應性衍生物, 例如對苯二甲酸、間苯二曱酸等芳族二羧酸,以及對苯二 曱酿氯、間笨二曱醯氯等苯二曱酸的反應性衍生物等等。 I2949£l4ifdoc 這些化合物可以單獨使用或多種併用。 〜^下將進-步例示適用為上述酸成分的芳族二叛酸、 方族^叛酸及芳族四紐等等,其可單獨使用或多種併用。 芳族二羧酸係芳香環上鍵結有兩個羧基者,其中芳香 環可含f環1且芳香環間可以烧撐基、氧或幾基等鍵結: 再者,芳香環上例如可以導入烷氧基、烯丙氧基或鹵素等 不參與縮合反應的取代基。上述芳族二羧酸例如是對苯二 曱酸、間苯二曱酸、二苯醚_4,4,_二羧酸、二苯砜_4,4,_二 _ 魏、聯苯_4,4’-二叛酸及萘-1,5-二叛酸等等,其中以對苯 二曱酸及間苯二曱酸較佳,因其較容易得到。 、 另外,上述芳族二羧酸的反應性衍生物可以是上述芳 族二羧酸的二醯氯及二酯等,其中以對苯二曱醯二氯及間 苯二曱醯二氯較佳。 … 曰 上述芳族三羧酸係芳香環上鍵結有三個羧基者,其中 有兩個羧基分別鍵結至相鄰的兩個碳原子上,芳香環可含 雜環,且芳香環間可以烷撐基、氧或羰基等鍵結。再者, φ 芳香環上例如可以導入烷氧基、烯丙氧基或_素等不參與 縮合反應的取代基。上述芳族三羧酸例如是偏苯三曱酸、' 一本酮-3,3,4’-三叛酸、聯苯_2,3,4’-三敌酸、咕唆_2,36_二 羧酸、苯甲醯苯胺_3,4,4,-三羧酸、萘-1,4,5-三羧酸、2,_甲 氧基一本_-3,4,4’-三缓酸及2’-氯苯甲酿苯胺_3,4,4,-三竣 酸等。 另外,上述芳族三羧酸之反應性衍生物例如是上述芳 族三羧酸的酸酐、醯鹵化物、酯、醯胺及銨鹽等衍生物,
18 (D I2949fl4if.doc 如偏笨二甲酸酐、偏苯三甲酸酐單醯氯、ι,4_二羧基_3_n,n_ 一甲基月女基曱酸基(胺基甲酸基:carbamoyl)笨、l,4-二緩 甲氧基-3-羧基苯、ι,4-二羧基_3_羧苯氧基苯、2,6_二羧基_3_ 羧曱氧基吡啶、1,6-二羧基-5-胺基甲醯基萘,以及由上述 芳知二羧酸與氨、二曱胺或三乙胺等所形成的銨鹽等等, 其中以偏苯三甲酸酐與偏苯三甲酸酐單醯氯較佳。
—上述芳族四羧酸係芳香環上鍵結有四個羧基者,其中 芳香環可含雜環,且芳香環間可以烷撐基、氧或羰基等鍵 結々。再者,芳香環上例如m从餘、糾氧基或鹵 素等不參與縮合反應的取代基。上述芳族四羧酸例如是笨 均四酸、二苯酮_3,3,,4,4,-四羧酸及聯苯-3,3,,4,4,-四羧酸 ^另外上述芳族四幾酸的反應性衍生物例如是苯均四 酉==酐、=苯酮_3,3’,4,4,_四叛酸二肝、聯苯_3,3,,4,4,_四叛 西义=酐一(3,‘二羧苯基)醚的二酐、二(3,4-二羧苯基)砜 的一酐一(3,4_二羧苯氧基)二苯颯的二酐、2,孓二(鄰苯二 六氟狀的二軒、2,2_二[4_(3,4_二鮮氧基)苯基] 、、酐又紛A二偏苯三曱酸酯的二酐、4 4,_二苯氧 j-二異丙標基,二甲酸的二針、4,4、二笨基—ti,: _ 曱基乙知基)]二偏苯三曱酸酯的二酐、萘四魏酸二
Lit醇二偏苯三曱酸酷的二酐,以及癸二醇二偏苯三 曱酸酯的二酐等等。 八偽it:在進行合成時,可以直接採用周知的使二胺成 人咬刀反應的方法,其各反應條件並無特別限制,而 ⑧ I29496Q^ifdoc 可以是任何周知的方法。 (Μ)ΪίΓ用之樹脂A與樹脂Μ自的重量平均分子量 40 3〇^130^000 ? 35,〇〇〇^〇〇,〇〇〇 , # = ^〜7G,_。當重量平均分子量不到孽〇時, 的:題性會過高’而產生黏著劑厚度大幅減少 平均破裂(refl〇W特性變差。反之,當重量 低:而使;I界面潤澤性與黏著性即會過 1文千V體I置的製程無法順利進行。 (GPC)測卜量:重^嶋透層析法 苯乙稀^物所作成的校正㈣者其仙使用聚 聚苯硫喊月::::熱ΪΪ3聚亞酿胺、聚酿胺、聚硬、 ^ ^ 醚醚酮、聚芳香酸酯、聚碳酸酯耸绍绦Ki# 為、。耐熱_厚度並無特贿制,但通常較佳 為5〜200輝,更佳為20〜75_。 吊罕乂 1 土 較佳在鳩或以下,更 或以=====一 f乂下的絕雜耐熱樹脂薄臈。由此觀點來看 薄膜是特佳的選擇。 有水亞酸月女 此外,耐熱膜的表面較佳經過處理, 劑層之間的附著力,從而防止其與點著劑層^:人黏著 20 ⑧ I2949i(4ifdoc 理等化學性處理,“===理、石_合劑處 處理或輝光放電處理等任一 Γ匕 理性處理、電漿 別適用化學性處理或電漿處理。 u,,、特 採用上形f咖的方法亦無特別限制,可 =: 百先將用以形成黏著劑層的樹脂溶解2 =_著劑清漆(即黏著劑组成物),= 土 月果上,然後加熱除去溶劑。如:ς : 兩面上形成有黏著劑層的黏著膜。 卩、到早面或 上述有機溶劑例如是二甲基甲醯胺、二 Ϊ:基:2,㈣甲紛,、環己二:ί甲 土 -、、;二乙—醇二甲基醚、四乙二醇二甲基醚、了 (Τ”雜環己烷、乙二醇單丁基趟乙酸 醇乙酉夂酉日(ethyl cellosolve acetate)或甲笨箄蓉, =土 Ϊ用:或2或多種併用。將樹脂溶解於有機溶劑時 =亚無特別限制,但由黏著劑層的表面狀態及二口 g亦清漆中樹脂成分的含量較佳為!㈣哪。再更作 =亦可依嶋擇之樹脂的組合來調整樹脂成 里以控制黏著劑層的相分離結構。 、 上述黏著劑組成物可以僅含有樹脂八與 以另行添加環氧樹脂或硬化劑、硬化促進劑等等曰。,也可 也可以添加陶瓷粉、玻璃粉、銀粉、鋼粉 ?外: 私顆粒等填充劑,或是_合劑。就封裝結構的可靠性;ζ古, ⑧ 1294簡 if.doc 所添加者較佳為搞合劑;而為提高I馬合劑的效果,樹脂的 主鏈中較佳含有反應性的官能基,特別是醯胺基。 另一方面’在添加填充劑的情形下,其添加量如以樹 脂A與樹脂b的總量1〇〇重量份為準,較佳為丨〜3〇重量 伤’更佳為5〜15重量份。
輕合劑可使用乙烯基矽烷、環氧基矽烷、胺基矽烷、 撒基石夕纟元、鈦酸鹽、I呂螯合劑或錯紹酸鹽等 耦合劑,但以矽烷類耦合劑為佳。矽烷類可為乙烯基三甲 ,矽烷、乙烯基三乙氧矽烷、乙烯基三(Θ甲氧乙氧基)矽 烷、菸(3,4-環氧環己烷基)乙基三甲氧矽烷、产脫水甘油氧 基Oglycidoxy)丙基三甲氧基矽烷、产脫水甘油氧基丙基曱 乙氧基矽烷、N-界(胺乙基)-产胺丙基曱基二曱氧基矽 虼、、产胺丙基二乙氧基矽烷、N_苯基-产胺丙基三甲氧基矽 =«^基三曱減魏料,分子末端具有有機反應 ίΐί基的魏衫劑’其中尤以具環氧基的環氧魏輕 =為佳。另外,上述有機反應性官能基可為環氧基、乙 =麻胺基或誠等官能基。添加魏耦合劑可以提高黏 ^層對_膜_著性,使得轉齡·3帆下被 ::吏用時,黏著劑層與耐熱膜之間不易產生剝離;同時, 以樹脂的總量⑽重量份為 旱其較佺為1〜15wt%,更佳為2〜1〇wt%。 時熱除去塗有黏著劑清漆之耐熱膜上的溶劑 ^所奴的處理溫度只要足叫切_可。 另外,塗布方法並無特別限制,其例如可以是滾筒㈣ 22 ⑧ I2949fl^if.d〇c ^^ it ^ (reverse roll coating)^ jhj (gravure) 塗布法、棒式塗布法(bar coating)、刮刀輪塗布法(c〇nima coating)。另外,令耐熱膜通過黏著劑清漆中以進行塗布也 可以,但此方法的塗布厚度難以控制。 耐熱膜上所形成之黏㈣層的厚度較佳4卜7一, 更佳為10〜30网。黏著劑層的厚度如不到—,黏著性及 生產性都會變差;如超過75/mi,則成本會變高。 #如使用本發明之黏著膜,即容易製得可靠性高的具黏 著版的導線架,其製程方便性及產率皆良好。例如,製程 上可先由本發明之黏著膜切出預定尺寸的膜片,再將 著到導線架上。裁_著_方法只要可正確地將薄膜^ ,預定的形狀’則任何方法皆可。不過,如由料方便性 來看,其較佳使用城切斷黏著膜,再將切下的 黏著在導線架上。此時的黏著温度可為15〇〜35〇cc 為200〜300。0如黏著溫度不到15〇〇c,黏著力奋不f仏 如超過350。〇則黏著劑層會因熱劣化。 ^ 2_>a,較佳G.3〜職Pa。如黏著壓力不狀丨著 力會不;如超過2〇MPa,_著财糾狀=者 壓時間可以是在上述黏著溫度與 ^ i力下可達成a者的任何長度的時間, 方便性,其較佳為0.3〜60秒,更佳為〇 5〜1〇秒。】作業 再者,如使用本發明之黏著膜,即可地 性佳的半導體裝置,其製程方便性及良率蚧好罪 舉例來說,如欲製造-半導體裝置,可^提供以前述 23 Φ 1294觀版 著膜膜的導線架,再將半導體晶片黏著在黏 二=:線架黏著的一面,然後以金線等導線連接導 封衣上述結構,而形成引線在晶片上(LOC)封裝結構。 250〇Γ半導體晶片的黏著溫度可為15G〜3GG°C,較佳為150〜 c ’更佳為150〜·。c。如黏著溫度不到i5〇〇c ,黏著 超過· %,則半導體晶片與黏著劑層會因 H匕。黏者壓力可為(U〜2〇MPa,較佳〇·3〜i〇Mpa。如 3塵力不到G.IMPa,黏著力會不如超過2QMpa,則 钻者诏會溢出預定位置外,而使尺寸精確度變差,且 體晶片也會被破壞。 、 加壓時間可以是在上述黏著溫度與黏著塵力下可達成 黏著的任何長度的時間,但考量到作業方便性,其較佳為 〇·3〜60秒,更佳為0.5〜10秒。 <實例> 以下將以數個實例進一步說明本發明,但其並非用以 限制本發明之範圍。 [製造例1] ^百先準備配備攪拌器、溫度計、氮氣導入管與氯化鈣 =的四頸燒瓶,再於其中加入1.83克(5毫莫耳)的4,4,-二 月女基-3,3’,5,5’_四異丙基二苯曱烷(1]?1)1)]^、2〇5克(5毫莫 耳)的2,孓二[4-(φ·胺基苯氧基)苯基]丙烷(BAPP)及28·3克 的Ν-曱基-2-吡咯酮(ΝΜρ),而使前二者溶解。接著在不使 ’皿度超過2〇〇C的冷卻條件下,於前述溶液中加人2 〇8克 24 I294m,〇c .,莫耳)的偏苯三甲酸酐單醯氯(TAC)。紐在室溫下 見小時,再於不使溫度超過,c的冷卻條件下加入 以人、(11晕莫耳)的三乙胺,之後於室溫下反應3小時, 6 口,聚醯胺酸。所得之聚醯胺酸清漆再於190〇C下反應 J日守,以合成聚醯胺亞醯胺。接著將水注入所 月女亞醯胺的清漆中,再將所得之沉殿分離、粉碎並乾燥, 即得聚醯胺亞醯胺共聚物的粉末,其以GPC法測得之聚苯 乙烯換算Mw為60000。接著,將此聚醯胺亞醯胺粉末溶於 N]V^P中,再將所得之清漆施加在玻璃板上,然後於1〇〇Τ 下乾燥10分鐘,再將其剝離,而後固定在鐵架上,於25〇〇C 下乾燥1小時而得薄膜。接著對所得薄膜進行 其係於1G克荷重、升溫速率㈣分鐘== 測量聚醯胺亞醯胺的丁g,測量結果為265〇c。 [製造例2】 首先提供配備溫度計、攪拌器、氮氣導入管及分餾管 的5升四頸燒瓶,再於氮氣環境下加入η5·2克(〇.6莫^^) 的1,3_二(3-胺基苯氧基)苯(ΑΡΒ)與352克(〇·4莫耳)的矽酮 二胺(信越化學工業公司產製,商品名為X-22_161AS),然 後以2400克的二乙二醇二曱基醚溶解之。接著將所得溶液 冷卻至-10〇C,再於此溫度下加入213克(1.00莫耳)的偏苯 三曱酸酐單醯氯(TAC)。然後在室溫下攪拌1小時,再於 不使溫度超過20QC的冷卻條件下加入115克的三乙胺,' 之後於室溫下反應3小時,以合成聚醯胺酸。所得之聚酉奋 胺酸清漆再於190°C下反應6小時,以合成聚醯胺 胺。接著將所得之反應溶液加入甲醇中,以分離出聚酿胺
(D 25 U9 侧 ifdoc 胺。將此聚醯胺亞醯胺乾燥後,再將其溶於二曱基曱 =胺中,然後將所得溶液加入甲醇中,以再度分離出聚醯 胺亞fe胺。之後進行減壓乾燥,即得聚矽氧烷_聚醯胺亞醯 胺共聚物的粉末,其]\^為47000,Tg為 82°C。 [製造例3] 首先提供配備溫度計、攪拌器、氮氣導入管及分餾管 的5升四頸燒瓶,再於氮氣環境下加入233·6克(〇 8莫耳) 的ΑΡΒ與176克(〇·2莫耳)的石夕酮二胺(信越化學工業公司 _ 產製,商品名X-22-161AS),然後以2000克的二乙二醇二 甲基醚洛解之。接著將所得溶液冷卻至-10。(3,再於此溫 度下加入213克(l.oo莫耳)的偏苯三曱酸酐單醯氯(丁Ac)。 然後在室溫下授拌j小時,再於不使溫度超過2〇〇c的冷 岭餘件下加入115克的三乙胺,之後於室溫下反應3小時, 以合成聚醯胺酸。所得之聚醯胺酸清漆再於19〇CDC下反應 6小時,以合成聚醯胺亞醯胺。接著將所得之反應溶液: ^甲%中,以分離出聚醯胺亞醯胺。將聚醯胺亞醯胺乾燥 • ’再將其溶於二甲基甲酿胺中,然後將所得溶液加入甲 醇=,以再度分離出聚醯胺亞醯胺。之後進行減壓乾燥, 即侍聚矽氧烷-聚醯胺亞醯胺共聚物的粉末,其Μ 46〇〇〇,Tg 為 132°c。 /、 w 匈 [製造例4] 首先提供配備溫度計、授拌器、氮氣導入管及分鶴管 的5升四頸燒瓶,再於氮氣環境下加入389·5克(〇·%莫 的ΒΑΡΡ與12·5克(〇·〇5莫耳)的石夕酮二胺(信越化學工業公 司產製,商品名LP-7100),然後以24〇〇克的ΝΜρ溶解之Α。
(D 26 U94輝doc 接著將所得溶液冷卻至—ΙΟ。。,再於此溫度下加入213克 (1 ·〇〇莫耳)的偏苯三甲酸酐單醯氯(TAC)。然後在室溫下攪 拌1小時,再於不使溫度超過20QC的冷卻條件下加入115 克的二乙胺,之後於室溫下反應3小時,以合成聚酿胺酸。 所得之聚醯胺酸清漆再於19〇QC下反應6小時,以合成聚 酿胺亞酿胺。接著將所得之反應溶液加入曱醇中,以分離 出聚醯胺亞醯胺。將此聚醯胺亞醯胺乾燥後,再令其溶於 一曱基曱醯胺中,然後將所得溶液加入曱醇中,以再度分 鲁 _出聚酸胺亞醯胺。之後進行減塵乾燥,即得聚石夕氧院_ 聚醯胺亞醯胺共聚物的粉末,其Mw為68000,Tg為225°C。 [製造例5] 此例係以製造例1之相同方法製得聚醯胺亞醯胺共聚 物粉末,除了使用2.13克(1〇毫莫耳)的TAC及4.32克、(⑺ 宅莫耳)的一[4_(3-胺基苯氧基)苯基]颯(m_Apps)之外。所 得之聚醯胺亞醯胺粉末的]\/^為62000,丁§為222〇C。 [製造例6] φ 此例係以製造例2之相同方法製得聚矽氧垸_聚醯胺 亞酸胺共聚物粉末,除了使用213克(1.〇〇莫耳)的丁八〇 204.4克(〇·7莫耳)的APB及75克(0.3莫耳)的LP-7100之 外。所得之聚醯胺亞醯胺粉末的]\^為54000,Tg為145。〇 [製造例7] § 此例係以製造例2之相同方法製得聚矽氧烷_聚醯胺 亞醯胺共聚物粉末,除了使用213克(1·〇〇莫耳)的TAC、 287克(〇·7莫耳)的BAPP及75克(〇.3莫耳)的Lp_7i⑻之 I2949^i4ifd〇c 為 58000,Tg 為 175。〇 外。所得之聚酿胺亞醯胺粉末的M [製造例8] 首先準備配備攪拌器、溫度計 ^巧頸燒瓶’再於其中加入以㈣莫耳 ^ 基二苯__、3·69克(9毫莫耳)的BApp及加克: NMP,亚使p者轉。接著在不使溫度超過啊的冷 卻條件下’於前述溶液中加入1〇2克(5毫莫耳
甲酸二醯雜CMW克(5毫莫耳)的對苯二甲酸二酿氣 (TPC)的混合物。然後在室溫下授拌i小時,再於不使溫度 超過20°c的冷卻條件下加人U1克⑴毫莫耳)三乙胺, 之後於室溫T反應6小時,时絲_。接著將水注入 所得之聚_的清漆巾,再將所得之㈣分離、粉碎並乾 燥,即得聚醯胺共聚物的粉末,其Μ*為59〇〇〇,丁為225%。 [製造例9】 §< 此例係以製造例8之相同方法製得聚醯胺共聚物粉 末,除了使用2·03克(1〇毫莫耳)的jpC及2·48克(丨〇毫莫 耳)的4,4’-二胺基二苯砜(DDS)之外。所得之聚醯胺粉末的 Mw為 45000,Tg 為 318QC。 [製造例10】 此例係以製造例8之相同方法製得聚醯胺共聚物粉 末,除了使用2.03克(1〇毫莫耳 耳)的APB之外。所得之聚醯胺粉末的Mw為53〇〇〇,Tg 為 183°C。
[實例1J
(D I2949ii4if.doc f先混合以製造例1之聚雜麵胺粉末30克、、容於 nmp所得之清漆和以製造例2之聚酿胺魏胺粉末冗克 所得之清漆’再添加樹脂重量糊 (Dow C。麵g Silicone公司生產,商品名sh6〇4〇)以樂: 脂含量28痛的清漆,_將其塗布在經 胺膜(宇部興產公司生產,商品名狐EX懒兩面再t Η)純,胁·。G 了錢1G分鐘,即得 兩面白有25㈣厚黏著劑層的黏著膜,其外觀 狀。黏著劑層的Μ 105〇c,且其在15〇〇c彈= 模t為8隐。_ 的邮崎料電_EM)二 可確I、具有製造例i之聚醯胺亞_為分散相、以 玉之?《胺亞_為連續相的連續相·分散相結構,八 If相的平均尺寸為3胸。另外,本發明中彈性儲存模= =用Rhe〇1〇gy公司製造的DVE版寧伽裝置,在= 為脈、振幅為10_及自動控制拉伸荷重二= 行。再者,此黏著膜係、以切_成短條狀 厚牛下進 Γ錄合金製導線架上,而與_.2贿、寬()=5 。讀於23代、聰_力下加壓 3心以加屋附者之’即得具黏著膜的導線 2〇〇°C、壓力3MPa及加壓時間3秒的條件下,將 件加墨黏著在上述具黏著膜導線架的具有黏著劑声的= 上,再於下用金線打線連接導線架與半導^面 未發現打線未受壓附著的情形。然後再% 壤乳樹脂娜(日立域X #公司生產,商品名cel_= 員) 29 12949Mu〇〇 結構)。令此封二:c圖::示之半導體裝置(封裝 4M、時的吸水處理後,再使其通過度,下進行 並未發現封裝上有裂缝。另外,圖 H爐,結果 4為半導體元件、5為導料、6^虎3者為黏著膜、 丨卞踝木、6為封膠、7 wire) ’ 8 則為匯流排條(bus bar)。 ’、、、¥、、泉(bondmg [比較例1] 本例係以實例1的相同方法製得著 製造例2的樹脂之外。此麟贈联除了僅使用 的τ心:: 的外觀透明,其黏著劑層 接著^吏用且G°C T的彈性儲存模數為G.8MPa。 黏者膜,以實例!的相同方法 置,此時發現打線製程中有許多導線未受 ¥體衣 [比較例2】 本例係以實例1的相同方法製得黏著膜,除了 ^造例1的樹脂之外。此黏著膜的外觀透明,其黏著劑層 的%為265〇C,且在150〇C下的彈性儲存模數為2 iGpa曰。 接者使用此㈣膜,以實例1的侧方法製做半導體裝 置,結果發現在其晶方黏著步驟中,於2〇〇〇c的黏著溫度 下晶片與導線架並無法黏合。 ’孤又
[實例2J 此例係以實例1的相同方法製得黏著膜,除使用製造 =1的聚醯胺亞醯胺粉末30克及製造例3的聚醯胺亞醯胺 粉末70克、清漆中樹脂佔2〇械%之外。此黏著膜的外觀 混濁,且其黏著劑層的Tg為145QC,150QC下的彈性儲存 ⑧ 1294爾 fdoc 桓數為8GGMPa。此黏著膜的外觀昭 =劑r面而得)及麵變化曲線 性料m即可確5忍黏著劑層有連續相與分散相,而针 :::線上可看到由混合前之錢脂所造成的,曲: 妝孤㈣刀政相、製造例3的聚醯胺 大’再置於厚0.2酿的鐵鎳合金製導線架上,== 、寬〇.2麵之内引腳接觸。之後於2厂着 =条件下祕3秒以使其_,即得具黏翻的= :耆,在2,、壓力職及加塵時間3秒的停夂 =+導體元件加壓黏著在上述具黏著膜導線架的具有 的:面上,再於峨下用金線打線連接導線架盥 W兀件’此時並未發現打線未受壓附著的情形。铁播 ^述脂封™以轉注成形;進行 對衣即侍圖2所示之半導體裝置(封裝結 結構在wc、85%相對濕度_下進行48小時 理後’使其通過245°C的迴龍’結果並未發現封裳上有 裂縫。 、, [實例3] 本例係以實例1的相同方法製得黏著膜,除使用製造 =4的聚軸亞gf胺粉末3Q克與製造例3的聚軸亞酿胺 釦末70克之外。此黏著膜的外觀混濁,且其外觀的照片(以 光學顯微鏡觀察黏著劑層表面而得)如圖5所示。黏著劑層 31 ⑧ ^2949〇4ifdoc 的1為l38cC,且在150〇C下的彈性儲存模數為75〇Mpa。 f ^劑層的剖面以SEM觀察,可確認其具有製造例4的 聚醯胺亞醯胺為分散相、製造例3的聚醯胺亞醯胺為連續 相的連續相-分散相結構。接著,此黏著膜以切模切成短: 狀,再置於厚〇.2mm的鐵鎳合金製導線架上,而與間距 〇,2mm、寬〇.2mm之内引腳接觸。之後於230%、3MPa 的ί卞件下力口壓3秒以使其附著,即得具黏著膜 接著,在游c、壓力遞a及加壓時間3秒==, 將半導體元件加壓黏著在上述具黏著膜導線 ^面上,再於歡下用金線打線連接導線= 導版7U牛,此時並未發現打線未受塵附著的情形。 用^述聯苯類環氧樹脂封膠咖_9以轉注成縣進行 圖2所示之半導體裝置(封裝結構)。令此封裝 Μ、85%相對濕度阳)下進行48小時的吸水處 =、通過MW的迴鲜爐’結果並未發現封裝上有 【實例4] 例二='二實!ιΠ的相同方法製得黏著膜,除使用製造 於太二Γ女亞酿胺粉末15克與製造例3的聚_亞酸胺 且清漆中樹脂濃度為33wt%之外。此黏著嫉 性儲存模數為740MPa。卖…,: 。下的评 石4切苴且古制 Pa黏者劑層的剖面以SEM觀察,町 的;_亞::=::= I2949〇]4if.d〇c ;X切模切成短條狀,再置於彳G.2mm的鐵鎳合金製 %未上而與間距〇_2mm、寬0.2mm之内引腳接觸。之 I ϋ2/0 C、3MPa的條件下加壓3秒以使其附著,即得具 1者版的導線架。接著,在200°C、壓力3MPa及加壓時
Lit的條件下,將半導體元件加壓黏著在上述具黏著膜 的具有黏著劑層的—面上,再於1帆下用金線打 、κ^導線架與半導體元件,此時並未發現打線未受麼附 者赫、月形然後使用前述聯苯類環氧樹脂封膠CEL- 9200 成形法進行封裝,即得圖2所示之半導體裝置(封裝 ^ 7此封裝結構在85°C、85%相對濕度(RH)下進行 8 ^的财處理後,使其通過2歡的迴賴, 未發現封裝上有裂縫。 [比較例3] 例1 以實例1的相同方法製得黏著膜,除使用製造 於東3(Γ ^胺髓胺粉末7g克與製造例2的魏胺亞酸胺 ^235。「克之外。此黏著膜的外觀混濁,其黏著劑層的% _的立1,且在15〇〇C下的彈性儲存模數為UGPa。黏著 SEM觀察’可確認其具有製造例2的聚酸 連散相、製造例1的聚_賴胺為連續相的 相結構。接著使耻黏著膜,以實例1的相同 度2〇Γ。^㈣裝置,結果發現在晶方黏著步驟的黏著溫 戾200 C下,晶片與導線架無法黏合。 [實例5] 本例係以實例1的相同方法製得混合清漆與黏著膜, ⑧ i2949fl4ifdoc 較用m例8的聚_粉末3G克與製造例2的聚_亞 &私粉末7G克之外。此例在混合清 …製得之黏她⑽有 本例係以實例1的相同方法製得混合清漆鱼黏著膜, 二== 《得之㈣膜的外觀也有明顯的相分= 本例係以實例i的相同方法製得黏著膜,除使用㈣ =的聚=^胺粉末3()克與製造例6的聚醯胺亞_ 二46。。', 1。此黏者膜的外觀混濁,其黏著劑層的A ί ^ C ’且在15G°C下的彈性儲存模數為聰a。所得 隻;化曲線及熱機械分析(雇)的拉伸長度變 = = == =線上顯現出混合前之各樹 ^ 1 ^ 黏者劑層的剖面以SEM觀察,可禮 有ΐΐ例1的聚酿胺亞醯胺為分散相、製造例6的 =讀亞酉监胺為連續相的連續相_分散相結構。接著,此點 ^膜以切模切成短條狀,再置於厚02m 導 ,,而與間距。.-、寬。.2mm的内引 著/Γ3Γα的條件下加壓3秒以使其附著’即得具黏 ¥線架。接著,在23代、壓力3MPa及加壓時間3 ϋϊί'將半導體元件加難著在上述具黏著膜導線 木、/、有黏著劑層的一面上,再於160OCT用金線打線連 34 I2949ft4ifdoc 情开^。導體兀件’此時並未發現打線未受壓附著的 注成形述聯ΐ類環氧樹脂封膠CEL•以轉 m〇 發現封裳上有裂縫。 ㈣〜爐,結果亚未 [實例8】 60 ^ , 見一氣仏例6的聚醯胺亞醯胺 =克了上。此黏著膜的外觀混濁,其黏著劑層q 得薄膜—在 下的彈性儲存模數為mGPa。所 ίΓί曲線如圖6所示,其上顯現出混合前 結果如圖Ί、的弓曲點。黏著劑層的剖面以sem觀察, 為分^制:彳確5忍其具有製造例1的聚醯胺亞酿胺 =6的聚_亞酿胺為連續相的連續相-構。另外,所得之黏著膜十分光滑,且幾乎不會 心。接著,此黏著臈以切模切成 =:錄合金製導線架上’而與間距。.2_、iL: =f=,3Mpa的條件下力挪以 及加㈣間3秒的條件下,將半導體元件加厂i =在上述具黏著膜導線架的具有黏著劑層的一面上,再於 線打線連接導線架與半導體元件,此時並未 每現打、、泉未受歷附著的情形。然後使用前述聯苯類環氧樹 、129的1 脂封膠CEL-9200以轉注成形 =導體裝置(封裝結構)。令此封二^ 對礙度_下進行48小時的吸 再在85 C、85/〇相
=盧’結果並未發現封裝上有;縫。’使其通過245°C 本例係以實例1的相同方法制 例5的聚_亞_粉使用製造 粉末85吉之冰# 兄/、裝^例7的聚醯胺亞醯胺 其具有製造例/It黏著劑層的剖面以SEM觀察,可確認 酿胺亞㉖胺為連,::“續題胺為讀相、*造例7的聚 [»Γι〇Γ 例湖雜麵,除使用製造 8〇克之夕克與製造例6的聚酿胺亞酿胺粉末 146°C。Μ,曰"者臊的外觀混濁,且其黏著劑層的T為 有製造例二=劑層的剖面以SEM觀察’可確認i具 以上各貫例的結果整理列示於下表i中: ⑧ 36 1294904
i<
實例 10 o (N in oo <N tint cn 4^ v〇 寸 T—( 1 着 1 1 實例 9 oo oo (N 〇|ra cn m '#、 卜 卜 r-H 1 I 1 1 實例 8 s o in oo <N Q|n m 00 寸 T—( 1050 碟 碟 實例 7 o 沄 00 (N 雙 cn 混濁 v〇 寸 r-H 1000 碟 實例 6 〇 uo 00 (N Q|m m 分離 雇 1 1 1 1 實例 5 〇 oo (N D|ra cn 分離 1 1 1 1 1 比較 例3 〇 m o 00 (N Q|ra cn 混濁 (η cn (N 1200 1 1 實例 4 oo cn m 〇|m cn 混濁 Ό m 〇 實例 3 o in 00 CN 雙 cn 混濁 00 m o 碟 實例 2 o 沄 〇 (N 〇|n cn tn 寸 o 比較 例2 o o 1—H 00 (N Q|ffl m 透明 vo (N 2100 1 1 比較 例1 〇 τ-Η 00 (N 〇|m m 透明 CN 00 oo o 1 實例 1 〇 沄 in 00 (N cn 混濁 in 〇 r—1 oo 碟 寸 老 in M v〇 vo M <N σ\ to 寸 m ί〇 清漆中的樹脂含量(wt%) 薄膜結構 目視外觀 有無連績相-分散相結構? 0 [T E’(MPa)(在 150°C 下) 20(TC下的黏著性 有無打線未受壓附著? 有無封裝裂缝? (N 〇〇 (N cn IT) 寸 卜 in Ό (N CN (N (N CN (N (N <N oo m 00 組成[()内為莫耳比] < τ-Η Co" Ph < /^s o < H /—'s < Ph < /^s o < H 0 0 ffl Ph < gs r-H < H & Ph < § o' < H S Pk < δ Q Q fc o' < H 〇 in' sS P^i < PQ o" < H /^N o s CL, pL, < 1 s gs r-H ί /^S r-H w Q 〇\ 〇r Oh < l£^ Ph (n r-H ΌΟ Q Q o Oh - _< Ph | τ-Η u Ph SH6040 (矽烷耦合劑) CN CO 卜 r-H 寸 to oo ON 〇 < < <d PQ PQ CQ PQ 31 鲁
4 6 I2949fl4>ifd〇c 雖然本發明已以較佳實施例揭露如上,然其並 限定本發明’任何熟習此技藝者’在不脫離本;明用以 和範圍内’當可作些許之更動_飾,因此本發明之^ 範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 分別二: 例之黏著膜的剖面圖,其中⑻、⑻ 二耐熱膜的兩面、單面上有黏著劑層的實施例。 刮每圖ί為使用本發明之黏著膜的半導體裝置的實施例的 =3為士發明貫例2之黏著劑層的外觀照片。 二:為實例2之黏著劑層的黏彈性變化曲線 _ 5為實例3之黏著劑層的外觀照片。 8之黏者劑層的黏彈性變化曲線圖。 Τ’層的熱機械分析(TMA)結果。 ^為貫例8之黏者劑層的剖面的職 牛符號說明】 耐熱膜 黏著劑層 黏著膜 半導體元件 導線架(lead frame) 封膠 導線(bonding wire) 匯流排條(bus bar) ⑧ 38
Claims (1)
- I2949iQ4pif.doc 十、申請專利範圍: 1. 一種黏著膜,用以將一半導體元件黏著在一被黏著 體上,包括: 一耐熱膜;以及 形成在該耐熱膜的單面或兩面上的黏著劑層, 其中該黏著劑層含有樹脂A與樹脂B,且具有連續相 -分散相結構,其中該樹脂A的玻璃轉換溫度(Tg)低於該樹 脂B ’該樹脂A為連績相’且該樹脂B為分散相。 2. 如申請專利範圍第1項所述之黏著膜,其中該樹脂 A與該樹脂B之一為聚醯胺亞醯胺、聚醯胺、芳香族聚酯、 聚石風、聚醚諷,或是含前述2或更多種聚合物的混合樹脂。 3. 如申請專利範圍第1項所述之黏著膜,其中該樹脂 A與該樹脂B各自為聚醯胺亞醯胺、聚醯胺、芳香族聚酯、 聚颯、聚醚颯,或是前述2或更多種聚合物的混合樹脂。 4. 如申請專利範圍第1項所述之黏著膜,其中該樹脂 A與該樹脂B二者中至少有一為聚醯胺亞醯胺、聚醯胺, 或是聚醯胺亞醯胺與聚醯胺的混合樹脂。 5. 如申請專利範圍第1項所述之黏著膜,其中該樹脂 A為聚醯胺亞醯胺、聚醯胺,或是二者的混合樹脂。 6. 如申請專利範圍第1項所述之黏著膜,其中該樹脂 A係由一單體組成物聚合而得,該單體組成物含有10wt%〜 80wt%的具有石夕S同結構的單體。 7. 如申請專利範圍第6項所述之黏著膜,其中該樹脂 B係由另一單體組成物聚合而得,該另一單體組成物不含 39 ⑧ I2949fl4ifdoc 具石夕幡構的單體,或是含有_%以上、i_%以下的具 有石夕i同結構的單體。 、 A =11請#利_第1項所述之黏著膜,其中該樹脂 、璃轉換溫度大於等於30oc且小於200oc,且該樹脂 的玻璃轉換溫度為2〇〇〇c〜4⑽。c。 A與專8項所述之黏轴,其中該樹脂 ”二3曰▲一者間的玻璃轉換溫度差異為20°C〜300。〇.如申明專利範圍第1項所述之黏著膜,苴哕 150〇C 劑層更対^目㈣嫩㈣,其愼著 12·如巾請專利範圍f u項所述之 合劑包括-魏麵合劑。 顿其中摘 13· —種具黏著膜的導線架,包括: 一導線架;以及 導線2請專利軸第1項所述絲著膜,其係貼附於該 以申請專利範圍第1項所 導體元件所得之結構。 、、14· 一種半導體裝置,其具有 述之黏著膜黏合一導線架與一半
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US6700185B1 (en) * | 1999-11-10 | 2004-03-02 | Hitachi Chemical Co., Ltd. | Adhesive film for semiconductor, lead frame and semiconductor device using the same, and method for manufacturing semiconductor device |
KR100644749B1 (ko) * | 2005-07-22 | 2006-11-14 | 삼성전기주식회사 | 동박적층판 및 다층 인쇄회로 기판 |
JP4719042B2 (ja) * | 2006-03-16 | 2011-07-06 | 株式会社東芝 | 半導体装置の製造方法 |
EP2053108A4 (en) * | 2006-08-04 | 2012-12-12 | Hitachi Chemical Co Ltd | FILM ADHESIVE, ADHESIVE SHEET, AND SEMICONDUCTOR DEVICE USING SAME |
EP3109214B1 (en) * | 2014-02-20 | 2020-11-11 | Sekisui Chemical Co., Ltd. | Interlayer for laminated glass, and laminated glass |
JP7003795B2 (ja) * | 2017-03-29 | 2022-01-21 | 荒川化学工業株式会社 | ポリイミド、接着剤、フィルム状接着材、接着層、接着シート、樹脂付銅箔、銅張積層板、プリント配線板、並びに多層配線板及びその製造方法 |
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KR0128814B1 (ko) * | 1993-07-05 | 1998-04-07 | 강박광 | 이소포론디아민 구조를 함유하는 신규 폴리아미드이미드수지 |
JP3347651B2 (ja) * | 1997-09-17 | 2002-11-20 | 株式会社巴川製紙所 | 電子部品用接着テープ |
JP3410642B2 (ja) * | 1997-09-26 | 2003-05-26 | 株式会社巴川製紙所 | 電子部品用耐熱性接着剤組成物 |
JP3950560B2 (ja) * | 1998-08-14 | 2007-08-01 | 株式会社巴川製紙所 | 電子部品用接着剤および電子部品用接着テープ |
CN1238458C (zh) | 2000-01-19 | 2006-01-25 | 日立化成工业株式会社 | 半导体用粘接膜、带有半导体用粘接膜的导线框及使用了该导线框的半导体装置 |
WO2001074962A1 (en) * | 2000-03-31 | 2001-10-11 | Hitachi Chemical Co., Ltd. | Adhesive composition, method for preparing the same, adhesive film using the same, substrate for carrying semiconductor and semiconductor device |
-
2005
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- 2005-04-30 KR KR1020050036463A patent/KR100701988B1/ko not_active IP Right Cessation
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KR20060047674A (ko) | 2006-05-18 |
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