TW200811259A - Adhesive composition, adhesion film, and peeling method - Google Patents
Adhesive composition, adhesion film, and peeling method Download PDFInfo
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- TW200811259A TW200811259A TW96125254A TW96125254A TW200811259A TW 200811259 A TW200811259 A TW 200811259A TW 96125254 A TW96125254 A TW 96125254A TW 96125254 A TW96125254 A TW 96125254A TW 200811259 A TW200811259 A TW 200811259A
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
- C09J125/14—Copolymers of styrene with unsaturated esters
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
Abstract
Description
200811259 九、發明說明 【發明所屬之技術領域】 本發明係有關黏著劑組成物、黏著薄膜及剝離方法， 特別是有關藉由加熱至200 °C以上後發泡之黏著劑組成物 ’黏著薄膜及經由發泡後由該黏著劑組成物所成之黏著劑 層輕易由基板剝離之方法。 【先前技術】 伴隨著手機、數據AV機器及1C卡等高機能化，對於 搭載半導體聚矽氧元件（以下稱元件）之小型化、薄型化 及筒集成化之要求提高。又，針對CSP ( chip size package )及MCP ( multi-chip package )所代表之複數元件之封裝 化集成電路亦被要求其薄型化。其中，於一個半導體封裝 之中搭載複數之半導體元件之封裝系統（SiP )係使所搭 載元件進行小型化、薄型化及高集成化，於實現電子檄器 高性能化、小型化且輕量化上，爲極重要之技術。 爲了實現電子機器之高性能化、小型化且輕量化，務 必使元件厚度薄至150//m以下。更於CSP及MCP中進，行硏 削元件至100 // m以下，1C卡中硏削元件至50 /z m以下，務 必進行爲薄板化之硏削步驟。惟，元件基板之半導體晶圓 經由硏削後變薄，因此其強度變弱，於半導體晶圓易產生 裂化及翹曲。又，薄板化之半導體晶圓無法自動化運送， 務必藉由人工進行。 因此’被開發一種於硏削半導體晶圓中藉由貼合稱爲 -5- 200811259 支撐板之玻璃或硬質塑膠等，保持半導體晶圓之強度，防 止裂化產生及半導體晶圓之翹曲產生之晶圓支撐系統。又 ，日本國公開專利公報：特開2005 - 1 9 1 550號公報（公開 日：平成17年7月14日）中被揭示藉由使用晶圓支撐系統 後，使硏削之半導體晶圓運送進行自動化之技術。 晶圓支撐系統中，爲暫時性貼合半導體晶圓與支撐板 之黏著物質不僅其黏著強度強，且最後支撐板爲由半導體 晶圓取出，務必易於由薄半導體晶圓，剝離，且無殘存於 半導體晶圓中。 爲剝離黏著物質，爲必須使剝離液浸漬於位於支撐板 與半導體晶圓間之黏著物質層（黏著劑層），故，由半導 體晶圓至剝離支撐板爲止之時間極爲耗時。因此，爲容易 剝離暫時黏著之支撐板與半導體晶圓，務必使黏著物質之 黏著力於剝離時做某程度之低減。 如：日本國公開專利公報：特開2004-43732號公報（ 公開日：平成1 6年2月1 2日）及日本國公開專利公報：特 開2 004-2 547號公報（公開曰：平成16年1月8日）中被揭 示有預先含有經由光及/或熱之發泡成份做爲黏著物質之 構成成份，於剝離時使黏著物質發泡，減少該黏著物質之 黏著力。 又，日本國公開專利公報：特開2005-290 1 46號公報 (公開日：平成17年10月20日）中被揭示有進一步含有經 由照射光產生酸之成份，不僅藉由發泡作用，亦藉由酸之 作用減少黏著物質之黏著力，做成容易剝離之方法。 -6- 200811259 藉由晶圓支撐系統之元件製作步驟中，具有加熱至 loot之步驟，因此，經由loot：加熱後發泡之先行技術之 黏著物質時，於加熱步驟中降低黏著力。又，具有至1 〇〇 °C之耐熱性黏著物質中，藉由200 °c以上加熱後，於剝離 液形成不溶物質，因而導致不易剝離之問題。 另外，上述硏削步驟中，於螢光燈等之光照射下進行 作業，因此務必使用經由光不降低黏著力之黏著物質。 【發明內容】 本發明鑑於上述問題點，其主要目的爲提供一種於 1 00 °C之加熱下不降低黏著力，加熱至200 °c以上後，仍可 輕易剝離之黏著劑組成物、黏著薄膜及此等剝離方法。 爲達成該目的之第1形態係以將含有苯乙烯與具有含 經由熱作用後由酯鍵所解離之基的環式構造之（甲基）丙 烯酸酯以及由鏈式構造所成之（甲基）丙烯酸烷基酯之單 量體組成物進行共聚所成之聚合物爲主成份者爲其特徵之 黏著劑組成物。 爲達成該目的之第2形態係以將含有苯乙烯與具有含 經由熱作用由酯鍵所解離之基的環式構造之（甲基）丙烯 酸酯以及由鏈式構造所成之（甲基）丙烯酸烷基酯之單量 體組成物進行共聚所成之聚合物作爲主成份，其特徵係藉 由進行2 0 0 °C以上之加熱後發泡之黏著劑組成物。 爲達成該目的之第3形態係於薄膜上具備有含有第1或 第2形態之黏著劑組成物的黏著劑層爲特徵之黏著薄膜。 200811259 爲達成該目的之第4形態係於基板上塗佈第1或第2形 態之黏著劑組成物’爲使該黏著劑組成物乾燥而進行預焙 燒，或於基板上經由黏著第3形態所記載之黏著薄膜，於 該基板上形成黏著劑層，由該基板剝離上述黏著劑層之方 法，於20 0 °C以上進行該基板及該黏著劑層之加熱步驟後 ，於該基板與該黏著劑層之間使剝離液進行滲透之步驟者 爲其特徵之剝離方法。 本發明其他目的、特徵、及優點可由下式所載充分理 解。又，本發明之優點可參考添附圖面之以下說明而理解 【實施方式】 [實施形態1] 針對本發明黏著劑組成物之一實施形態進行以下說明 〇 本發明黏著劑組成物係以將含有苯乙烯與具有含經熱 作用後由酯鍵解離之基的環式構造之（甲基）丙烯酸酯以 及由鏈式構造所成之（甲基）丙烯酸烷基酯之單量體組成 物進行共聚所成之聚合物做爲主成份之黏著劑組成物。 該黏著劑組成物只要爲黏著劑之用途使用者，其具體 用途並未特別限定。本實施形態中，列舉用於暫時性，爲 使該黏著劑組成物爲晶圓支撐系統之半導體晶圓黏著於支 撐板之用途時，進行說明。 其中，本明細書等中所謂「主成份」係指含於組成物 -8- 200811259 之總成份中’超出5〇質量％之成份’較佳者爲7〇質量％以 上，更佳者爲1 0 0質量％。 又，本明細書等中所謂「支撐板」係指硏削半導體晶 圓時，經由貼合於半導體晶圓後，爲保護硏削後薄化之半 導體晶圓不產生裂化及翹曲所使用之基板。 本實施形態中，首先針對構成黏著劑組成物主成份之 單量體組成物之種類進行說明，再針對該單量體組成物之 配合量進行說明。 (具環式構造之（甲基）丙烯酸酯之種類） 具有構成本實施形態之黏著劑組成物主成份之聚合物 的單量體組成物之一構成成份之環式構造的（甲基）丙烯 酸酯爲含有由經由熱作用之酯鍵解離之基。更具體者上述 ((甲基）丙烯酸酯爲具有下述一般式（1):200811259 IX. INSTRUCTIONS OF THE INVENTION [Technical Fields of the Invention] The present invention relates to an adhesive composition, an adhesive film, and a peeling method, and more particularly to an adhesive composition which is foamed by heating to a temperature above 200 ° C. A method in which an adhesive layer formed of the adhesive composition is easily peeled off from a substrate after foaming. [Prior Art] With the increase in the functionality of mobile phones, data AV equipment, and 1C cards, the requirements for miniaturization, thinning, and integration of semiconductor polysilicon devices (hereinafter referred to as components) have increased. Further, packaged integrated circuits for a plurality of components represented by CSP (chip size package) and MCP (multi-chip package) are also required to be thinned. Among them, a package system (SiP) in which a plurality of semiconductor elements are mounted in one semiconductor package is used to reduce the size, thickness, and integration of the mounted components, thereby achieving high performance, miniaturization, and weight reduction of the electronic device. , is a very important technology. In order to achieve high performance, miniaturization, and weight reduction of electronic equipment, it is necessary to make the thickness of the element as thin as 150//m or less. In the CSP and MCP, the boring component is below 100 // m, and the boring component is below 50 /z m in the 1C card. Be sure to perform the boring step for thinning. However, since the semiconductor wafer of the element substrate is thinned by dicing, the strength thereof is weak, and the semiconductor wafer is liable to be cracked and warped. Moreover, thin-filmed semiconductor wafers cannot be automated, and must be performed manually. Therefore, it has been developed to maintain the strength of semiconductor wafers by preventing the cracking and the warpage of semiconductor wafers by bonding glass or rigid plastics called 5-5.011259 support plates in boring semiconductor wafers. Wafer support system. In addition, Japanese Laid-Open Patent Publication No. 2005-1191 550 (Publication Date: July 14, 1997) is disclosed to transport smashed semiconductor wafers by using a wafer support system. The technology to automate. In the wafer support system, the adhesive material for temporarily bonding the semiconductor wafer and the support plate not only has strong adhesive strength, but also the final support plate is taken out from the semiconductor wafer, and must be easily peeled off from the thin semiconductor wafer, and there is no residual In semiconductor wafers. In order to peel off the adhesive material, it is necessary to immerse the peeling liquid in the adhesive layer (adhesive layer) between the support plate and the semiconductor wafer, so that the time from the semiconductor wafer to the peeling of the support plate is extremely time consuming. Therefore, in order to easily peel off the temporarily adhered support plate and the semiconductor wafer, it is necessary to make the adhesion of the adhesive substance to a certain extent and to reduce it. For example, Japanese Laid-Open Patent Publication No. 2004-43732 (Publication Date: February 12, 2002) and Japanese Laid-Open Patent Publication No. 2 004-2 547 (Publication: Heisei In January 8th, 2016, it was revealed that a foaming component which is a light-and/or heat-containing foaming component is contained in advance, and the adhesive substance is foamed at the time of peeling to reduce the adhesive force of the adhesive substance. Further, Japanese Laid-Open Patent Publication No. 2005-290 1 46 (Publication Date: October 20, 2009) is disclosed to further contain a component which generates an acid via irradiation light, not only by foaming action, It also reduces the adhesion of the adhesive by the action of acid, making it easy to peel off. -6- 200811259 In the component fabrication step of the wafer support system, there is a step of heating to loot. Therefore, when the adhesive material of the prior art is foamed by the loot: heating, the adhesion is lowered in the heating step. Further, in the heat-resistant adhesive material having a temperature of up to 1 〇〇 ° C, after heating at 200 ° C or higher, an insoluble matter is formed in the peeling liquid, which causes a problem that peeling is less likely to occur. Further, in the boring step, the operation is performed under the irradiation of light such as a fluorescent lamp, and therefore it is necessary to use an adhesive which does not lower the adhesive force by light. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its main object is to provide an adhesive composition and an adhesive film which can be easily peeled off without being lowered under heating at 100 ° C and heated to 200 ° C or more. And these stripping methods. The first aspect for achieving the object is a (meth) acrylate containing a styrene structure having a ring structure which is dissociated by an ester bond via a thermal action, and a chain structure. An adhesive composition characterized by a polymer obtained by copolymerizing a monolithic composition of an alkyl acrylate. The second aspect for achieving the object is a (meth) acrylate containing a styrene structure having a ring structure which is dissociated by an ester bond via a thermal action, and a (meth) structure formed by a chain structure. A polymer obtained by copolymerizing a single-component composition of an alkyl acrylate is used as a main component, and is characterized in that it is an adhesive composition which is foamed by heating at 200 ° C or higher. The third aspect for achieving the object is an adhesive film comprising a pressure-sensitive adhesive layer containing the adhesive composition of the first or second aspect on the film. 200811259 In order to achieve the fourth aspect of the invention, the first or second embodiment of the adhesive composition is applied to the substrate to dry the pre-baking or drying the adhesive composition on the substrate. The adhesive film is described, an adhesive layer is formed on the substrate, and the adhesive layer is peeled off from the substrate. After the substrate and the adhesive layer are heated at 20 ° C or higher, the substrate and the adhesive are adhered to the substrate. A peeling method characterized by a step of infiltrating the stripping liquid between the layers. Other objects, features, and advantages of the present invention will be fully understood from the following description. Further, the advantages of the present invention can be understood by referring to the following description of the accompanying drawings. [Embodiment 1] An embodiment of the adhesive composition of the present invention will be described below. The adhesive composition of the present invention will contain Copolymerization of styrene with a (meth) acrylate having a cyclic structure containing a group which is thermally dissociated by an ester bond, and a monomeric composition of an alkyl (meth) acrylate formed by a chain structure The resulting polymer is used as the adhesive composition of the main component. The adhesive composition is not particularly limited as long as it is a user of the adhesive. In the present embodiment, a description will be given for the purpose of temporarily attaching a semiconductor wafer in which the adhesive composition is a wafer supporting system to a support plate. In addition, the term "main component" in the present specification refers to a component of more than 5% by mass in the total composition of the composition -8-200811259, preferably 7 〇 mass% or more, and more preferably 1 0 0 mass%. In addition, the term "support plate" in the present specification refers to a semiconductor wafer that is bonded to a semiconductor wafer after being diced to a semiconductor wafer, and is used for protecting the thinned semiconductor wafer from cracking and warpage. Substrate. In the present embodiment, the type of the single-body composition constituting the main component of the adhesive composition will be described first, and the blending amount of the single-body composition will be described. (Type of (meth) acrylate having a ring structure) The (meth)acrylic acid having a ring structure of one of the monolithic compositions constituting the polymer of the main component of the adhesive composition of the present embodiment The ester is a group containing a group which is dissociated by an ester bond via heat. More specifically, the above ((meth) acrylate has the following general formula (1):
(R1代表氫原子或甲基，R3代表單鍵，或具有第3級碳原 子之碳數3〜5之伸烷基，R4代表氫原子，碳數1〜4之烷基， R5代表與鄰接之碳原子同時形成具有取代基亦可之烴環之 碳數3〜1 9之烴基，惟上述一般式（1 )中，R3爲單鍵，R4 爲氫原子時之化合物除外） 所示構造之單量體。 -9 - 200811259 該一般式（1 )中R4所示之低級烷基只要分別爲碳數 1〜4之烷基，可爲直鏈狀，亦可爲支鏈。具體例如：甲基 、乙基、η-丙基、異丙基、n_ 丁基、第二-丁基及第三-丁 基等例。 又’ R3代表單鍵或具有第3級碳原子之碳數3〜5之伸烷 基’做爲具有第3級碳原子之碳數3〜5之伸烷基例者如以下 之例。(R1 represents a hydrogen atom or a methyl group, R3 represents a single bond, or a alkyl group having a carbon number of 3 to 5 having a carbon atom of a 3rd stage, R4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and R5 represents adjacency The carbon atom may simultaneously form a hydrocarbon group having a carbon number of 3 to 19 in the hydrocarbon ring which may have a substituent, except that in the above general formula (1), R3 is a single bond, and R4 is a compound in the case of a hydrogen atom) Single body. -9 - 200811259 The lower alkyl group represented by R4 in the general formula (1) may be a linear or branched chain as long as it is an alkyl group having 1 to 4 carbon atoms, respectively. Specific examples thereof include methyl, ethyl, η-propyl, isopropyl, n-butyl, second-butyl and tert-butyl. Further, 'R3 represents a single bond or an alkylene group having a carbon number of 3 to 5 having a third-order carbon atom', and examples of the alkylene group having a carbon number of 3 to 5 having a third-order carbon atom are as follows.
—CH：3. C-gHg"- 另外’ R5係與鄰接之碳原子同時形成具有取代基亦可 之碳數3〜19之單環式或多環式烴環。做爲單環式烴環之具 體例者如：環戊烷、環己烷、環庚烷、環辛烷等例。又， 做爲多環式烴環者如：2環式烴環、3環式烴環、4環式烴 環等例。具體例如：金剛烷、原菠烷、異原菠烷、三環癸 院、四環月桂院等之多環式烴環等例。做爲與鄰接之碳原 子同時具有取代基亦可之烴環者於上述具體例中，特別以 環己烷或金剛烷爲最佳。 做爲此上述一般式（1 )所示之（甲基）丙烯酸酯之 更理想具體例如：下述式（2 )或（3 )所示之（甲基）丙 烯酸酯例。 -10- 200811259—CH:3. C-gHg"- Further 'R5 is a monocyclic or polycyclic hydrocarbon ring having a carbon number of 3 to 19 which may have a substituent at the same time as the adjacent carbon atom. Examples of the monocyclic hydrocarbon ring include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Further, examples of the polycyclic hydrocarbon ring include a 2-ring hydrocarbon ring, a 3-ring hydrocarbon ring, and a 4-ring hydrocarbon ring. Specifically, for example, a polycyclic hydrocarbon ring such as adamantane, protocorane, isopentane, tricyclic urn, or a four-ring laurel. As the hydrocarbon ring which may have a substituent at the same time as the adjacent carbon atom, in the above specific examples, cyclohexane or adamantane is particularly preferable. More preferably, the (meth) acrylate represented by the above formula (1) is exemplified by a (meth) acrylate represented by the following formula (2) or (3). -10- 200811259
(式中，R1爲氫原子或甲基，R4爲碳數1〜4之烷基，R6爲 氫原子或碳數1〜4之烷基，a爲0、1或2 )。 此等中又以1-甲基-1 -環戊基（甲基）丙烯酸酯、1 -乙 基-1-環戊基（甲基）丙烯酸酯、1-甲基-1-環己基（甲基 )丙烯酸酯、1-乙基-1-環己基（甲基）丙烯酸酯、2-甲 基-2-金剛院基（甲基）丙嫌酸酯、2·乙基-2 -金剛院基（ 甲基）丙烯酸酯等爲較佳，更佳者爲1 -乙基-1 -環己基（甲 基）丙烯酸酯、2-甲基-2-金剛烷基（甲基）丙烯酸酯。 (由鏈式構造所成之（甲基）丙烯酸烷基酯之種類） 本明細書等中「由鏈式構造所成」（甲基）丙烯酸烷 基酯係指烷基之碳數爲1〜20之（甲基）丙烯系烷基酯。其 中，方便上，該（甲基）丙烯酸系烷基酯中，烷基之碳數 爲15〜20之（甲基）丙烯酸系烷基酯稱爲丙烯酸系長鏈院 基酯，碳數爲1〜14之（甲基）丙烯酸系烷基酯稱爲丙烯酸 系短鏈烷基酯。 做爲該丙烯酸系長鏈烷基酯例者如：烷基由η-戊癸基 、η -己癸基、η -庚癸基、η -辛癸基、、η -壬癸基、η -二十 -11 - 200811259 碳癸基等所成之丙烯酸或甲基丙烯酸之烷基酯例。 又，丙烯酸系長鏈烷基酯之烷基可爲直鏈狀，亦可爲 支鏈。 做爲該丙烯系短鏈烷基酯例者如：先行技術之（甲基 )丙烯系黏著劑所使用之公知的酯例。其代表例如：烷基 爲由甲基、乙基、丙基、丁基、2-乙基己基、異辛基、異 壬基、異癸基、月桂基、三癸基等所成之丙烯酸或甲基丙 烯酸之烷基酯例。 又，由構成黏著劑組成物主成份之聚合物之鏈式構造 所成之（甲基）丙烯酸烷基酯可單獨使用，或混合2種以 上使用之。 (苯乙烯之配合量） 構成黏著劑組成物主成份之聚合物之單量體組成物中 ，當總量100質量份之（甲基）丙烯酸酯及（甲基）丙烯 酸烷基酯時，其所配合苯乙烯之量爲10〜7 0質量份者宜， 較佳者爲20〜70質量份，更佳者爲30〜70質量份。 當苯乙烯配合量爲10質量份以上時，則可提昇耐熱性 。且，70質量份以下則可抑制黏著劑層之裂化。 (具環式構造之（甲基）丙烯酸酯之配合量） 構成黏著劑組成物主成份之聚合物之單量體組成物中 ，當總量1 〇 〇質量份之（甲基）丙烯酸酯，及（甲基）丙 烯酸烷基酯時，（甲基）丙烯酸酯之配合量以20〜50質量 -12- 200811259 份爲宜，較佳者爲20〜45質量份，更佳者爲20〜40質量份。 當（甲基）丙烯酸酯之配合量爲20質量份以上後，加 熱至200 °C以上時，則由黏著劑組成物之氣體產生量充足 ，可易於剝離。如：使黏著劑組成物用於半導體晶圓與支 撐板之黏著時，於半導體晶圓與支撐板間形成充分的空隙 ，可充分滲透剝離液，縮短由半導體晶圓剝離支撐板之時 間。又，（甲基）丙烯酸酯之配合量爲50質量份以下則可 取得支撐板與半導體晶圓之良好黏著性。 (由鏈式構造所成之（甲基）丙烯酸烷基酯之配合量） 構成主成份聚合物之單量體組成物中，當總量1 00質 量份之苯乙烯、（甲基）丙烯酸酯、及（甲基）丙烯酸烷 基酯時、（甲基）丙烯酸酯之配合量爲10〜50質量份者宜 ，較佳者爲15〜40質量份，更佳者爲20〜35質量份。藉由該 範圍後，可提昇黏著性及柔軟性。 又，構成黏著劑組成物主成份之聚合物之（甲基）丙 烯酸烷基酯只要於上述配合量之範圍者，即可單獨使用， 或混合2種以上使用之。 另外，黏著劑組成物中，在不損及本發明本質特性範 圍下，可進一步添加含有所期待具混合性之添加物，如： 爲改良黏著劑性能之附加樹脂、可塑劑、黏著塑劑、穩定 劑、著色劑、介面活性劑等慣用添加劑。 黏著劑組成物更於不損及本發明本質特性範圍下，爲 了調整黏度亦可利用有機溶劑進行稀釋。做爲具體之該有 -13- 200811259 機溶劑例如：丙酮、丁酮、環己酮、甲基異戊酮、2-庚酮 等酮類；乙二醇、乙二醇單乙酸酯、二乙二醇、二乙二醇 單乙酸酯、丙二醇、丙二醇單乙酸酯、二丙二醇或二丙二 醇單乙酸酯之單甲醚、單乙醚、單丙醚、單丁醚或單苯醚 等多價醇類及其衍生物；二氧陸圜類之環式醚類；及乳酸 甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮 酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯 等酯類等例。此等可單獨使用，亦可混合2種以上使用之 。特別又以乙二醇、丙二醇、二乙二醇單乙酸酯、丙二醇 單乙酸酯、二乙二醇單乙酸酯或此等單甲醚、單乙醚、單 丙醚、單丁醚或單苯醚等多價醇類及其衍生物爲最佳。又 ，爲提昇黏著劑層之膜厚均一性，亦可於此等中添加活性 劑。有機溶劑之使用量可依塗佈黏著劑組成物之膜厚進行 適當設定，黏著劑組成物只要可塗佈於半導體晶圓等之濃 度即可，並未特別限定。通常，黏著劑組成物之固形份濃 度以20〜70質量％使用爲宜，較佳者爲25〜60質量％。 (黏著劑組成物之用途） 上述之黏著劑組成物特別做爲使爲保護半導體晶圓之 半導體晶圓用於爲黏著於支撐板之黏著劑組成物使用後， 可發揮良好的效果。上述黏著劑組成物亦可做爲保護膠帶 等黏著薄膜之黏著劑層之使用，此時亦可發揮良好的特性 〇 又，該黏著劑組成物依其用途，亦可任意使用如：液 -14- 200811259 狀之支撐板或塗佈於半導體晶圓後，形成黏著劑層之方法 ’或，於具有可對應基材的彎曲、變形之可撓性薄膜上預 先形成黏著劑層’乾燥放置，將此薄膜（乾薄膜）貼附於 支撐板後使用之方法（黏著薄膜法）。 [實施形態2] 針對使用實施形態1之黏著劑組成物的黏著薄膜，做 爲實施形態2於以下進行說明。黏著薄膜係指於薄膜（支 撐薄膜）上至少具備由黏著劑組成物所成之黏著劑層。 該黏著薄膜只要用於做爲黏著薄膜之黏著用途者，並 未特別限定。本實施形態中，列舉用於爲做成晶圓支撐系 統使半導體晶圓暫時黏著於支撐板之用途時，進行說明。 黏著薄膜進一步於黏著劑層上被覆薄膜（保護薄膜） 時，由黏著劑層剝離保護薄膜，將露出之黏著劑層重疊於 支撐板或半導體晶圓後，由黏著劑層剝離支撐薄膜後，可 使黏著劑層容易設定於支撐板或半導體晶圓上。 使用黏著薄膜後，相較於直接塗佈黏著劑組成物於支 撐板或半導體晶圓後，形成黏著劑層時，其較可形成膜厚 均一性及表面平滑性良好之黏著劑層。 做爲用於黏著薄膜製造之支撐薄膜者’只要可使製膜 於支撐薄膜之黏著劑層輕易由支撐薄膜剝離之，可於支撐 板或晶圓等被處理面上複製該黏著劑層之脫模薄膜即可， 並未特別限定。 做爲此支撐薄膜者，如：具有可對應基材之彎曲、變 -15- 200811259 形之可撓性薄膜例。具體例如：由膜厚1 5〜1 2 5 // m之聚對 苯二甲酸乙二醇酯、聚乙烯、聚丙烯、聚碳酸酯、聚氯化 乙烯等之合成樹脂薄膜所成之薄膜例。該支撐薄膜於必要 時，使黏著劑層易於複製於支撐板或半導體晶圓等之被處 理面上，進行脫模處理者宜。 於支撐薄膜上形成黏著劑層時，以調製黏著劑組成物 後，使用塗佈輥、棒塗佈機、線棒塗佈機、滾輥塗佈機、 簾流塗佈機，於支撐薄膜上塗佈本發明黏著劑組成物呈乾 燥後膜厚爲5〜100 // m。又特別以滾輥塗佈機使用後，可有 效形成良好的膜厚均一性，且可形成厚度厚的膜，因此最 爲理想。 做爲保護薄膜者使氟樹脂進行塗佈或燒鍍之厚度1 5〜 125//m之聚對苯二甲酸乙二醇酯薄膜、聚丙烯薄膜及聚乙 烯薄膜等爲宜。 (黏著薄膜之使用方法） 由黏著薄膜剝離保護薄膜後，將露出之黏著劑層重疊 於支撐板或半導體晶圓，由支撐薄膜上移動加熱滾輥後’ 將黏著劑層於支撐板或半導體晶圓表面上進行熱壓延。 另外，由黏著薄膜所剝離之保護薄膜可依序經由捲繞 膠帶捲繞成輥狀保存後可再利用之。 [實施形態3] 針對由實施形態1之黏著劑組成物所成之黏著劑層進 -16- 200811259 行剝離之方法，做成實施形態3於以下進行說明。 該黏著劑組成物只要用於做爲黏著劑之用途即可，其 具體用途並未特別限定。本實施形態中，列舉爲做成晶圓 支撐系統，使該黏著劑組成物用於暫時將半導體晶圓黏著 於支撐板之用途時，進行說明。 本實施形態中，首先，說明之後將剝離之黏著劑層形 成於半導體晶圓之方法，再針對由該半導體晶圓剝離該黏 著劑層之方法進行說明。 於半導體晶圓上形成黏著劑層之方法係含有以下2個 步驟；（1)塗佈黏著劑組成物之步驟；（2)爲乾燥塗佈 之黏著劑組成物之預焙燒步驟。 又，於半導體晶圓上形成黏著劑層之步驟亦可爲將實 施形態2所載之黏著薄膜貼附於半導體晶圓之步驟。 另外，由半導體晶圓剝離黏著劑層之方法爲含有以下 2個步驟；（1 )使半導體晶圓及黏著劑層加熱至200 °C以 上之步驟；（2 )於半導體晶圓與黏著劑層之間滲透剝離 液之步驟。 (塗佈黏著劑組成物之步驟） 做爲塗佈黏著劑組成物於半導體晶圚之被處理面的方 法者，可使用旋轉塗層法、狹縫塗層法、滾輥塗層法、網 版印刷法及薄層塗佈法等方法。進行黏著劑組成物之塗佈 時，使用上述方法後，於半導體晶圚之周邊部形成更高的 錐部。形成錐部時，於黏著劑組成物之乾燥步驟中預先以 -17- 200811259 溶劑去除錐部爲宜。 (半導體晶圓上形成黏著劑層之步驟） 接著，爲使黏著劑組成物乾燥，而進行預焙 塗佈之黏著劑組成物流動性，形成黏著劑層。預 度依其黏著劑組成物中各成份之種類，配合比例 層之膜厚而異，一般以70〜200°C者宜，更佳者爲 。又，預焙燒時間以3〜30分鐘者宜。 黏著劑層之厚度依形成於半導體晶圓表面之 而決定。另外，爲增加黏著劑層之厚度，亦可複 進行黏著劑組成物之塗佈與乾燥。又，藉由預焙 於控制黏著劑層之膜厚。 又，針對黏著薄膜之貼附方法，於實施形I 之，故於此省略其說明。 於形成之黏著劑層壓緊支撐板後，可將半導 著於支撐板上。 (將半導體晶圓及黏著劑層加熱至200°C以上之歩 進行半導體晶圓薄板化之硏削步驟後，由支 剝離時，將半導體晶圓及黏著劑層加熱至200 °C 爲加熱至20(TC以上之方法者使用熱板。 經由加熱至200 °C以上後，使黏著劑層發泡 黏著劑層之黏著力，同時於半導體晶圓與支撐板 隙0 燒，降低 焙燒之溫 及黏著劑 90 〜200〇C 電路凹凸 數次重覆 燒後可易 i 2已說明 體晶圓黏 驟） 撐板進行 以上。做 ，可降低 間產生間 -18- 200811259 (滲透剝離液之步驟） 於黏著劑層發泡產生之半導體晶圓與支撐板之間隙中 經由滲透剝離液後，由輕易且縮短由半導體晶圓剝離支撐 板。 做爲用於爲由半導體晶圓剝離支撐板之剝離液者，可 使用稀釋該黏著劑組成物之溶媒、或甲醇、乙醇、丙醇、 異丙醇及丁醇等一價醇類、丁內酯等環狀內酯類、二 乙酯及茴香醚、等醚類，以及二甲基甲醛、二甲基乙醛、 等之醛類。其中又特別以丙二醇單用甲醚乙酸酯及乳酸乙 酯爲主成份之剝離液，其環境負荷及剝離性爲最理想。 本發明並未受限於上述各實施形態，於申請項所示範 圍內可進行各種變更，於不同實施形態中，針對分別所揭 示技術性之手段經適當組合取得之實施形態，亦含於本發 明之技術範圍。 以下，代表本發明黏著劑組成物之實施例。另外，以 下所示實施例不僅爲本發明理想之說明示例，並未受限任 意之本發明。 [實施例] (實施例1〜2 ) 將附有攪拌裝置、迴流器、溫度計及滴入槽之燒瓶進 行氮取代後，於燒瓶內置入1 〇〇質量份聚合溶媒之丙二醇 單甲醚乙酸酯（PGMEA )，進行攪拌。之後，攪拌之同時 -19- 200811259 ，使PGMEA之溫度上昇至80°C。接著，以下表所示之配合 比（質量份）將下表各種單體置入滴入槽，進行攪拌至全 部成份相互溶解爲止，由滴入槽以3個小時的時間均勻滴 入燒瓶內，持續於8 (TC下進行攪拌5小時，同時進行聚合 。之後，冷卻至室溫後，取得實施例1〜2之丙烯酸系聚合 物。 (比較例1〜3) 將附有攪拌裝置、迴流器、溫度計及滴入槽之燒瓶進 行氮取代後，於燒瓶內置入1 〇〇質量份聚合溶媒之丙二醇 單甲醚乙酸酯（PGMEA )，進行攪拌。之後，攪拌之同時 使PGMEA之溫度上昇至80°C。接著，以下表所示之配合比 (質量份）將下表各種單體置入滴入槽，進行攪拌至全部 成份相互溶解爲止，由滴入槽以3個小時的時間均勻滴入 燒瓶內，持續於80 °C下進行攪拌5小時，同時進行聚合。 之後，冷卻至室溫後，取得比較例1〜3之丙烯酸系聚合物 實施例及比較例 實® 酬 比較例 1 2 1 2 3 甲基丙烯酸-η-丁酯 15 15 15 11 9 甲基丙烯酸甲酯 15 15 13 15 15 苯乙烯 50 50 52 60 70 1-乙基-1-環己基丙烯酸酯 20 - 14 6 2-甲基-2-金剛烷丙烯酸酯 - 20 - - - 環己基丙烯酸酯 - - 20 - - -20- 200811259 將上表之丙烯酸系聚合物分別溶於丙二醇單甲醚乙酸 酯’其丙烯酸系聚合物之濃度調整爲40質量％之黏著劑組 成物。 (測定及算出項目） 利用實施例1〜2及比較例1〜3之各黏著劑組成物，進行 測定由黏著劑層所釋出之氣體量及質量平均分子量，算出 理論之玻璃轉移點（Tg )溫度。 (質量平均分子量及理論玻璃轉移點溫度） 該實施例及比較例之各黏著劑組成物之質量平均分子 量係藉由凝膠滲透色譜法（GPC)依聚苯乙烯換算基準求 取之。又’理論玻璃轉移點（Tg)溫度係分別測定使用各 單體所合成之均聚物Tg後，利用單體置入量比率所計算之 値（以實施例爲例進行說明後，甲基丙烯酸n-丁基均聚物 之Tgx0.15+甲基丙烯酸甲酯均聚物之Tgx〇.l5 +苯乙烯均聚 物之TgxO.5 + 1·乙基-1-環己基丙烯酸酯之均聚物之Tgxo.2 )〇 下表代表該實施例及比較例各黏著劑組成物之質量平 均分子量及理論玻璃轉移點（Tg )溫度。 實施例及比較例 實方彳 _ 比較例 _ 1 2 1 2 3 _ 理論玻璃轉移點(Tg)溫度(°c) 50 80 45 63 74 _ 質里平均分子量(RI檢出） 38100 40000 43100 34200 34300 -21 - 200811259 (由黏著劑層所釋出之氣體量） 由黏著劑層所釋出之氣體量係利用TDS法（Thermal Desorption Spectroscopy ’昇溫脫離分析法）進行測定之 。此所謂T D S法係指將該實施例及比較例之各黏著劑組成 物塗佈於8 i n c h聚矽氧晶圓上，於熱板上經由1 8 〇 °C，5分 鐘加熱乾燥後形成黏著劑層。接著，使分別黏著劑層之溫 度由未達50 °C開始昇溫至25 0 °C後，測定由黏著劑層所釋 出之氣體重之方法。TDS裝置（釋放氣體測定裝置）係使 用電子科學股份公司製之EMD-WA1000。 TDS裝置之測定條件如下。(wherein R1 is a hydrogen atom or a methyl group, R4 is an alkyl group having 1 to 4 carbon atoms, R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a is 0, 1 or 2). In this case, 1-methyl-1 -cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-methyl-1-cyclohexyl (A) Acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 2-methyl-2-goldenyl (meth) propyl acrylate, 2 · ethyl-2 - ruthenium (Methyl) acrylate or the like is preferable, and more preferably 1-ethyl-1-cyclohexyl (meth) acrylate or 2-methyl-2-adamantyl (meth) acrylate. (Type of alkyl (meth) acrylate formed by a chain structure) In the detailed description, etc., "made by a chain structure" (alkyl methacrylate) means that the carbon number of the alkyl group is 1~ 20 (meth) propylene alkyl ester. In the above (meth)acrylic alkyl ester, the (meth)acrylic alkyl ester having an alkyl group having a carbon number of 15 to 20 is referred to as an acrylic long-chain polyester, and the carbon number is 1. The (meth)acrylic alkyl ester of ～14 is called an acrylic short-chain alkyl ester. As the acrylic long-chain alkyl ester, for example, an alkyl group is composed of η-pentamethylene, η-hexyl, η-g-decyl, η-octyl, η-fluorenyl, η-twen -11 - 200811259 An alkyl ester of acrylic acid or methacrylic acid formed by a carbon sulfhydryl group or the like. Further, the alkyl group of the acrylic long-chain alkyl ester may be linear or branched. As an example of the propylene short-chain alkyl ester, a known ester example used in the prior art (meth) propylene-based adhesive is used. It is represented, for example, that the alkyl group is acrylic acid formed from methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isodecyl, isodecyl, lauryl, tridecyl or the like. An alkyl ester of methacrylic acid. Further, the alkyl (meth)acrylate formed from the chain structure of the polymer constituting the main component of the adhesive composition may be used singly or in combination of two or more. (a compounding amount of styrene), when a total amount of 100 parts by mass of the (meth) acrylate and the alkyl (meth) acrylate is in the monolith composition of the polymer constituting the main component of the adhesive composition, The amount of the styrene to be blended is preferably 10 to 70 parts by mass, more preferably 20 to 70 parts by mass, still more preferably 30 to 70 parts by mass. When the amount of styrene is 10 parts by mass or more, heat resistance can be improved. Further, 70 parts by mass or less can suppress cracking of the adhesive layer. (a compounding amount of a (meth) acrylate having a ring structure), in a monolith composition of a polymer constituting a main component of the adhesive composition, when the total amount is 1 part by mass of the (meth) acrylate, When the alkyl (meth)acrylate is used, the amount of the (meth) acrylate is preferably 20 to 50 mass -12 to 200811259 parts, preferably 20 to 45 parts by mass, more preferably 20 to 40 parts by weight. Parts by mass. When the amount of the (meth) acrylate is 20 parts by mass or more, when it is heated to 200 ° C or more, the amount of gas generated from the adhesive composition is sufficient and peeling can be easily performed. For example, when the adhesive composition is used for bonding a semiconductor wafer to a support plate, a sufficient gap is formed between the semiconductor wafer and the support plate to sufficiently penetrate the stripping liquid and shorten the time for the support wafer to be peeled off from the semiconductor wafer. Further, when the amount of the (meth) acrylate is 50 parts by mass or less, good adhesion between the support sheet and the semiconductor wafer can be obtained. (a compounding amount of an alkyl (meth)acrylate formed by a chain structure), in a single-body composition constituting a main component polymer, when a total amount of 100 parts by mass of styrene or (meth) acrylate In the case of the alkyl (meth)acrylate, the amount of the (meth) acrylate is preferably 10 to 50 parts by mass, preferably 15 to 40 parts by mass, more preferably 20 to 35 parts by mass. With this range, adhesion and softness can be improved. Further, the alkyl (meth) acrylate which is a polymer constituting the main component of the adhesive composition may be used singly or in combination of two or more kinds as long as it is in the range of the above-mentioned compounding amount. Further, in the adhesive composition, an additive containing a desired mixing property may be further added, such as an additional resin, a plasticizer, an adhesive, or a plasticizer, for improving the performance of the adhesive, without impairing the essential characteristics of the present invention. Conventional additives such as stabilizers, colorants, and surfactants. The adhesive composition can be diluted with an organic solvent in order to adjust the viscosity without impairing the essential characteristics of the present invention. Specifically, there are 13-200811259 machine solvents such as: acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone and other ketones; ethylene glycol, ethylene glycol monoacetate, two Ethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Polyvalent alcohols and derivatives thereof; cyclic ethers of dioxane; and methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate Examples of esters such as methyl methoxypropionate and ethyl ethoxypropionate. These may be used singly or in combination of two or more. In particular, ethylene glycol, propylene glycol, diethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate or such monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or Polyvalent alcohols such as monophenyl ether and derivatives thereof are preferred. Further, in order to improve the film thickness uniformity of the adhesive layer, an active agent may be added thereto. The amount of the organic solvent to be used can be appropriately set depending on the film thickness of the application of the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is not particularly limited as long as it can be applied to a semiconductor wafer or the like. Usually, the solid content of the adhesive composition is preferably 20 to 70% by mass, preferably 25 to 60% by mass. (Use of Adhesive Composition) The above-mentioned adhesive composition is particularly useful as a semiconductor wafer for protecting a semiconductor wafer for use as an adhesive composition adhered to a support plate. The above adhesive composition can also be used as an adhesive layer for an adhesive film such as a protective tape, and can also exhibit good characteristics at this time. Further, the adhesive composition can be used arbitrarily according to its use, such as: liquid-14 - 200811259 A support plate or a method of forming an adhesive layer after being applied to a semiconductor wafer, or a pre-formed adhesive layer on a flexible film which can be bent and deformed corresponding to a substrate, This film (dry film) is attached to the support plate (adhesive film method). [Embodiment 2] An adhesive film using the adhesive composition of the first embodiment will be described below as Embodiment 2. The adhesive film means that at least the adhesive layer formed of the adhesive composition is provided on the film (support film). The adhesive film is not particularly limited as long as it is used as an adhesive for adhesive films. In the present embodiment, a description will be given of a case in which a semiconductor wafer is temporarily adhered to a support plate by a wafer support system. When the adhesive film is further coated on the adhesive layer (protective film), the protective film is peeled off by the adhesive layer, and the exposed adhesive layer is superposed on the support plate or the semiconductor wafer, and the support film is peeled off by the adhesive layer. The adhesive layer is easily set on a support plate or a semiconductor wafer. When the adhesive film is used, the adhesive layer can be formed to have a film thickness uniformity and a good surface smoothness as compared with the case where the adhesive composition is directly applied to the support sheet or the semiconductor wafer to form an adhesive layer. As the support film for the adhesive film manufacturing, as long as the adhesive layer formed on the support film can be easily peeled off from the support film, the adhesive layer can be reproduced on the treated surface such as the support plate or the wafer. The mold film is not particularly limited. For the support film, for example, a flexible film having a shape corresponding to the bending of the substrate and having a shape of -15-200811259. Specifically, for example, a film formed of a synthetic resin film of polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, or polyvinyl chloride having a film thickness of 15 to 1 2 5 // m. . The support film is preferably used to release the adhesive layer on a surface to be treated such as a support plate or a semiconductor wafer, if necessary. When the adhesive layer is formed on the support film, the adhesive composition is prepared, and then coated on the support film by using a coating roll, a bar coater, a bar coater, a roll coater, and a curtain coater. The adhesive composition of the present invention is coated to have a film thickness of 5 to 100 // m after drying. Further, in particular, after use in a roll coater, it is effective to form a good film thickness uniformity and to form a film having a large thickness. As the protective film, a polyethylene terephthalate film, a polypropylene film, a polyethylene film or the like having a thickness of 15 to 125/m which is coated or fired with a fluororesin is preferably used. (How to use the adhesive film) After peeling off the protective film by the adhesive film, the exposed adhesive layer is superposed on the support plate or the semiconductor wafer, and the adhesive roller is layered on the support plate or the semiconductor crystal after the heating roller is moved on the support film. Hot rolling is performed on the round surface. Further, the protective film peeled off from the adhesive film can be sequentially wound and wound into a roll through a winding tape to be reused. [Embodiment 3] A method in which the adhesive layer formed by the adhesive composition of the first embodiment is peeled off from -16 to 200811259 is described in the third embodiment. The adhesive composition may be used as an adhesive, and the specific use thereof is not particularly limited. In the present embodiment, a description will be given of a wafer support system in which the adhesive composition is used for temporarily attaching a semiconductor wafer to a support plate. In the present embodiment, first, a method of forming a peeled adhesive layer on a semiconductor wafer, and a method of peeling off the adhesive layer from the semiconductor wafer will be described. The method of forming an adhesive layer on a semiconductor wafer comprises the following two steps; (1) a step of applying an adhesive composition; and (2) a pre-baking step of the dry-coated adhesive composition. Further, the step of forming an adhesive layer on the semiconductor wafer may be a step of attaching the adhesive film of the second embodiment to the semiconductor wafer. In addition, the method of peeling off the adhesive layer from the semiconductor wafer comprises the following two steps; (1) a step of heating the semiconductor wafer and the adhesive layer to 200 ° C or higher; and (2) a semiconductor wafer and an adhesive layer; The step of penetrating the stripping solution between them. (Step of coating the adhesive composition) As a method of applying the adhesive composition to the treated surface of the semiconductor wafer, a spin coating method, a slit coating method, a roll coating method, or a net can be used. Methods such as plate printing method and thin layer coating method. When the application of the adhesive composition is carried out, a higher taper portion is formed in the peripheral portion of the semiconductor wafer after the above method. When the tapered portion is formed, it is preferred to remove the tapered portion with a solvent in advance in the drying step of the adhesive composition. (Step of Forming Adhesive Layer on Semiconductor Wafer) Next, in order to dry the adhesive composition, the adhesive composition is pre-baked and fluidity is formed to form an adhesive layer. The thickness of each component in the composition of the adhesive composition varies depending on the film thickness of the proportion layer, and is generally preferably 70 to 200 ° C, more preferably. Moreover, the pre-baking time is preferably 3 to 30 minutes. The thickness of the adhesive layer is determined by the surface of the semiconductor wafer. Further, in order to increase the thickness of the adhesive layer, application and drying of the adhesive composition may be repeated. Further, the film thickness of the adhesive layer is controlled by prebaking. Moreover, since the method of attaching the adhesive film is carried out in the form I, the description thereof is omitted here. After the formed adhesive is laminated to the support plate, the semiconductor can be semi-conducted on the support plate. (When the semiconductor wafer and the adhesive layer are heated to 200 ° C or higher, the semiconductor wafer is thinned, and then the semiconductor wafer and the adhesive layer are heated to 200 ° C for heating. 20 (The method above TC uses a hot plate. After heating to 200 °C or higher, the adhesive layer foams the adhesive layer, and simultaneously burns the semiconductor wafer and the support plate gap to reduce the temperature of the baking. Adhesive 90 ~ 200 〇 C circuit concave and convex several times after repeated burning can be easy i 2 has described the body wafer adhesion step) struts carry out the above. Do, can reduce the inter-generation -18- 200811259 (step of osmotic stripping solution) After the permeable stripping solution is passed through the gap between the semiconductor wafer and the support sheet which is foamed by the adhesive layer, the support sheet is peeled off from the semiconductor wafer easily and shortened. As a stripping liquid for peeling the support sheet from the semiconductor wafer A solvent for diluting the adhesive composition, or a monovalent alcohol such as methanol, ethanol, propanol, isopropanol or butanol, a cyclic lactone such as butyrolactone, diethyl ester and anisole may be used. Ethers, and dimethyl An aldehyde such as dimethyl acetaldehyde or the like, and particularly a retort liquid containing propylene glycol monomethyl ether acetate and ethyl lactate as the main component, and the environmental load and the peeling property are optimal. The present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the invention, and the embodiments obtained by appropriately combining the disclosed technical means are also included in the technical scope of the present invention. Hereinafter, the embodiment of the adhesive composition of the present invention is shown. In addition, the following examples are not only illustrative examples of the present invention, but are not limited to any of the present invention. [Embodiment] (Examples 1 to 2) After a nitrogen-substrate was placed in a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 1 part by mass of a polymerization solvent of propylene glycol monomethyl ether acetate (PGMEA) was placed in the flask and stirred, followed by stirring. At the same time, -19-200811259, the temperature of PGMEA was raised to 80 ° C. Then, the mixing ratio (mass parts) shown in the following table was placed in the dropping tank in the following table, and the mixture was stirred until all. The mixture was uniformly dissolved in the flask by a dropping tank for 3 hours, and the mixture was stirred at 8 ° C for 5 hours while being polymerized. Thereafter, after cooling to room temperature, Examples 1 to 2 were obtained. Acrylic polymer. (Comparative Examples 1 to 3) After a nitrogen-substituted flask was placed in a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 1 part by mass of a polymerization solvent of propylene glycol monomethyl ether B was placed in the flask. The acid ester (PGMEA) was stirred, and the temperature of PGMEA was raised to 80 ° C while stirring. Then, the mixing ratios (mass parts) shown in the following table were placed in the dropping tank for the following monomers. The mixture was stirred until all the components were dissolved, and the mixture was uniformly dropped into the flask over a period of 3 hours from the dropping tank, and the mixture was stirred at 80 ° C for 5 hours while being polymerized. Thereafter, after cooling to room temperature, the acrylic polymer examples and comparative examples of Comparative Examples 1 to 3 were obtained. Comparative Example 1 2 1 2 3 Methacrylic acid-η-butyl ester 15 15 15 11 9 Methacrylic acid Methyl ester 15 15 13 15 15 Styrene 50 50 52 60 70 1-Ethyl-1-cyclohexyl acrylate 20 - 14 6 2-Methyl-2-adamantane acrylate - 20 - - - Cyclohexyl acrylate - - 20 - - -20- 200811259 The acrylic polymer of the above table was each dissolved in propylene glycol monomethyl ether acetate, and the concentration of the acrylic polymer was adjusted to 40% by mass of the adhesive composition. (Measurement and Calculation Items) Using the adhesive compositions of Examples 1 to 2 and Comparative Examples 1 to 3, the amount of gas released from the adhesive layer and the mass average molecular weight were measured to calculate a theoretical glass transition point (Tg). )temperature. (mass average molecular weight and theoretical glass transition point temperature) The mass average molecular weight of each of the adhesive compositions of the examples and the comparative examples was determined by gel permeation chromatography (GPC) on a polystyrene basis. Further, the theoretical glass transition point (Tg) temperature is measured by using the monomer Tg synthesized by using each monomer, and the enthalpy calculated by using the ratio of the monomer implantation amount (method of exemplification by way of an example) Hg of a Tgx0.15+methyl methacrylate homopolymer of n-butyl homopolymer Tgx〇.l5 + homopolymer of TgxO.5 + 1·ethyl-1-cyclohexyl acrylate Tgxo.2) The following table represents the mass average molecular weight and theoretical glass transition point (Tg) temperature of each of the adhesive compositions of the examples and comparative examples. EXAMPLES AND COMPARATIVE EXAMPLES 比较 COMPARISON _ 1 2 1 2 3 _ Theoretical glass transition point (Tg) temperature (°c) 50 80 45 63 74 _ Mean average molecular weight (RI detected) 38100 40000 43100 34200 34300 -21 - 200811259 (Amount of gas released from the adhesive layer) The amount of gas released from the adhesive layer was measured by the TDS method (Thermal Desorption Spectroscopy). The TDS method refers to coating the adhesive compositions of the examples and the comparative examples on an 8 inch polyfluorene oxide wafer, and drying on a hot plate at 18 ° C for 5 minutes to form an adhesive. Floor. Next, the temperature of each of the adhesive layers was raised from 25 ° C to 25 ° C, and the weight of the gas released from the adhesive layer was measured. The TDS device (release gas measuring device) uses the EMD-WA1000 manufactured by Electronic Science Corporation. The measurement conditions of the TDS device are as follows.
Width ： 100Width : 100
Center Mass Number * 50 Gain* 9 Scan Speed · 4 Emult Volt ： 1 . 3 kVCenter Mass Number * 50 Gain* 9 Scan Speed · 4 Emult Volt : 1 . 3 kV
測定溫度：40〜250 °C 藉由TDS裝置之測定係將黏著劑層運送於測定室內，i 分鐘後開始測定。該TDS測定結果之曲線圖示於圖1。測定 曲線圖之橫軸爲昇溫（測定）溫度，縱軸爲任意強度（ intensity )。測定條件之「Emult Volt」係指「Electron Multiplayer Acceleration Voltage」 之蒽，一般記爲「Q-mass」（四重極子質量分析器）加速電壓」。 圖1中，達100°C爲止之溫度下的釋放氣體爲水蒸氣或 -22- 200811259 與水之共沸氣體。對於此’於1 00 °c以上爲之溫度下釋放 氣體爲水蒸氣或與水共沸氣體以外，亦即由黏著劑組成物 所產生之氣體。因此，達1 00 °c以上之強度大者代表經由 熱其黏著劑組成物被分解之。 實施例1之黏著劑組成物中出現於比較例各黏著劑組 成物所未見之於200 °C附近急劇上昇強度。藉由此，實施 例1之黏著劑組成物於100°c下，不釋放氣體，保持黏著力 ，於2 0 0 °c附近經由熱而被分解，出現氣體之釋放。 本發明黏著劑組成物之構成，經由200 °C以上加熱後 ，具有環式構造之（甲基）丙烯酸酯之官能基由酯鍵解離 ，因此可使黏著劑組成物發泡。藉由此，可有效降低黏著 劑組成物之黏著力，輕易由基板剝離黏著劑層。 使用本發明之黏著劑組成物，黏著薄膜及剝離方法後 ，可輕易進行使用晶圓支撐系統之附有聚矽氧貫通電極元 件之製作，可實現高性能之SiP。又，往後，MEMS ( Micro Electro Mechanical Systems，微電機系統）元件等 之廣範圍領域中其晶圓支撐系統之應用時，亦可期待合倂 本發明之應用。 發明之詳細S兌明項中其具體之實施形態或實施例至少 清楚說明瞭本發明之技術內容，其具體例並未受限於狹義 之解釋，可依本發明之見解與以下記載之申請專利範圍內 ，進行各種更動。 【圖式簡單說明】 -23- 200811259 圖1代表實施例及比較例中各黏著劑組成物之TDS測定 結果之曲線圖。Measurement temperature: 40 to 250 ° C The adhesive layer was transported to the measurement chamber by the measurement system of the TDS apparatus, and measurement was started after i minutes. A graph of the results of this TDS measurement is shown in Fig. 1. The horizontal axis of the measurement graph is the temperature rise (measurement) temperature, and the vertical axis is the intensity (intensity). The "Emult Volt" of the measurement conditions is referred to as "Electron Multiplayer Acceleration Voltage" and is generally referred to as "Q-mass" (Quad Dipole Mass Analyzer) Accelerating Voltage". In Fig. 1, the released gas at a temperature up to 100 ° C is water vapor or azeotrope gas of -22-200811259 with water. For the case where the gas released at a temperature of 100 ° C or higher is water vapor or azeotrope with water, that is, a gas generated by an adhesive composition. Therefore, a person having a strength of more than 100 ° C or more represents decomposition of the composition by heat of the adhesive. The adhesive composition of Example 1 appeared in the adhesive composition of the comparative example and showed no sharp rise in strength near 200 °C. As a result, the adhesive composition of Example 1 did not release gas at 100 ° C, remained adhesive, and was decomposed by heat at around 200 ° C, and gas evolution occurred. When the composition of the adhesive composition of the present invention is heated at 200 ° C or higher, the functional group of the (meth) acrylate having a cyclic structure is dissociated from the ester bond, so that the adhesive composition can be foamed. Thereby, the adhesion of the adhesive composition can be effectively reduced, and the adhesive layer can be easily peeled off from the substrate. By using the adhesive composition of the present invention, the adhesive film and the peeling method, it is possible to easily fabricate a polysilicon-containing through-electrode element using a wafer supporting system, thereby realizing high-performance SiP. Further, in the future, when a wafer supporting system is applied in a wide range of fields such as MEMS (Micro Electro Mechanical Systems) components, the application of the present invention can be expected. DETAILED DESCRIPTION OF THE INVENTION The specific embodiments or examples of the invention are at least clearly described in the technical description of the present invention. The specific examples are not limited to the narrow interpretation, and the invention can be applied according to the present invention. Within the scope, make various changes. BRIEF DESCRIPTION OF THE DRAWINGS -23- 200811259 Fig. 1 is a graph showing the results of TDS measurement of each of the adhesive compositions in the examples and the comparative examples.
-24--twenty four-
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| JP2006215070A JP5048980B2 (en) | 2006-08-07 | 2006-08-07 | Adhesive composition, adhesive film, and peeling method |
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| TW200811259A true TW200811259A (en) | 2008-03-01 |
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| JP2005314453A (en) * | 2004-04-27 | 2005-11-10 | Sumitomo Chemical Co Ltd | Acrylic resin and adhesive containing the resin |
| JP5020496B2 (en) * | 2005-10-28 | 2012-09-05 | 東京応化工業株式会社 | Adhesive composition and adhesive film |
| US8193285B2 (en) * | 2006-05-16 | 2012-06-05 | Nippon Soda Co., Ltd. | Block copolymers |
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