201139595 六、發明說明： 【發明.所屬之技術領域】 本發明係關於一種具有高接著力而又可容易地剝離， 且耐熱性亦優異之接著劑組成物。 【先前技術】 含有接著劑成分之接著劑組成物廣泛地使用於接著 劑、密封劑、塗料、塗佈劑等之黏合劑，黏著帶或自立膠 帶等之黏著劑等。 根據其用途不同而有多種該等接著劑組成物所要求之 性能，根據用途，有要求僅於所需時顯示接著性而於其後 可谷易地剝離之情況。 例如提出有如下方法：於半導體晶片之製造步驟中， 於將自高純度之矽單晶等切下之厚膜晶圓研磨至特定之厚 度而製成薄膜晶圓之步驟等中，將厚膜晶圓接著於支撐板 而進行加強，轉此有效率地進行作業。另外，於將磨削至 特疋厚度之薄膜晶圓切割為單個之半導.體晶片時，亦使用 稱為切割膠帶之膠帶。對於此種半導體之製造步驟中使用 之接著劑組成物，要求於步驟中牢固地接著，且於步驟結 束後能夠在不損傷所獲得之薄膜晶圓或半導體晶片等之情 況下_ (以下，亦稱為「高接著易剝離」）。 下—代之技術，使用使複數個半導體晶片積層而使裝 v置大幅地高性能化、小型化之TSV (石夕穿孔/Through Sl νιγ)之三維積層技術受到注目。Tsv能夠實現半導體構裝 之门饴度化，存取速度大幅地加快，使用中所產生之熱之 201139595 釋放亦優異。 於此種TSV之製造中，必須進行如下等2〇〇。(：以上之 尚溫處理製程：將磨削所得之薄膜晶圓進行凸塊技術 (bumping) ’或於背面形成凸塊’或於三維積層時進行回焊。 因此，對於TSV之製造步驟中使用之接著劑組成物，除高 接著易剝離以外’亦要求即便於25〇〇c左右之高溫下亦可維 持接著性之对熱性。 實現高接著易剝離之接著劑組成物，於專利文獻丨中 揭示有使用藉由照射紫外線等光進行硬化而黏著力下降之 2硬化型黏著劑之黏著帶。此種黏著帶於加工步驟中可確 貫地固定半導體，且藉由照射紫外線等可容易地剝離。然 而關於專利文獻丨所揭示之膠帶照射紫外、線等之後之 黏著力之下降不足，於不損❹膜晶圓以導體晶片等之 情況下進行剝離較為困難。 於專利文獻2中揭示有具有含有熱膨脹性微球之黏著 層之加熱制離型黏著片。若將專利讀2之加熱剝離型黏 者片加熱至特定之溫度以上’則熱膨脹性微球膨脹，黏著 層整體發泡而於表面形成凹ώ，與被黏著體之接著面積減 ’因此可容易地剝離被點著體。然而關於專利文獻2所 ::…剝離型黏著片’係加熱而熱膨脹性微球膨脹， 被=表面產生細微之凹凸。藉由該形狀變化而於面與 :者體之間接著者雖然於膨脹過程中表現出自被黏著體 剝離黏者層之應力而進行你 呈點接著，接著力會殘餘，因此==與被黏著體 U此要於不知傷薄膜晶圓或半 4 201139595 導體晶月等之情況下、仓― 進仃剝離較為困難。s & . 謂於剝離後之被黏著 ' 另外，亦存在所 而，即便於使用耐二二糊劑殘留之問題。進 時，亦頂多僅為13〇t左六^之熱膨脹性微球之情形 中使用較為.困難。 之于熱性，於TSV之製造步驟 於專利文獻3中椙千括输 T揭不一種雙面膠帶 偶氮化合物等之刺激而 係、具“有會因 若對專利文獻3 “ 體產生劑的黏著層。 右耵寻扪文獻3之雙面膠帶施加 生之氣體被釋放至膠帶I ，由氣體產生劑產 著體之至…八：被黏著體間之界面，被黏 者體之至/ 一。p分會因該壓力而剝離 之雙面膠帶，則可於不ϋ 吏用專利文獻3 不知傷溥膜晶圓或半導體曰Κ犛，Η 不產生殘留_之情況下進行^ 雙面膠帶亦於耐熱性之方+ ㈣又馱3之 乃由存在問碭’於Tsv 制 中使用較為困難。 W之h步驟 目前，於TSV之製造步 4 7鄉甲，係進行如下方法：使用 3石厌黑之類的光吸收體料在和k 體微粒子粉之黏接著劑進行接著，利 用雷射導弓丨熱而進行分解、分離（非專利文獻1)。然而， 於使用非專利文獻i之技術時，除存在需要雷射照射裝置 之設備上之問題以外，亦存在微粒子粉會因雷射照射所致 之黏接著劑分解而飛散，使製造環境之潔淨度下降之問題。 專利文獻 專利文獻1 :日本特開平5 — 32946號公報 專利文獻2:曰本特開平u— 166164號公報 專利文獻3 :日本特開2〇〇3一 231872號公報 201139595 非專利文獻 非專利文獻1 :「接著之技術」Vol. 28 Ν0· 1 (2008)全 集9〇號P.28 【發明内容】 本發明之目的在於提供一種具有高接著力而又可容易 地剝離，且耐熱性亦優異之接著劑組成物。 本發明係一種接著劑組成物，其含有接著劑成分、及 下述式（1 )所示之羧酸化合物或其鹽： ?—coon R6 式（1 )中’ R1〜R7分別表示氫或有機基。R1〜R7可相 同亦可不同。R1〜R7中之兩個亦可相互鍵結而形成環狀結 構。 以下’對本發明進行詳細敍述。 本發明人發現’上述式（丨）所示之羧酸化合物或其鹽 藉由照射紫外線等光而產生氣體 面具有即便於200 t左右之高 性。並且發現，併用該黧仆人,, 體（二氧化碳氣體），另一方BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition which has high adhesion and which can be easily peeled off and which is excellent in heat resistance. [Prior Art] The adhesive composition containing an adhesive component is widely used as an adhesive for an adhesive, a sealant, a paint, a coating agent, or the like, an adhesive such as an adhesive tape or a self-supporting tape, or the like. Depending on the application, there are a plurality of properties required for such an adhesive composition, and depending on the application, there is a case where it is required to exhibit adhesiveness only when necessary, and then peel off easily thereafter. For example, in the manufacturing process of a semiconductor wafer, a thick film is formed by polishing a thick film wafer cut from a high-purity germanium single crystal or the like to a specific thickness to form a thin film wafer. The wafer is then reinforced by the support plate, and the work is efficiently performed. In addition, when cutting a thin film wafer that has been ground to a special thickness into a single semiconductor wafer, a tape called a dicing tape is also used. The adhesive composition used in the manufacturing step of such a semiconductor is required to be firmly adhered to in the step, and after the step is completed, the obtained thin film wafer or semiconductor wafer can be obtained without damage (hereinafter, also It is called "high and easy to peel off". In the next-generation technique, a three-dimensional layering technique in which a plurality of semiconductor wafers are stacked to sufficiently improve the size and size of the TSV (Shih-Through/Through Sl νιγ) is attracting attention. Tsv can achieve the threshold of semiconductor structure, the access speed is greatly accelerated, and the release of heat generated during use is also excellent. In the manufacture of such a TSV, the following must be performed. (The above temperature processing process: the bumped wafer wafer is subjected to bumping 'or bumping on the back side' or reflowed when three-dimensionally laminated. Therefore, it is used in the manufacturing steps of the TSV. The adhesive composition is not limited to high and then easily peeled off. It is also required to maintain the thermal properties of the adhesive even at a high temperature of about 25 ° C. A high-adhesive and easily peelable adhesive composition is disclosed in the patent document. An adhesive tape using a curable adhesive which is cured by irradiation with light such as ultraviolet rays and has a reduced adhesive force is disclosed. The adhesive tape can surely fix the semiconductor in the processing step and can be easily peeled off by irradiation of ultraviolet rays or the like. However, it is difficult to reduce the adhesion of the tape after the ultraviolet light, the wire, etc., which is disclosed in the patent document, and it is difficult to peel off the film wafer without using the conductor wafer or the like. Patent Document 2 discloses that A heated release adhesive sheet containing an adhesive layer of heat-expandable microspheres. If the heat-peelable adhesive sheet of Patent No. 2 is heated to a specific temperature or higher, then The expansive microspheres swell, and the adhesive layer is entirely foamed to form a concave ridge on the surface, and the adhesion area to the adherend is reduced, so that the smear can be easily peeled off. However, Patent Document 2::... peeling type adhesive sheet 'The heat is heated and the heat-expandable microspheres are swollen, and the surface is caused by fine irregularities. The change between the surface and the body is caused by the stress of the adhesive layer peeling off from the adherend during the expansion process. After you click on the point, then the force will be remnant, so == and the adherend U is not known to damage the film wafer or the semiconductor film, etc., and it is difficult to peel off the warehouse. It is said that it is adhered after peeling off. In addition, there is also the problem of using the residue of the two-two paste. In the case of the heat-expandable microsphere of only 13〇t left. It is difficult to use. In terms of heat, the manufacturing steps of TSV are disclosed in Patent Document 3, and there is no stimuli such as a double-sided tape azo compound. Body agent adhesion Right-handed looking for the double-sided tape of the document 3, the raw gas is released to the tape I, and the gas generating agent produces the body to... Eight: the interface between the adherends, the body is stuck to the body. The double-sided tape which is peeled off by the pressure by the branch can be used in the case of the patent document 3, the flawed film wafer or the semiconductor chip, and the residual tape is not generated. The party + (4) and 驮3 are difficult to use in the Tsv system by the existence of the question. The step of W is currently in the manufacturing step of TSV. The following method is used: using 3 stone black The light-absorbing body material is then decomposed and separated by the adhesion of the k-type fine particle powder, and is decomposed and separated by the heat of the laser beam (Non-Patent Document 1). However, when the technique of the non-patent document i is used, In addition to the problem of equipment requiring a laser irradiation device, there is also a problem that the fine particle powder is scattered by the decomposition of the adhesive due to the laser irradiation, and the cleanliness of the manufacturing environment is lowered. CITATION LIST Patent Literature Patent Literature 1: Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Established Technology" Vol. 28 Ν0·1 (2008) Complete Works No. 9 P.28 [Description of the Invention] An object of the present invention is to provide a high adhesion force which can be easily peeled off and which is excellent in heat resistance. The composition of the agent. The present invention is an adhesive composition comprising an adhesive component and a carboxylic acid compound represented by the following formula (1) or a salt thereof: ?-coon R6 wherein R1 to R7 represent hydrogen or organic, respectively. base. R1 to R7 may be the same or different. Two of R1 to R7 may be bonded to each other to form a ring structure. The present invention will be described in detail below. The present inventors have found that the carboxylic acid compound represented by the above formula (A) or a salt thereof has a high gas content of about 200 t by irradiation with light such as ultraviolet rays. And found that the servant, the body (carbon dioxide gas), and the other party
201139595 本發明之接著劑組成物含有接著劑成分。 上述接著劑成分並無特別限定，可含有非硬化型接著 劑、硬化型接著劑之任一者。 於上述接著劑成分為含有非硬化型接著劑之情形時， 藉由對本發明之接著劑組成物照射光且利用專利文獻2所 揭示之態樣之剝離機構來產生剝離。即，藉由照射光，而 由上述式（1)所示之羧酸化合物或其鹽產生氣體，柔軟之 接著劑成分之整體由於所產生之氣體而發泡，於表面形成 凸藉此產生剝離應力，另外與被黏著體之接著面積減 小而剝離。 於上述接著劑成分含有硬化型接著劑之情形時，藉由 對本發明之接著劑組成物照射光且利用專利文獻3所揭示 之態樣之剝離機構來產生剝離。即，藉由照射光而由上述 式ji)所示之羧酸化合物或其鹽產生氣體，所產生之氣體 自/經硬化之接著劑成分中釋放至與被黏著體之界面，被黏 著體之至少一部分因該壓力而剝離。 其中，由於可不產生糊劑殘餘而確實地進行剝離故 較佳為含有會因刺激而彈性模數上升之硬化型接著劑。 9上述非硬化型接著劑並無特別限定，例如可舉出：橡 ’系接著劑、丙烯酸系接著齊丨、乙烯基烷基醚系接著劑、 聚石夕氧系接著劑、聚®旨系接著劑、聚醯胺系接著劑、胺s| 系接著劑、苯乙烯·二烯嵌段共聚物系接著劑等。 a ^上述硬化型之接著劑並無特別限定，例如可舉出：以 聚“生聚合物作為主成分’含有光聚合起始劑或熱聚合起 201139595 始劑之光硬化型接著劑或熱硬化型接著劑。 此種光硬化型接著劑或熱硬化型接著劑由於會因光之 照射或加熱而使接著劑之整體均勻且迅速地聚合交聯而一 體化，故由聚合硬化所致之彈性模數之上升變得顯著，接 者力大幅度下降。另外，於彈性模數上升之較硬之硬化物 中’右由上述式（1)所示之羧酸化合物或其鹽產生氣體， 則所產生之氣體之大部分釋放至外部，所釋放之氣體使黏 著劑之接著面之至少一部分自被黏著體剝離而使接著力下 降。 上述聚合性聚合物例如可藉由如下方法獲得：預先合 成於分子内具有官能基之（甲基）丙烯酸系聚合物（以下，稱 為含S忐基之（曱基）丙烯酸系聚合物），使其與分子内具有 與上述g能基反應之官能基與自由基聚合性不飽和鍵之化 &物（以下，稱為含官能基之不飽和化合物）反應。 上述含官能基之（甲基）丙烯酸系聚合物作為常溫下具 有黏著性之聚合物，與一般之（曱基）丙烯酸系聚合物之情形 相同，係藉由如下方法獲得：以烷基之碳數通常於2〜i 8 之範圍内之丙烯酸烷基酯及/或甲基丙烯酸烷基酯作為主 單體，藉由常規方法使其與含官能基之單體，進而根據需 要與可與該等共聚合之其他改質用單體共聚合。上述含官 能基之（甲基）丙烯酸系聚合物之重量平均分子量通常為2〇 萬〜200萬左右。 上述含官能基之單體’例如可舉出：丙稀醵、甲基丙 烯酸等含绎基之單體，或丙烯酸羥乙酯、曱基丙烯酸羥乙 201139595 西曰：：&基之單體’或丙烯酸環氧丙冑、甲基丙烯酸環氧 丙自曰.等3 %氧基之單體，或丙烯酸異氰酸酯基乙酯、曱基 丙烯酸：氰酸醋基乙s旨等含異氰酸醋基之單體，或丙烯： 胺基乙sa甲基丙稀酸胺基乙酯等含胺基之單體等。 上述可共聚合之其他改質用單體，例如可舉出：乙酸 乙烯醋、丙烯腈、笨乙烯等用於—般之（甲基）丙缔酸系聚合 物之各種單體p 使上述含官能基之（甲基）丙烯酸系聚合物反應之含官 能基之不飽和化合物，根據上述含官能基之（甲基）丙烯酸系 聚合物之官能基，可使用與上述含官能基之單體同樣者。 例士於上述3 g月包基之（曱基）丙烯酸系聚合物之官能基為 羧基之情形時，可使用含環氧基之單體或含異氰酸酯基之 單體；於該官能基為羥基之情形時，可使用含異氰酸酯基 之單體，於該官能基為環氧基之情形時，可使用含羧基之 單體或丙烯醯胺等含醯胺基之單體；於該官能基為胺基之 情形時，可使用含環氧基之單體。 上述光聚合起始劑係，例如可舉出藉由照射2 5 〇〜 800nm之波長之光而活化者此種光聚合起始劑，例如可舉 出.甲氧基笨乙酮等苯乙酮衍生物化合物，或安息香丙喊、 安息香異丁醚等安息香醚系化合物，或苯二甲基縮酮 (Benzyl dimethyl ketal)、苯乙酮二乙基縮酮（Acet0 phen〇ne diethyl ketal)等縮酮衍生物化合物，或氧化膦衍生物化合 物，或雙（77 5 — %戊一稀基）二茂鈦衍生物化合物，二苯曱 酮、米其勒酮（Michiler’s ketone)、氣硫雜蒽酮、十二烷基 201139595 硫雜蒽酮、二甲基硫雜蒽酮、_ 一乙基硫雜蒽酮、α _羥基 環己基苯基酮、2-μ基甲基苯基丙烧等光自由基聚合起始 劑。該等光聚合起始劑可單獨使用，亦可併用2種以上。 上述熱聚合起始劑，可舉出藉由熱而分解，產生使聚 合硬化開始之活性自由基者，例如可舉出：雙異苯丙基過 氧化物、過氧化二第三丁基、過氧化苯甲酸第三丁醋、氫 過氧化第三丁基、過患仆笑审納 &。 "尥乳化本甲醯、氫過氧化異丙苯、氮過 氧化二異丙基#、氫過氧化對薄荷烷(Pa職enthane hydroperoxide)、過氧化二第三丁基等。 其中，為使本發明之接著劑組成物發揮高耐熱性，上 述熱聚合起始劑較佳為使用熱分解溫度為2〇〇1以上之熱 聚合起始劑。此種熱分解溫度較高之熱聚合起始劑可舉 出：氫過氧化異丙苯、氫過氧化對薄荷烷、過氧化二第三 丁基等》 一 該等熱聚合起始劑中之市售品並無特別限定，較佳為 例如 Perbutyl D、Perbutyl η、Perbutyl p、卜取咖 h (以 上均為日油公司製造）等。該等熱聚合起始劑可單獨使用， 亦可併用2種以上。 上述光硬化型接著劑或熱硬化型接著劑較佳為進而含 有自由基聚合性之多官能寡聚物或單體。藉由含有自由基 聚合性之多官能寡聚物或單體，而使光硬化性、熱硬化性 提南。 上述多官能寡聚物或單體較佳為分子量為丨萬以下 者’為了藉由加熱或光照射而高效率地實現黏著劑層之三 10 201139595 維網狀化，更佳為其分子量為5000以下且分子内之自由基 聚合性之不飽和鍵之個數為2〜20個者。 上述多官能寡聚物或單體係例如可舉出：三經曱基丙 烷三丙烯酸酯、四羥曱基曱烷四丙烯酸酯、新戊四醇三丙 稀酸酯、新戊四醇四丙烯酸酯、二新戊四醇一羥基五丙烯 酸酯、二新戊四醇六丙烯酸酯或與上述同樣之曱基丙烯酸 酯類等。其他可舉出：M— 丁二醇二丙烯酸醋、丨，6—已二 醇二丙烯酸酿、聚乙二醇二丙烯酸酯、市售之寡酯丙烯酸 酉旨、與上述同樣之曱基丙烯酸醋類等。該等多官能寡聚物 或單體可單獨使用，亦可併用2種以上。 本發明之接著劑組成物含有上述式 1 )所示之羧酸化 合物或其鹽。上述式（1)中，Ri〜 R1〜R7可相同亦可不同。Ri〜R7 形成環狀結構》 r7分別表示氫或有機基。 中之兩個亦可相互鍵結而 ，么、U丞、内基、丁基、 異丁基等烧基，或甲氧基、乙氧基等絲基，或竣基，或 經基，或硝基，或苯基等芳香族基，或萘基、葬某 等多環式烴基，或聯苯基等隼合 土 土 Μ 基’或啊基等雜環基 #。 其中’較佳為式（！）中 3 7 一 ）干之R〜R中之1個為下述式（2、 所示之有機基，或式（1)中之r3 7 ‘ ^ ^ R〜R中之相鄰之兩個相互 鍵結而形成下述式（3 )戶斤千夕碑山 所不之環狀結構者。 11 (2)201139595 The adhesive composition of the present invention contains an adhesive component. The adhesive component is not particularly limited, and may contain either a non-curing adhesive or a curable adhesive. In the case where the above-mentioned adhesive component contains a non-curing adhesive, the peeling mechanism is irradiated with the adhesive composition of the present invention and the peeling mechanism of the aspect disclosed in Patent Document 2 is used. In other words, by the irradiation of light, a gas is generated from the carboxylic acid compound represented by the above formula (1) or a salt thereof, and the entire adhesive component is foamed by the generated gas to form a protrusion on the surface to cause peeling. The stress is additionally peeled off by the reduction in the area of the adherend. In the case where the adhesive component contains a curable adhesive, the peeling mechanism is irradiated with the adhesive composition of the present invention and the peeling mechanism of the aspect disclosed in Patent Document 3 is used to cause peeling. That is, a gas is generated by the carboxylic acid compound represented by the above formula (ji) or a salt thereof by irradiation of light, and the generated gas is released from the hardened adhesive component to the interface with the adherend, and is adhered to the adherend. At least a portion is peeled off due to the pressure. Among them, since the peeling can be reliably performed without causing the residue of the paste, it is preferable to contain a hardening type adhesive which increases the modulus of elasticity due to the stimulation. The non-hardening type adhesive agent is not particularly limited, and examples thereof include an rubber-based adhesive, an acrylic-based adhesive, a vinyl alkyl ether-based adhesive, a polyoxin-based adhesive, and a poly-based system. The adhesive, a polyamine-based adhesive, an amine s|-based adhesive, a styrene-diene block copolymer-based adhesive, and the like. a ^ The above-mentioned curing type adhesive is not particularly limited, and examples thereof include a photopolymerization initiator containing a "green polymer as a main component" or a photocurable primer or a thermal curing polymerization agent starting from 201139595. The above-mentioned photocurable adhesive or thermosetting adhesive is integrated by the polymerization hardening due to uniform and rapid polymerization and cross-linking of the entire adhesive due to irradiation or heating of light. The increase in the modulus is remarkable, and the strength of the contact is greatly reduced. Further, in the harder hardened product in which the elastic modulus is increased, the gas is generated by the carboxylic acid compound represented by the above formula (1) or a salt thereof. Most of the generated gas is released to the outside, and the released gas causes at least a part of the adhesion surface of the adhesive to be peeled off from the adherend to lower the adhesion force. The above polymerizable polymer can be obtained, for example, by the following method: a (meth)acrylic polymer having a functional group in the molecule (hereinafter referred to as an sulfonium-containing (fluorenyl) acrylic polymer) having an inverse relationship with the above-mentioned g group in the molecule The functional group is reacted with a radically polymerizable unsaturated bond and an object (hereinafter referred to as a functional group-containing unsaturated compound). The functional group-containing (meth)acrylic polymer has adhesion as a normal temperature. The polymer is obtained in the same manner as the general (fluorenyl) acrylic polymer by the following method: an alkyl acrylate having a carbon number of the alkyl group usually in the range of 2 to 8 and/or The alkyl methacrylate is used as a main monomer, and is copolymerized with a functional group-containing monomer by a conventional method, and further copolymerized with other modifying monomers copolymerizable with the above. The weight average molecular weight of the (meth)acrylic polymer is usually from about 20,000 to 2,000,000. The monomer containing the functional group is, for example, a thiol-containing monomer such as acrylonitrile or methacrylic acid. Or hydroxyethyl acrylate, hydroxyethyl methacrylate 201139595 oxime:: & base monomer' or acrylic epoxihydrene, methacrylic acid propylene acrylate, etc., 3% oxy monomer, or acrylic acid Isocyanate ethyl ester, sulfhydryl Acrylic acid: cyanic acid acetate, etc., or an isocyanate group-containing monomer, or propylene: an amine group, an amino group, an amino group, an amino group, an amine group-containing monomer, etc. Examples of the other monomer for reforming include vinyl acetate vinegar, acrylonitrile, stupyl ethylene, and the like, and various monomers p such as a (meth) propionic acid-based polymer. The functional group-containing unsaturated compound to be reacted with the methyl group-based acrylic polymer may be the same as the above-mentioned functional group-containing monomer, depending on the functional group of the functional group-containing (meth)acryl-based polymer. In the case where the functional group of the above 3 g of the (indenyl) acrylic polymer is a carboxyl group, an epoxy group-containing monomer or an isocyanate group-containing monomer may be used; in the case where the functional group is a hydroxyl group In the case where the functional group is an epoxy group, a carboxyl group-containing monomer or a mercaptoamine-containing monomer such as acrylamide may be used; the functional group is an amine group. In the case of the case, an epoxy group-containing monomer can be used. The photopolymerization initiator may, for example, be a photopolymerization initiator activated by irradiation with light having a wavelength of from 25 Å to 800 nm, and examples thereof include acetophenone such as methoxyacetophenone. a derivative compound, or a benzoin ether compound such as benzoin, benzoin isobutyl ether, or Benzyl dimethyl ketal or acetophenone diethyl ketal a ketone derivative compound, or a phosphine oxide derivative compound, or a bis(77 5 - pentyl) ferrocene derivative compound, benzophenone, Michiler's ketone, thiazepine , dodecyl 201139595 thioxanthone, dimethyl thioxanthone, _ ethyl thioxanthone, α-hydroxycyclohexyl phenyl ketone, 2-μ methyl propyl propyl ketone, etc. Base polymerization initiator. These photopolymerization initiators may be used singly or in combination of two or more. The thermal polymerization initiator may be one which decomposes by heat and generates active radicals which initiate polymerization hardening, and examples thereof include bisisophenylpropyl peroxide and dibutyl butyl peroxide. Oxidized benzoic acid, third butyl vinegar, tert-butyl hydroperoxide, sorrow and appreciator &"尥Emulsified methacrylate, cumene hydroperoxide, diisopropyl nitric oxide #, hydroperoxide p-menthane (Pa enthane hydroperoxide), dibutyl butyl peroxide, and the like. In particular, in order to impart high heat resistance to the adhesive composition of the present invention, the thermal polymerization initiator is preferably a thermal polymerization initiator having a thermal decomposition temperature of 2 〇〇 1 or more. Examples of the thermal polymerization initiator having a high thermal decomposition temperature include: cumene hydroperoxide, hydrogen peroxide, menthane, dibutyl butyl peroxide, etc., among the thermal polymerization initiators. Commercially available products are not particularly limited, and are, for example, Perbutyl D, Perbutyl η, Perbutyl p, and Bu Kah (all manufactured by Nippon Oil Co., Ltd.). These thermal polymerization initiators may be used singly or in combination of two or more. The photocurable adhesive or the thermosetting adhesive is preferably a polyfunctional oligomer or monomer further containing a radical polymerizable property. Photocurability and thermosetting property are promoted by a polyfunctional oligomer or a monomer containing a radical polymerizable property. The polyfunctional oligomer or monomer is preferably one having a molecular weight of 10,000 or less. In order to efficiently realize the reticulation of the adhesive layer by heating or light irradiation, the molecular weight is preferably 5000. Hereinafter, the number of radically polymerizable unsaturated bonds in the molecule is 2 to 20. Examples of the above polyfunctional oligomer or single system include: tri-propyl mercaptan triacrylate, tetrahydrononyl decane tetraacrylate, neopentyl alcohol triacrylate, and neopentyl alcohol tetraacrylate. Ester, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or the same mercapto acrylates as described above. Other examples include M-butanediol diacrylate vinegar, hydrazine, 6-hexanediol diacrylic acid brewing, polyethylene glycol diacrylate, commercially available oligoester acrylic acid, and the same thioglycolic acid vinegar as described above. Classes, etc. These polyfunctional oligomers or monomers may be used singly or in combination of two or more. The adhesive composition of the present invention contains the carboxylic acid compound represented by the above formula 1) or a salt thereof. In the above formula (1), Ri to R1 to R7 may be the same or different. Ri~R7 form a cyclic structure" r7 represents hydrogen or an organic group, respectively. Two of them may be bonded to each other, such as U, an internal group, a butyl group, an isobutyl group or the like, or a methoxy group, an ethoxy group or the like, or a fluorenyl group, or a thiol group, or a thiol group, or An aromatic group such as a nitro group or a phenyl group, or a naphthyl group, a polycyclic hydrocarbon group such as a burial group, or a heterocyclic group such as a biphenyl group or the like. Wherein 'preferably in the formula (!), 3 7 a) one of R to R is an organic group represented by the following formula (2, or r3 7 ' ^ ^ R in the formula (1) The two adjacent ones of R are bonded to each other to form a ring structure of the following formula (3).
(3) 相同亦可不同 f分別表示氳或有機基，狄8 結構。 中之兩個亦可相互鍵結而升、可 式（3) 〜狀 中，H13〜Rl6 八 β, ± 可相同亦可不 刀別表示氫或，有機基，R 13 叫，H13〜〇16士々工y ^〜Rh 狀結構。 中之兩個亦可相互鍵結而 另外，上述式， 飞（㈠中之R1較佳為甲基。 上述式（1)所- 叮不之羧酸化合物之具體例，例如 苯基乙酸、二贫I 舉出： 麥 一本基乙酸、三苯基乙酸、2 —苯基丙酸、22 一二苯基丙酸、2,2,2 一三苯基丙酸、2 —苯基丁酸、α_甲 氧基苯基乙酸、苯乙醇酸（Mandelic acid)、2 —苯乳酸 (atrolactonk add)、二苯乙醇酸、顛茄醇酸、苯基丙二酸、 苯基丁二酸、3—曱基一2—苯基丁酸、鄰曱苯醯基乙酸、 12 201139595 甲基f苯醯基乙酸、4一異丁基一 α —甲基苯基乙酸、對甲 苯醯基乙酸、1,2_伸苯基二乙酸、〗，3—伸苯基二乙酸、1，4 —伸苯基二乙酸、2—$氧基苯基乙酸、2—羥基苯基乙酸' 2 —硝基苯基乙酸、3 —硝基苯基乙酸、4 一硝基苯基乙酸、 2 — (4 —硝基苯基）丙酸、3 — (4 ~硝基苯基）丙酸、4 一（4 一硝 基笨基）丙酸、3,4 —二甲氧基苯基乙酸、3,4 —（亞甲基二氧 基）苯基乙酸、2,5—二甲氧基苯基乙酸、3,5_二甲氧基苯基 乙酸、3,4,5—三曱氧基苯基乙酸、2,4—二硝基苯基乙酸、斗 ~聯苯基乙酸、1—萘基乙酸、2_萘基乙酸、6 —曱氧基— α -曱基-2—萘基乙酸、卜r匕乙酸、9— f曱酸或 山口星_ 9 —甲酸等。 9H- ~ 1 ) 酸。 其中上述式（1)所示之羧酸化合物較佳為 所示之酮洛芬、或下述式（丨—2) 巧（] '、之2 ~~ d山_乙(3) The same or different f denotes 氲 or organic, Di 8 structure. Two of them can also be bonded to each other, and can be typed (3) ~ in the shape, H13~Rl6 八β, ± can be the same or not, or hydrogen, organic group, R 13 is called, H13~〇16 Completion y ^ ~ Rh-like structure. Two of them may be bonded to each other, and in the above formula, fly (in R) is preferably a methyl group. Specific examples of the carboxylic acid compound of the above formula (1), such as phenylacetic acid, Lean I: wheat-based acetic acid, triphenylacetic acid, 2-phenylpropionic acid, 22-diphenylpropionic acid, 2,2,2-triphenylpropionic acid, 2-phenylbutyric acid, _-methoxyphenylacetic acid, Mandelic acid, 2-trolactonk add, diphenyl glycolic acid, belladonnaic acid, phenylmalonic acid, phenyl succinic acid, 3- Mercapto-2-phenylbutyric acid, o-phthalyl acetic acid, 12 201139595 methyl f-benzoyl acetic acid, 4-isobutyl-α-methylphenylacetic acid, p-tolyl acetic acid, 1, 2 _ phenyl diacetic acid, 〗 〖, 3-phenylene diacetic acid, 1,4 -phenylene diacetic acid, 2- oxyphenyl acetic acid, 2-hydroxyphenyl acetic acid ' 2 -nitrophenyl acetic acid , 3-nitrophenylacetic acid, 4-nitrophenylacetic acid, 2-(4-nitrophenyl)propionic acid, 3-(4-nitrophenyl)propionic acid, 4-(4-nitro) Stupid base) propionic acid, 3,4-dimethoxyphenyl Acid, 3,4-(methylenedioxy)phenylacetic acid, 2,5-dimethoxyphenylacetic acid, 3,5-dimethoxyphenylacetic acid, 3,4,5-triazine Oxyphenylacetic acid, 2,4-dinitrophenylacetic acid, bucket-biphenylacetic acid, 1-naphthylacetic acid, 2-naphthylacetic acid, 6-decyloxy-α-mercapto-2-naphthalene Acidic acid, bromoacetic acid, 9-f citric acid or Yamaguchi _ 9 - formic acid, etc. 9H- ~ 1 ) acid. The carboxylic acid compound represented by the above formula (1) is preferably ketoprofen as shown, or the following formula (丨-2) 巧(] ', 2~~d mountain_B
ΟΙ 0 ΗI c—COOH CH3 (1 — 1〉ΟΙ 0 ΗI c—COOH CH3 (1 – 1>
(1 — 2) 13 201139595 上述式（l)所不之叛酸化合物之鹽亦具有源自上述式 ⑴所示之叛酸化合物之骨架，因此若照射光，則可容易 引起脫叛’可產生二氧化碳氣體。 上述式⑴所示之幾酸化合物之鹽僅藉由將上述式⑴ 所不之叛酸化合物與驗性化合物於容器中混合，不經過複 雜之合成路徑即可簡單地製備。 上述驗性化合物並益转3丨阳 1热符別限疋，例如可舉出：胺、肼 化合物 '氫氧化四級銨鹽 '膦化合物等。 上述胺並無特別限定，可佶用一 J使用 級胺、二級胺及三級 胺之任一者。 f中上述驗性化合物較佳為單院基胺或二烧基胺。於 使用單烷基胺或二烷基胺之情形時，可使所得之上述式（〇 所示之羧酸化合物之鹽之極性低極性化，可提高與接著劑 成分之溶解性。更佳為錢6〜12<單燒基胺或二烧基胺。 含有藉由刺激而彈性模數上升之硬化型接著劑作為上 述接著劑成分之情形時’上述式⑴所示之叛酸化合物或 其鹽較佳為溶解於接著劑成分。藉由上述式（丨）所示之羧 酉文化合物或其鹽溶解於接著劑，而使該等化合物自身不會 成為發泡之核心，產生之氣體幾乎全部自接著劑成分釋放 至與被黏著體之界面，因此可更加確實地進行剝離。因此， 較佳為溶解性更高之上述式（1)所示之羧酸化合物之鹽。 於使用上述含官能基之（甲基）丙烯酸系聚合物作為上 述接著劑成分’上述式（υ所示之羧酸化合物為上述式（夏 —1)所示之酮洛芬之情形時，酮洛芬及其鹽均顯示出對接 201139595 著劑成分之高溶解性。 於使用上述含官能基之（甲基）丙烯酸系聚合物作為上 述接著劑成分，上述式（1 )所示之羧酸化合物為上述式（！ 酸較佳為用 —2 )所示之2 — 〇山酮乙酸之情形時，2 — d山酮乙 作為進行低择性化而提高對接著劑成分之溶解性的鹽 上述式（1)所示之羧酸化合物或其鹽之含量相對於上 述接著劑成分100重量份之較佳下限為5重量份，較佳上 限為50重量份。若上述式（1)所示之羧酸化合物或其鹽 之含量未達5重量份，則存在由光照射所引起之二氧化碳 氣體之產生變少而無法進行充分之剝離之情況，若超過5〇 重置份，則存在無法完全溶解於接著劑成分令而導致接著 力下降之情況。上述式（1)所示之羧酸化合物或其鹽之含 1之更佳下限為10重量份，更佳上限為3〇重量份。 本發明之接著劑組成物亦可含有光敏劑。 由於上述光敏劑具有增大光對上述式（1)所示之羧酸 口物或其鹽之刺激之效果，因此可藉由更少之光照射而 釋放出氣體。另外’可藉由更寬之波段之光而釋放出氣體。 上述光敏劑只要為耐熱性優異者，則並無特別限定。 耐熱性優異之光敏劑例如可舉出具有至少1個以上之 燒氧基之多環芳香族化合物。其中較佳為具有-部分由環 乳丙基❹基取代之烧氧基之取代院氧基多環芳香族化合 物。該等光敏劑之耐昇華性較高，可於高溫下使用。另外， y元氧基《部由環氧丙基或羥基取代，故對上述接著 劑成分之溶解性提高，可防止滲出。 15 201139595 上述多環芳香族化合物較佳為蒽衍生 ，〜p v ，八·；，也、 季交佳為碳數J 1 ”” 1 8者’更佳為碳數為1〜8者。 具有至少1個以上之上述烧氧基 例如可舉出：9，10、…其… 方香私化合物 基葱、2—m 乙基―9，10-二甲氧 乐一 丁基〜9，10—二曱氧基蒽、2,3—二 —二曱氯美笛、0 土 ~~ 9，1〇 T氧基蒽、9—曱氧基_1〇—曱基蒽 蒽、2 —乙美—q1a —乙氧基 土 ，10—二乙氧基蒽、2—第三丁基—9 乙氧基蒽、2,3— -甲A 〇 1Λ & ^ ，ϋ〜二 ‘曱基蒽、”:Γ— 蒽、9—乙氧基〜 心、5 —丙氧基蒽、2一乙基一9,1〇〜二 基蒽、2 -第二丁基—9，1〇_二丙氧基蒽、2，卜二〜 -二丙氧基蒽、9—異丙氧基—1〇_甲基蒽、9 1〇一 9’10 基蒽、9，10—二苄氧其贫9_ 7 . η ， 一丁氧 H、2-乙基—9’10—二节氧基葱、2 第二丁基-9，10〜二节氧基葱、2,3—二甲基m 氡基葱、9-节氧基—1〇—甲基葱、9，1〇_ ’ ：节 氣基葱、2—乙基…。—二1 —甲基节氧基葱、JJ节 丁基-9，1〇-二…甲基节氧基葱、2,3一二甲 二 缓基乙氧基）蒽等蒽衍生物等 -二…甲基节氧基葱、9—(α_甲基节氧基卜1〇，1: 基蒽、9，Η)-二（2〜經基乙氧基）葱、2—乙基—一甲 ~ 'dh. Μ. 7 ^ ^· \ s± ^ ^ ’ — (2 上述具有一部分由環氧丙基或經基取代之炫氧 代炫氧基多環芳香族化合物例如可舉出：9，W_ : 基氧基）蒽、2 —乙基—91〇 一一 衣氧丙 ，ί〇 一（¾氧丙基氧基）蒽、笛一 丁基-9，I0-二（縣丙基氧基）蒽、2,3—巧基 第: (環氧丙基氧基環氧丙基氧基）—1〇 ㉟ ^ ^ '951〇 16 201139595 —二（2 —乙烯氧基乙氧基）蒽、2—乙基~9,1〇—二（2_乙烯 氧基乙氧基）蒽、2 —第三丁基一 9,10 —二（2 —乙烯氧基乙氧 基）蒽、2,3—二曱基一 9,10 —二（2 —乙烯氧基乙氧基）蒽、9 —(2 —乙稀氧基乙氧基）一 10—曱基蒽、9,10 —二（3 一曱基一 3 —氧雜環丁烷基曱氧基）蒽、2—乙基一9,10—二（3 —甲基 —3 —氧雜環丁烷基曱氧基）蒽、2 —第三丁基_ 9,1〇 一二（3 —曱基一3 —氧雜環丁烷基曱氧基）蒽、2,3—二f基—9,10 —一（3—曱基一3 —氧雜環丁烧基甲氧基）蒽、9一（3—甲基 —3 —氧雜環丁烧基甲氧基）—1〇 —甲基蒽、9, i〇_二（對環 氧苯基曱氧基）蒽、2 —乙基一9,10—二（對環氧苯基甲氧基） 蒽、2 —第三丁基—9，10_二（對環氧苯基甲氧基）蒽、2,3_ 二曱基一9,1 0 —二（對環氧苯基曱氧基）蒽、9 —(對環氧苯基 曱氧基）一10 —甲基蒽、9,10—二（對乙烯基苯基曱氧基）蒽、 2 -乙基一9,10 —二（對乙烯基苯基曱氧基）蒽、2_第三丁基 —9，10 —二（對乙烯基苯基曱氧基）蒽、2,3 —二甲基—9，1〇_ 二（對乙烯基苯基甲氧基）蒽、9-(對乙烯基苯基甲氧基1〇 —曱基恩、9,10 —二（2 —經基乙氧基）蒽、9,10—二（2 —經基 丙氧基）蒽、9,10 —二（2 -羥基丁氧基）蒽、9,10 —二（2—羥 基一 3 — 丁氧基丙氧基）蒽'9,1〇 —二（2 —羥基一3—(2 —乙基 己氧基）丙氧基）蒽、9,10 —二（2—經基一3 —稀丙氧基丙氧基） 蒽、9,10 —二（2—經基一3 —苯氧基丙氧基）蒽、9,10 —二（2,3 一二羥基丙氧基）蒽等。 上述光敏劑之含量相對於上述接著劑成分1〇〇重量份 之較佳下限為〇. 〇 5重量份，較佳上限為1 〇重量份^若上述 17 201139595 光敏劑之含量未達0.05.重量份，則存在無法獲得充分之敏 化效果之情況，若超過1〇重量份，則存在源自光敏劑之殘 餘物增加，無法進行充分之剝離之情況。上述光敏劑之含 量之更佳下限為0.1重量份，更佳上限為5重量份。 本發明之接著劑組成物以實現作為黏著劑之凝聚力之 調節為目的，亦可根據需要而適當地含有摻合於異氰酸酯 化合物'三聚氰胺化合物、環氧化合物等一般之黏著劑之 各種多官能性化合物。 本發明之接著劑組成物亦可含有塑化劑、樹脂、界面 活性劑、蠟、微粒子填充劑等公知之添加劑。 本發明之接著劑組成物具有較高之接著力，另一方面. 藉由進行光照射或加熱可容易地剝離。另外，由於耐熱性 亦優異，故而亦可用於以下用途：在TSV之製造步驟中， 進行將晶圓固定於支撐板上等之20(rc以上之高溫處理。 本發明之接著劑組成物可用於各種接著性製品。 上述接著性製品，例如可舉出：將本發明之接著劑組 成物用作為黏合劑樹脂之接著劑、黏著劑、塗料、塗佈劑、 也、封劑等，或將本發明之接著劑組成物用作為黏著劑之單 面黏著帶、雙面黏著帶、無支撐帶（自立膠帶）等膠帶等。 於基材之至少一面上具有由本發明之接著劑組成物所 構成之接著層之接著帶亦為本發明之一。 上述基材例如可舉出：由丙烯酸、烯烴、聚碳酸酯' 氣乙烯、ABS、聚對苯二甲酸乙二酯（PET )、尼龍、胺酯、 聚醯亞胺等透明之樹脂構成之片材，具有網狀構造之片 18 201139595 材’開孔之片材等。 根據本發明，可提供一種具有高接著力而又可容易地 剝離’且耐熱性亦優異之接著劑組成物。 【實施方式】 以下列舉實施例更加詳細地說明本發明之態樣，但本 發明並不僅限定於該等實施例。 (實施例1 ) 準備具備溫度計、攪拌機、冷卻管之反應器，於該反 應器内添加丙烯酸2一乙基己酯94重量份、丙烯酸丄重量 伤、丙烯酸2—羥乙酯5重量份、月桂硫醇〇 〇1重量份、 及乙敲乙酯1 80重量份後’加熱反應器而開始回流。繼而， 於上述反應器内添加U—雙（過氧化第三己基）—3,3,5—三 曱基環己烧G.G1重量份作為聚合起始劑，於回流下使聚合 開始。其次，於聚合開始丨小時後及2小時後，均分別添 f 11 ~~雙（過氧化第三己基3,3,5一三甲基環己烧〇 〇1重 里伤，進而！於聚合開始4小時後添加過氧異丁酸三級己 酉曰（tert~heXyl per〇xypivaUte)〇 〇5重量份而使聚合反應繼 、只進仃。並且，於聚合開始8小時後，獲得固體含量55重 里％、重量平均分子量6〇萬之丙稀酸共聚物。 相對於含有所得之丙烯酸共聚物之乙酸乙酯溶液之樹 月曰口體含罝1 〇〇重量份，添加曱基丙烯酸2 —異氰酸基乙酯 3 ·5重里份而使其反應，進而，相對於反應後之乙酸乙酯溶 之祕知固體含量】〇〇重量份混合光聚合起始劑（Esacure 0ne，日本SiberHegner公司製造）〇」重量份、聚異氰酸酯 19 201139595 系交聯劑（c_ate L45,日本聚胺醋公司製造）2旦 份’製備接著劑（1 )之乙酸乙酯溶液。 相對於接著劑（1 )之乙酸乙酯溶 合狀之树脂固體含量1 00 重罝份，混合嗣洛芬（東京化成工業公司製造）Μ重量份、 之W0-二環氧丙氧m重量份，獲得接著 劑組成物。 將所得之接著劑組成物以乾燥皮膜之厚度成為30_ 之方式利用刮刀塗佈於單面實施電暈處理之厚度m之 透明聚對笨二甲酸乙二酯膜之電暈處理面上，於"代加熱 5分鐘而使塗佈溶液乾燥。其後， … ^進仃3天靜置固 化’而獲得接著帶。 (實施例2) 除摻合9，10-雙（2一經基丙氧基）葱i重量份代替㈣ —二環氧丙氧基蒽丨重量份來作為光敏劑以外，與實施例1 同樣地操作而獲得接著劑組成物及接著帶。 (實施例3) 除摻合9’10-二丁氧基蒽！重量份代替9，ι〇—二環氧 丙氧基蒽1重量份作為光敏劑以外，與實施例i同樣地操 作而獲得接著劑組成物及接著帶。 (實施例4) 外 除摻合2—卩山酮乙酸2〇重量份代替酮洛芬2〇重量份以 與實施例1同樣地操作而獲得接著劑組成物及接著帶。 (實施例5) 除摻合2 —汕酮乙酸二硬脂基胺鹽2〇重量份代替酮洛 20 201139595 芬20重量份以外，與實施例i同樣地操作而獲得接著劑組 成物及接著帶。 (比較例1 ) 除不摻合酮洛芬以外，與實施例丨同樣地操作而獲得 接著劑組成物及接著帶。 (比較例2) 除推合2,2，-偶氮雙-(N- 丁基_2_甲基丙酿胺）2〇 重量份代替酮洛芬2G重量份，換合二乙基硫雜蒽綱3重量 份代替9,10-二環氧丙絲基复' 丄重量份以外，與實施例^ 同樣地操作而獲得接著劑組成物及接著帶。 (比較例3) 冷卻管之反應器，於該反 94重量份、丙烯酸1重量 、月桂硫醇0 · 〇 1重量份、 準備具備溫度計、攪拌機、 應器内添加丙烯酸2 —乙基己酯 份、丙烯酸2 —羥乙酯5重量份 及乙酸乙酿180重量份後，加熱反應器而開始回流。繼而， 於上述反應器内添力σ i，卜雙(過氧化第三己基卜三 f己烷0.01重里份作為聚合起始劑人 開始。其次，於聚合開始H、時後及2… 丁说夂2小時後，均分別添 :，-雙(過氧化第三己基卜3,3,5—三甲基環己烧〇 〇1重 =，進而’於聚峰4小時後添加過氧異丁酸三級己 :曰"二重量份而使聚合反應繼續進行。並且，於聚合開始 :夺後，獲得固體含量55重量％、重量平均分子量6〇萬 之丙烯酸共聚物。 相對於所得之丙稀酸系黏著劑1〇〇重量份（固體含 21 201139595 量），混合Microsphere F — 50D (松本油脂公司製造）50重 量份而獲得接著劑組成物。 將所得之接著劑組成物以乾燥皮膜之厚度成為30 A m 之方式利用刮刀塗佈於單面實施電暈處理之厚度5〇//m< 透明聚對苯二曱酸乙二酯膜之電暈處理面上，於u〇(»c進行 5分鐘加熱而使塗佈溶緣乾燥。其後，於4(^c進行3天靜 置固化，而獲得接著帶。 (評價） 針對實施例及比較例所得 進行評價。 將結果不於表1。 (1 )接著性評價、剝離性評價 將切割為直徑2〇cm之圓形之接著帶貼附於直徑 20cm、厚度約750 /z m之矽晶圓上。 接著性評價，係於該狀態下拉伸接著帶，將完全I、、去 剝離之情形評價為「〇」，將相較之下可輕鬆地剝離之情形 汗價為「△」，將可幾乎無阻礙地剝離之情形評價為「χ」。 :而’使用超高壓水銀燈，以對玻璃板表面之照射強 成為40tmw/cm2之方式調節照纟，自玻璃板側照射 nm之紫外線2分鐘。紫外结 伸捸装胜 ％卜線…射後之剥離性評價，係拉 冑，將可完全無阻礙地剝離之情形評價為 有阻礙但可剝離之情形 形評價為「9 賈為△」’將元全無法剝離之情 (2 )耐熱性評價 201139595 將切割為直徑 20cm之圓形之接著帶貼附於直徑 20cm、厚度約750 # m之矽晶圓。將該積層體於200°C加熱 2小時後，恢復至室溫。 針對加熱後之積層體，進行上述接著性評價、剝離性 評價。 23 201139595 於200進行2小時熱處理 剝離性 〇 〇 〇 〇 〇 X 1 1 接著性 〇 〇 〇 〇 〇 〇 X X 無熱處理 |剝離性| 〇 〇 〇 〇 〇 X 〇 <3 @著性1 〇 〇 〇 〇 〇 〇 〇 〇 光敏劑 9,10—二環氧丙基氧基蒽 9，10_雙(2 —羥基丙氧基)蒽 9,10 —二丁氧基蒽 9，10—二環氧丙氧基蒽 9，10—二環氧丙氧基蒽 9，10_二環氧丙氧基蒽 二乙基硫雜蒽酮 1 化合物 酮洛芬 ' 酮洛芬 酮洛芬 2_α山酮乙酸 2—D山酮乙酸二硬脂基胺鹽 1 2,2’一偶氮雙一(Ν-丁基一2-曱基丙醯胺） 熱膨脹性微球 實施例1 I實施例2 1 |實施例3 | |實施例4 | |實施例5 | |比較例11 |比較例2 | |比較例3 1 201139595 [產業上之可利用性] 根據本發明，可提供一種具有高接著力而又可容易地 剝離，且財熱性亦優異之接著劑組成物。 【圖式簡單說明】 無 【主要元件符號說明】 益 < »»、 25(1 - 2) 13 201139595 The salt of the tickling compound which is not in the above formula (1) also has a skeleton derived from the tickic acid compound represented by the above formula (1), so that if light is irradiated, it is easy to cause defection" Carbon dioxide gas. The salt of the acid compound represented by the above formula (1) can be simply prepared by mixing the tickic acid compound of the above formula (1) with the test compound in a container without passing through a complicated synthesis route. The above-mentioned test compound is preferably converted to a hydrazine, and is exemplified by an amine, a hydrazine compound, a quaternary ammonium hydroxide salt, a phosphine compound, and the like. The above amine is not particularly limited, and any one of a primary amine, a secondary amine, and a tertiary amine can be used. The above-mentioned test compound in f is preferably a single-complex amine or a dialkylamine. When a monoalkylamine or a dialkylamine is used, the polarity of the salt of the obtained carboxylic acid compound represented by the above formula (低) can be made low, and the solubility with the adhesive component can be improved. (6) The acid-reducing compound represented by the above formula (1) or a salt thereof, in the case where a hardening type adhesive having an elastic modulus increased by stimulation is used as the above-mentioned adhesive component. Preferably, it is dissolved in an adhesive component. The carbaryl compound represented by the above formula (丨) or a salt thereof is dissolved in the adhesive, so that the compounds themselves do not become the core of foaming, and almost all of the gas is generated. Since the adhesive component is released to the interface with the adherend, the peeling can be performed more reliably. Therefore, a salt of the carboxylic acid compound represented by the above formula (1) having higher solubility is preferred. When the (meth)acrylic polymer is used as the above-mentioned binder component 'the above formula (the carboxylic acid compound shown by υ is ketoprofen represented by the above formula (Summer-1)), ketoprofen and a salt thereof Both show docking 201139595 The solubility of the component is high. The carboxylic acid compound represented by the above formula (1) is the above formula (the acid is preferably used for the above-mentioned binder component). -2) In the case of 2 - oxanthone acetate, 2 - d ketone B is a salt of the above formula (1) as a salt for improving solubility in an adhesive component as a low selectivity The preferred lower limit of the content of the salt or the salt thereof is 5 parts by weight, and the upper limit is preferably 50 parts by weight. The content of the carboxylic acid compound or the salt thereof represented by the above formula (1) is less than In the case of 5 parts by weight, the generation of carbon dioxide gas caused by light irradiation is reduced, and sufficient peeling cannot be performed. If the replacement portion exceeds 5 〇, the adhesive component may not be completely dissolved in the adhesive component, resulting in a decrease in the adhesion force. In the case of the carboxylic acid compound represented by the above formula (1) or a salt thereof, the lower limit of the content of 1 is 10 parts by weight, and the upper limit is more preferably 3 parts by weight. The adhesive composition of the present invention may further contain a photosensitizer. Because the above photosensitizer has increased The effect of the large light on the stimulating effect of the carboxylic acid mouth or the salt thereof represented by the above formula (1), so that the gas can be released by irradiation with less light. In addition, it can be released by a wider band of light. The above-mentioned photosensitizer is not particularly limited as long as it is excellent in heat resistance. The photosensitizer excellent in heat resistance is, for example, a polycyclic aromatic compound having at least one or more alkoxy groups. - a substituted polyoxy aromatic compound substituted by an alkoxy group substituted by a cyclopropyl fluorenyl group. These photosensitizers have high sublimation resistance and can be used at high temperatures. Substituted by a propylene group or a hydroxy group, the solubility of the above-mentioned adhesive component is improved to prevent bleed out. 15 201139595 The above polycyclic aromatic compound is preferably hydrazine-derived, ~pv, 八;; The carbon number J 1 "" 1 8 ' is more preferably a carbon number of 1 to 8. Examples of the above-mentioned alkoxy group having at least one or more of the above-mentioned alkoxy groups include: 9,10, ..., ..., a fragrant compound onion, 2-methyl-9,10-dimethoxy-butyl- 9,10 —dimethoxy oxime, 2,3-di-dioxin chloroform, 0 soil~~ 9,1〇T oxime, 9-methoxyl_1〇-曱 蒽蒽, 2 —Bmei— Q1a—ethoxylate, 10-diethoxyanthracene, 2-t-butyl- 9-ethoxylated hydrazine, 2,3-methyl-A 〇1Λ & ^, ϋ~2' 曱 蒽," :Γ—蒽, 9-ethoxy~heart, 5-propoxy oxime, 2-ethyl-9,1〇~diyl fluorene, 2 -second butyl-9,1〇-dipropoxy蒽, 2, 卜二~-dipropoxy fluorene, 9-isopropoxy- 1 〇-methyl hydrazine, 9 1 〇 1 9'10 hydrazine, 9,10-dibenzyloxy, 9 9 . η , monobutoxy H, 2-ethyl-9'10-dioxylated onion, 2 second butyl-9,10~diethoxylated onion, 2,3-dimethyl m fluorene onion, 9-ethoxyl group - 1 〇 - methyl onion, 9,1 〇 _ ': solar-powered onion, 2-ethyl .... - 2 - methyl oxy-onion, JJ butyl -9, 1 〇-two...methyl oxy-onion, 2,3-two Indole derivatives such as methyl succinyl ethoxy) oxime, etc. - bis... methyl oxy-onion, 9-(α-methyl ethoxy bromide, 1: quinone, 9, fluorene-di) 2~Phenyloxy) onion, 2-ethyl-monomethyl~'dh. Μ. 7 ^ ^· \ s± ^ ^ ' — (2 The above has a part of the epoxy group or the trans group substituted Examples of the oxomethoxy polycyclic aromatic compound include: 9,W_: groupoxy)anthracene, 2-ethyl-91-oxime-oxypropyl, oxime-(3⁄4-oxypropyloxy)anthracene , flute-butyl-9, I0-di (county propyloxy) fluorene, 2,3-carboxyl: (epoxypropyloxyepoxypropyloxy)-1〇35 ^ ^ '951 〇16 201139595—bis(2-vinyloxyethoxy)anthracene, 2-ethyl~9,1〇-bis(2-vinyloxyethoxy)anthracene, 2-tert-butyl-n- 9,10 —bis(2-vinyloxyethoxy)anthracene, 2,3-dimercapto- 9,10-di(2-vinyloxyethoxy)anthracene, 9 —(2-ethyloxyoxyethoxy) Base) a 10-mercaptopurine, 9,10-bis(3-indolyl-3-oxetanyloxy)anthracene, 2-ethyl-n- 9,10-di(3-methyl- 3 - oxetanyl decyloxy) fluorene, 2 - tert-butyl _ 9, 1 〇 二 (3 - fluorenyl 3 - oxetanyl decyloxy) fluorene, 2, 3 - Difyl-9,10-(3-mercapto-3-oxobutenylmethoxy)anthracene, 9-(3-methyl-3-oxecyclobutenylmethoxy)- 1〇-methyl hydrazine, 9, i〇_ bis (p-epoxyphenyl fluorenyloxy) fluorene, 2-ethyl- 9,10-di(p-epoxyphenyl methoxy) fluorene, 2 - Tributyl-9,10-bis(p-epoxyphenylmethoxy)anthracene, 2,3-diindenyl- 9,10-di(p-epoxyphenyloximeoxy)anthracene, 9-(pair Epoxyphenyl decyloxy)-10-methylindole, 9,10-di(p-vinylphenyl decyloxy) fluorene, 2-ethyl-, 9,10-di(p-vinylphenyl fluorene蒽, 2_t-butyl-9,10-di(p-vinylphenyl decyloxy) fluorene, 2,3-dimethyl-, 9,1 〇 bis (p-vinylphenyl methoxy)蒽, 9-(p-vinylphenylmethoxy 1 fluorene fluorenyl, 9,10-di(2-cyanoethoxy) fluorene, 9,10-di(2-cyanopropoxy) Base, 9,10-di (2-hydroxyl) Oxy) ruthenium, 9,10-bis(2-hydroxy-3-methoxybutoxypropoxy) 蒽'9,1〇-bis(2-hydroxy-3-(2-ethylhexyloxy)propoxy , 9, 9,10 — 2 (2-—trans-l- 3 —l-propoxypropoxy) fluorene, 9,10 —di(2-trans-amino-3-phenoxypropoxy) fluorene, 9 , 10-bis(2,3-dihydroxypropyloxy)anthracene, and the like. The preferred lower limit of the content of the photosensitizer relative to 1 part by weight of the above-mentioned adhesive component is 〇. 5 parts by weight, preferably the upper limit is 1 〇 by weight, if the above 17 201139595 photosensitizer content is less than 0.05. When the amount is more than 1 part by weight, the residue derived from the photosensitizer increases, and sufficient peeling cannot be performed. A more preferred lower limit of the content of the photosensitizer is 0.1 part by weight, and a more preferred upper limit is 5 parts by weight. In order to achieve the adjustment of the cohesive force of the adhesive, the adhesive composition of the present invention may suitably contain various polyfunctional compounds which are blended with a general adhesive such as an isocyanate compound, a melamine compound or an epoxy compound, as needed. . The adhesive composition of the present invention may further contain a known additive such as a plasticizer, a resin, an surfactant, a wax, or a fine particle filler. The adhesive composition of the present invention has a high adhesion, and on the other hand, it can be easily peeled off by light irradiation or heating. In addition, since it is excellent in heat resistance, it can also be used for a high temperature treatment in which the wafer is fixed to a support plate or the like in a TSV manufacturing step. The adhesive composition of the present invention can be used for Various adhesive products. For example, the adhesive composition of the present invention may be used as an adhesive for an adhesive resin, an adhesive, a paint, a coating agent, a sealant, or the like. The adhesive composition of the invention is used as an adhesive for a single-sided adhesive tape, a double-sided adhesive tape, an unsupported tape (self-supporting tape), etc., and has an adhesive composition of the present invention on at least one side of the substrate. The subsequent layer of the layer is also one of the inventions. The substrate is exemplified by acrylic acid, olefin, polycarbonate 'gas ethylene, ABS, polyethylene terephthalate (PET), nylon, amine ester. a sheet made of a transparent resin such as polyimide, having a mesh structure 18 201139595 material 'opening sheet, etc. According to the present invention, it is possible to provide a high adhesion and easy peeling An adhesive composition which is excellent in heat resistance. [Embodiment] Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. (Example 1) Prepared with a thermometer, a reactor of a stirrer and a cooling tube, wherein 94 parts by weight of 2-ethylhexyl acrylate, ruthenium acrylate weight loss, 5 parts by weight of 2-hydroxyethyl acrylate, 1 part by weight of lauryl thiol, and After knocking the ethyl ester to 80 parts by weight, the reactor was heated to start refluxing. Then, U-double (peroxidized third hexyl)-3,3,5-trimethylcyclohexene was added to the above reactor. G1 parts by weight as a polymerization initiator, the polymerization was started under reflux. Secondly, after 11 hours and 2 hours after the start of the polymerization, respectively, f 11 ~~ double (peroxidized third hexyl 3, 3, 5 - 3) Methylcyclohexanone was smashed, and further, after 4 hours from the start of polymerization, 5 parts by weight of tert~heXyl per〇xypivaUte was added to make the polymerization reaction. Further, after 8 hours from the start of the polymerization, a solid content was obtained. An amount of 55 wt% of an acrylic acid copolymer having a weight average molecular weight of 60,000. The thioglycol 2 is added in an amount of 罝1 〇〇 by weight of the saponin containing the ethyl acetate solution of the obtained acrylic copolymer. -Isocyanate ethyl ester 3 ·5 parts by weight to react, and further, the solid content is dissolved relative to the ethyl acetate after the reaction] 〇〇 part by weight of the mixed photopolymerization initiator (Esacure 0ne, Japan SiberHegner Manufactured by the company) 重量" parts by weight, polyisocyanate 19 201139595 crosslinking agent (c_ate L45, manufactured by Japan Polyurethane Co., Ltd.) 2 deniers 'Preparation of ethyl acetate solution of the adhesive (1). Relative to the adhesive (1) The solid content of the resin in the form of ethyl acetate was 100 parts by weight, and the weight fraction of Wolmannone, which is manufactured by Tokyo Chemical Industry Co., Ltd., was mixed in m parts by weight to obtain an adhesive composition. The obtained adhesive composition is applied by a doctor blade to a corona-treated surface of a transparent poly-p-ethylene dicarboxylate film having a thickness of m on one side, and is applied to the surface by a doctor blade at a thickness of 30 Å. The coating solution was dried by heating for 5 minutes. Thereafter, ... ^ was allowed to stand for 3 days to be solidified and the belt was obtained. (Example 2) The same procedure as in Example 1 except that the weight fraction of 9,10-bis(2-propionyloxy) onion was added in place of (4)-diglycidoxy fluorene as a photosensitizer. The operation proceeds to obtain an adhesive composition and an adhesive tape. (Example 3) In addition to blending 9'10-dibutoxy oxime! An adhesive composition and an adhesive tape were obtained in the same manner as in Example i except that 1 part by weight of the oxime-diepoxypropoxy fluorene was used as the photosensitizer. (Example 4) An adhesive composition and an adhesive tape were obtained in the same manner as in Example 1 except that 2 parts by weight of 2-oxanone acetic acid was blended in place of ketoprofen 2 parts by weight. (Example 5) An adhesive composition was obtained in the same manner as in Example i except that 2 parts by weight of 2-nonyl ketone acetate distearylamine salt was blended in place of 20 parts by weight of ketopro 20 201139595 fen. . (Comparative Example 1) A subsequent composition and a subsequent tape were obtained in the same manner as in Example except that ketoprofen was not blended. (Comparative Example 2) In place of 2,2,-azobis-(N-butyl-2-methylpropenamide) 2 parts by weight instead of 2 g parts by weight of ketoprofen, diethyl thialate was added. An adhesive composition and an adhesive tape were obtained in the same manner as in Example 2, except that 3 parts by weight of the oxime was used instead of the 9,10-dipropylene propyl group. (Comparative Example 3) A reactor for cooling a tube was prepared by adding a weight of 94 parts by weight, 1 part of acrylic acid, and 1 part by weight of lauryl mercaptan, and preparing a thermometer, a stirrer, and a 2-ethylhexyl acrylate. After 5 parts by weight of 2-hydroxyethyl acrylate and 180 parts by weight of acetic acid, the reactor was heated to start reflux. Then, in the above reactor, the force σ i, Bu Shuang (peroxidized third hexyl b tri-f-hexane 0.01 reciprocal portion as a polymerization initiator) is started. Secondly, at the start of polymerization H, after and 2... After 2 hours, add:, - double (peroxidized third hexyl bromide 3,3,5-trimethylcyclohexanthene oxime 1 weight =, and then 'addition of peroxyisodine after 4 hours of peaking The acid tertiary reaction is carried out by the acid three-stage: 曰 " two parts by weight. And, after the start of the polymerization, an acrylic copolymer having a solid content of 55% by weight and a weight average molecular weight of 60,000 is obtained. 1 part by weight of a dilute acid-based adhesive (solid content: 21 201139595), and 50 parts by weight of Microsphere F - 50D (manufactured by Matsumoto Oil Co., Ltd.) was mixed to obtain an adhesive composition. The obtained adhesive composition was dried. The thickness is 30 A m by means of a doctor blade coated on one side to achieve a corona treatment thickness of 5 〇 / / m < transparent polyethylene terephthalate film on the corona treatment surface, in u〇 (»c Heat the coating for 5 minutes to dry the coating. After that, it was dried at 4 (^c for 3 days). The evaluation was carried out to obtain the adhesive tape. (Evaluation) The evaluations of the examples and the comparative examples were carried out. The results are not shown in Table 1. (1) Adhesive evaluation and peelability evaluation were cut into circular bands of 2 cm in diameter. It is attached to a tantalum wafer having a diameter of 20 cm and a thickness of about 750 /zm. The next evaluation is to stretch the tape in this state, and the case of completely I and peeling is evaluated as "〇". In the case where the peeling can be easily peeled off, the sweat price is "△", and the case where the peeling can be almost unimpeded is evaluated as "χ": and 'Ultra-high pressure mercury lamp is used to make the surface of the glass plate strong to 40 tmw/cm2. The method is to adjust the illumination, and the ultraviolet light of nm is irradiated from the side of the glass plate for 2 minutes. The UV-extension is 捸 胜 胜 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离However, the shape of the peelable case was evaluated as "9 Jia is △", and the whole can not be peeled off. (2) Heat resistance evaluation 201139595 A circular tape with a diameter of 20 cm was attached to a diameter of 20 cm and a thickness of about 750 # The wafer of m After heating for 2 hours at 200 ° C, the mixture was returned to room temperature. The laminate was evaluated for adhesion and peelability after heating. 23 201139595 Heat treatment at 200 for 2 hours Peelability 〇〇〇〇〇X 1 1 Next 〇〇〇〇〇〇XX no heat treatment|peelability|〇〇〇〇〇X 〇<3 @性性1 〇〇〇〇〇〇〇〇 photosensitizer 9,10-diepoxypropyloxy蒽9,10_bis(2-hydroxypropoxy)fluorene 9,10-dibutoxyanthracene 9,10-diepoxypropoxy fluorene 9,10-diepoxypropoxy fluorene 9,10_ Diepoxypropoxypurine diethyl thianonanone 1 compound ketoprofen' ketoprofenone 洛芬 2_α ketone acetic acid 2-D ketone acetate distearylamine salt 1 2,2'-azo Double-(Ν-butyl- 2-mercaptopropionamide) Heat-expandable microspheres Example 1 I Example 2 1 |Example 3 | |Example 4 | |Example 5 | |Comparative Example 11 |Comparative Example 2 | |Comparative Example 3 1 201139595 [Industrial Applicability] According to the present invention, it is possible to provide an adhesive agent which has high adhesion and which can be easily peeled off and which is excellent in heat recovery. As it was. [Simple description of the diagram] None [Key component symbol description] Benefits < »», 25