TWI555809B - Adhesive composition containing aromatic polyether derivative - Google Patents

Adhesive composition containing aromatic polyether derivative Download PDF

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TWI555809B
TWI555809B TW100128348A TW100128348A TWI555809B TW I555809 B TWI555809 B TW I555809B TW 100128348 A TW100128348 A TW 100128348A TW 100128348 A TW100128348 A TW 100128348A TW I555809 B TWI555809 B TW I555809B
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group
adhesive composition
methyl
polymer
carbon atoms
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TW201219527A (en
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田村護
染谷安信
荻野浩司
榎本智之
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日產化學工業股份有限公司
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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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • 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
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

含有芳香族聚醚衍生物之接著劑組成物Adhesive composition containing an aromatic polyether derivative

本發明係關於接著劑組成物。更詳言之係關於在形成IC晶片等半導體製品或光學系製品等層合物之步驟中使被層合物間接著的接著劑組成物。The present invention relates to an adhesive composition. More specifically, it relates to an adhesive composition which is followed by a laminate in a step of forming a laminate such as a semiconductor article such as an IC wafer or an optical system.

近年、伴隨行動電話或IC卡等電子機器的高機能化、小型化，追求半導體裝置之高積體化。該手法係探討使半導體本身的微細化或半導體元件堆疊在縱方向的堆疊構造。In recent years, high-performance and miniaturization of electronic devices such as mobile phones and IC cards have been pursued, and the integration of semiconductor devices has been pursued. This technique is a stacking structure in which the semiconductor itself is miniaturized or the semiconductor elements are stacked in the longitudinal direction.

在堆疊構造製作中，於半導體元件間之接合使用接著劑。In the fabrication of the stacked structure, an adhesive is used for bonding between the semiconductor elements.

但，習知接著劑已知的丙烯酸樹脂或環氧樹脂、矽酮樹脂耐熱性僅有250℃左右，有無法使用於金屬凸塊的電極接合或離子擴散步驟等、要求在250℃以上高溫之步驟的問題。However, the known acrylic resin, epoxy resin, and fluorenone resin have a heat resistance of only about 250 ° C, and may be used in an electrode bonding or ion diffusion step of a metal bump, and are required to have a high temperature of 250 ° C or higher. The problem with the steps.

另一方面，揭示於玻璃基材含浸矽酮樹脂的無機系絕緣基板上，形成含有30體積%乃至45體積%聚醚醚酮樹脂粉末與熱硬化性樹脂之底切膜的厚膜技術用基板(專利文獻1)。On the other hand, it is disclosed that a thick film technical substrate containing 30% by volume or 45% by volume of an undercut film of a polyetheretherketone resin powder and a thermosetting resin is formed on an inorganic insulating substrate impregnated with a fluorenone resin on a glass substrate. (Patent Document 1).

[先前技術文献][Previous Technical Literature] [專利文獻][Patent Literature]

[專利文獻1]　特開2009-070875[Patent Document 1] Special Opening 2009-070875

上述形成底切膜的基板為對水分或熱之尺寸改變非常小且耐濕性等優異者。但，此等底切膜所含聚醚醚酮在溶劑或樹脂溶液中不溶，故無法作為塗佈型接著劑，而採用做成糊狀油墨形態以網版印刷法被覆基板之方法。又，因在該組成物中聚醚醚酮樹脂之含量過度增加則無法形成可網版印刷的油墨，故該樹脂僅能含有30體積%乃至45體積%之比例，有耐熱性問題。The substrate on which the undercut film is formed is excellent in that the size of moisture or heat is extremely small, and the moisture resistance is excellent. However, since the polyetheretherketone contained in these undercut films is insoluble in a solvent or a resin solution, it cannot be used as a coating-type adhesive, but a method of coating a substrate by a screen printing method in the form of a paste ink. Further, since the content of the polyetheretherketone resin in the composition is excessively increased, the screen-printable ink cannot be formed. Therefore, the resin can only contain a ratio of 30% by volume or 45% by volume, which has a problem of heat resistance.

如上述作為習知接著劑已知的丙烯酸樹脂或環氧樹脂、矽酮樹脂，耐熱性僅在250℃左右，無法在250℃以上高溫下使用。An acrylic resin, an epoxy resin, or an anthrone resin which is known as a conventional adhesive agent has a heat resistance of only about 250 ° C and cannot be used at a high temperature of 250 ° C or higher.

另一方面，專利文獻1雖揭示聚醚醚酮般全芳香族聚醚之接著劑，但溶劑溶解性極低而無溶解性，溶劑選擇性少、難以厚膜化。進而有塗佈性亦不足的問題。On the other hand, in Patent Document 1, an adhesive of a polyetheretherketone-like wholly aromatic polyether is disclosed, but the solvent solubility is extremely low and there is no solubility, and the solvent selectivity is small, and it is difficult to form a thick film. Further, there is a problem that the coatability is also insufficient.

溶劑溶解性提升的方法，雖提案有導入以長鏈烷基為代表的柔軟構造，但有總和來說耐熱性降低的問題。In the method of improving solvent solubility, it is proposed to introduce a soft structure typified by a long-chain alkyl group, but there is a problem that heat resistance is lowered in total.

本發明係有鑑於上述問題點而成者，其目的在於提供易溶於種種有機溶劑，塗佈性佳、可形成足夠厚度之接著層，且該接著層在金屬凸塊接合、CVD、離子擴散步驟等高溫製程中，熱重量減少極少，且密著性良好的高耐熱性接著劑組成物。The present invention has been made in view of the above problems, and an object thereof is to provide an adhesive layer which is easily soluble in various organic solvents and has good coatability and can form a sufficient thickness, and the adhesive layer is bonded by metal bumps, CVD, and ion diffusion. In the high-temperature process such as the step, the composition of the high heat-resistant adhesive having little thermal weight reduction and good adhesion is obtained.

本發明第1觀點方面，係含有含下述式(1)：According to a first aspect of the present invention, the method comprises the following formula (1):

【化1】【化1】

(式中，X為磺醯基或羰基，Ar1及Ar2各自為碳原子數6乃至30之伸芳基，T1為氟伸烷基、環狀伸烷基、具有取代基之伸芳基、或可具有取代基的伸芳基與氟伸烷基或者環狀伸烷基之組合。)所表示之單元構造的聚合物之接著劑組成物、第2觀點方面，為前述伸芳基係伸苯基、伸萘基、或伸蒽基之第1觀點記載之接著劑組成物、第3觀點方面，為前述聚合物係具有1種類單元構造的單獨聚合物之第1觀點或第2觀點記載之接著劑組成物、第4觀點方面，為前述聚合物為具有至少2種類單元構造之共聚合物的第1觀點或第2觀點記載之接著劑組成物、第5觀點方面，為含有含前述Ar1及Ar2各自係下述式(2)：(wherein X is a sulfonyl group or a carbonyl group, each of Ar 1 and Ar 2 is an exoaryl group having 6 to 30 carbon atoms, and T 1 is a fluoroalkyl group, a cyclic alkyl group, and a substituent having a substituent. a combination of a aryl group which may have a substituent and a fluorine-extended alkyl group or a cyclic alkyl group, and a binder composition of a polymer having a unit structure represented by the above, and a second aspect, a aryl group The first aspect or the second aspect of the polymer having one type of unit structure, the binder composition described in the first aspect of the present invention, and the third aspect of the present invention. In the fourth aspect of the present invention, the binder composition is a binder composition having a polymer structure having at least two types of unit structures, and a binder composition according to the first aspect or the second aspect. The foregoing Ar 1 and Ar 2 are each represented by the following formula (2):

【化2】[Chemical 2]

(式中，R1為碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、羥基、烯丙基、烯丙氧基、胺基、氰基、硝基、醯基、醯基氧基、羧基、具有第3級碳構造的基、環狀烷基、或彼等之組合，n1為0乃至4之整數。)所表示之基的上述式(1)所表示之單元構造之聚合物的第1觀點乃至第4觀點中任一項記載之接著劑組成物、第6觀點方面，為含有含前述T1係下述式(3)所表示之基的上述式(1)所表示之單元構造、前述T1係下述式(4)所表示之基的上述式(1)所表示之單元構造、或彼等之單元構造之組合的聚合物之第1觀點乃至第5觀點中任一項記載之接著劑組成物、(wherein R 1 is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, a nitro group or a fluorenyl group; a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and n1 is an integer of 0 to 4.) The group represented by the above formula (1) according to any of the first aspect and the fourth aspect of the polymer unit is configured according to one of the adhesive composition, the sixth aspect aspect, containing a system containing the following formula T above formula (3) represented by the group ( 1) The unit structure shown in the above, the first viewpoint of the polymer structure represented by the above formula (1) represented by the following formula (4), or the combination of the unit structures of the above T 1 is even The adhesive composition according to any one of the fifth aspects,

【化3】[化3]

(式中，R2、R3及R4各自為碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、羥基、烯丙基、烯丙氧基、胺基、氰基、硝基、醯基、醯基氧基、羧基、具有第3級碳構造的基、環狀烷基、或彼等之組合，n2、n3及n4各自為0乃至4之整數，T2為氟伸烷基、環狀伸烷基、或此等之組合。)、第7觀點方面，為前述式(3)中，R2為含有至少具有第3級碳構造的基之基，n2為1乃至4之整數的第6觀點記載之接著劑組成物、第8觀點方面，更含有含式(5)：(wherein R 2 , R 3 and R 4 are each an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, and a cyanogen group; a group, a nitro group, a fluorenyl group, a decyloxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and each of n2, n3 and n4 is an integer of 0 to 4, T 2 In the above formula (3), R 2 is a group containing a group having at least a third-order carbon structure, and n2 is a fluorine-containing alkyl group, a cyclic alkyl group, or a combination thereof. The adhesive composition described in the sixth aspect which is an integer of 1 to 4, and the eighth aspect, further contains the formula (5):

【化4】【化4】

(式中，X為磺醯基或羰基，Ar3及Ar4各自為碳原子數6乃至30之伸芳基，T3為伸烷基、磺醯基、羰基、碳原子數6乃至30之伸芳基、或此等之組合。)所表示之基的單元構造之聚合物的第1觀點、第2觀點及第4觀點乃至第7觀點中任一項記載之接著劑組成物、第9觀點方面，前述伸芳基為伸苯基、伸萘基、或伸蒽基的第8觀點記載之接著劑組成物、第10觀點方面，前述T3為式(6)：(wherein X is a sulfonyl group or a carbonyl group, each of Ar 3 and Ar 4 is an exoaryl group having 6 to 30 carbon atoms, and T 3 is an alkylene group, a sulfonyl group, a carbonyl group, or a carbon number of 6 or 30. The arsenic group, or a combination of these, the first embodiment, the second aspect, the fourth aspect, and the seventh aspect of the polymer of the unit structure of the base group, the ninth aspect, and the ninth aspect In view of the above, the above-mentioned exoaryl group is an adhesive composition according to the eighth aspect of the present invention, which is a phenylene group, a naphthyl group, or a mercapto group. The tenth aspect is that the T 3 is a formula (6):

【化5】【化5】

(式中，R5及R6各自為碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、羥基、烯丙基、烯丙氧基、胺基、氰基、硝基、醯基、醯基氧基、羧基、具有第3級碳構造的基、環狀烷基、或彼等之組合，n5及n6各自為0乃至4之整數，T4為伸烷基、磺醯基、羰基、碳原子數6乃至30之伸芳基、或此等之組合。)所表示之基的第8觀點或第9觀點記載之接著劑組成物、第11觀點方面，前述具有第3級碳構造的基為第三丁基的第1觀點乃至第10觀點中任一項記載之接著劑組成物、第12觀點方面，前述聚合物之重量平均分子量為500乃至5000000的第1觀點乃至第11觀點中任一項記載之接著劑組成物、第13觀點方面，更含有交聯劑的第1觀點乃至第12觀點中任一項記載之接著劑組成物、第14觀點方面，更含有溶劑且具有0.001乃至5000Pa‧s之黏度的第1觀點乃至第13觀點中任一項記載之接著劑組成物、第15觀點方面，含有至少2個的被接著物、與在該被接著物間所設置的第1觀點乃至第14觀點中任一項記載之接著劑組成物所形成的0.1μm乃至200μm之接著層的層合物、第16觀點方面，前述被接著物各自為選自矽基板、玻璃基板、樹脂基板、或陶瓷基板所成組群的第15觀點記載之層合物。(wherein R 5 and R 6 are each an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, and a nitrate a group, a mercapto group, a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, each of n5 and n6 is an integer of 0 to 4, and T 4 is an alkylene group, The sulfonate group, the carbonyl group, the aryl group having 6 to 30 carbon atoms, or the combination thereof; the binder composition according to the eighth aspect or the ninth aspect, and the eleventh aspect, The first aspect of the third aspect of the present invention is the third aspect of the present invention, wherein the polymer has a weight average molecular weight of 500 to 5,000,000. The adhesive composition according to any one of the first aspect of the present invention, the fourth aspect, the fourth aspect, the fourth aspect, and the fourth aspect, An adhesive agent according to any one of the first aspect to the thirteenth aspect, further comprising a solvent and having a viscosity of 0.001 to 5000 Pa s The object of the present invention, the 15th aspect, the 0.1 μm formed of the adhesive composition of at least two of the adherends, and the adhesive composition described in any one of the first aspect to the fourteenth aspect In the laminate of the laminate of 200 μm and the 16th aspect, each of the substrates to be tested is a laminate according to the fifteenth aspect selected from the group consisting of a tantalum substrate, a glass substrate, a resin substrate, and a ceramic substrate.

根據本發明，本發明之接著劑組成物藉由含有具芳香族聚醚醚酮或芳香族聚醚醚碸等之芳香族聚醚構造的聚合物，可在種種溶劑中容易溶解、得到良好的塗佈性。又，本發明之接著劑組成物可形成接著所需足夠厚度的接著層、且在金屬凸塊接合、CVD、離子擴散步驟等之高溫製程中熱重量減少極少、高溫製程後亦可形成具高密著性的接著層。According to the present invention, the adhesive composition of the present invention can be easily dissolved and obtained in a variety of solvents by a polymer having an aromatic polyether such as an aromatic polyether ether ketone or an aromatic polyether ether oxime. Coating properties. Moreover, the adhesive composition of the present invention can form an adhesive layer of a sufficient thickness to be subsequently required, and has a small thermal weight reduction in a high-temperature process such as a metal bump bonding, a CVD, an ion diffusion step, etc., and a high density can be formed after a high-temperature process. The next layer of sex.

藉此，本發明之含有具有聚醚構造的聚合物之接著劑組成物可用於高溫製程中加工所必要的半導體裝置等所使用的電子基板等之被加工物(例如透過加熱處理、加壓處理、或微影術等加工的層合物質)之接著。In this way, the adhesive composition containing the polymer having a polyether structure of the present invention can be used for a workpiece such as an electronic substrate used in a semiconductor device or the like necessary for processing in a high-temperature process (for example, by heat treatment or pressure treatment). Followed by processing of laminated materials such as lithography.

又，本發明之層合物因具有高耐熱性的接著層，在高溫製程中可加工被接著物及可在高溫條件下使用。Further, the laminate of the present invention can be processed into an adherend in a high-temperature process and can be used under high temperature conditions due to an adhesive layer having high heat resistance.

[實施發明之最佳形態][Best Mode for Carrying Out the Invention]

本發明係含有含式(1)所表示之單元構造之聚合物的接著劑組成物。The present invention is an adhesive composition containing a polymer having a unit structure represented by the formula (1).

上述接著劑組成物含有含式(1)所表示之單元構造之聚合物與溶劑、且可再含有任意成分的改善接著劑性能用之加成的樹脂、黏著賦予劑、可塑劑、接著助劑、安定劑、著色劑、界面活性劑等。The above-mentioned adhesive composition contains a polymer containing a unit structure represented by the formula (1) and a solvent, and may further contain an optional component to improve the adhesive performance, a resin, an adhesion-imparting agent, a plasticizer, and an auxiliary agent. , stabilizers, colorants, surfactants, etc.

本發明之接著劑組成物之固形分為0.1乃至80質量%、較佳為1乃至60質量%。固形分相對接著劑組成物，以由該接著劑組成物除去溶劑的殘餘部分之比例表示。固形分中占有的含式(1)所表示之單元構造的聚合物之比例為30乃至100質量%、較佳為50乃至100質量%。The solid content of the adhesive composition of the present invention is 0.1 to 80% by mass, preferably 1 to 60% by mass. The solid content relative to the adhesive composition is expressed by the ratio of the residual portion of the solvent removed from the adhesive composition. The proportion of the polymer having a unit structure represented by the formula (1) which is contained in the solid content is from 30 to 100% by mass, preferably from 50 to 100% by mass.

本發明所使用的聚合物以熱可塑性樹脂為佳。The polymer used in the present invention is preferably a thermoplastic resin.

本發明所使用的聚合物之分子量以重量平均分子量計為500乃至5000000、較佳為1000乃至1000000、更較佳為1000乃至100000。The molecular weight of the polymer used in the present invention is from 500 to 5,000,000, preferably from 1,000 to 1,000,000, more preferably from 1,000 to 100,000, based on the weight average molecular weight.

式(1)中，X為磺醯基或羰基，Ar1及Ar2各自為碳原子數6乃至30之伸芳基，T1為氟伸烷基、環狀伸烷基、具有取代基之伸芳基、或可具有取代基的伸芳基與氟伸烷基或者環狀伸烷基之組合。In the formula (1), X is a sulfonyl group or a carbonyl group, each of Ar 1 and Ar 2 is an exoaryl group having 6 to 30 carbon atoms, and T 1 is a fluoroalkyl group, a cyclic alkyl group, and a substituent. A combination of an aryl group or a aryl group which may have a substituent with a fluoroalkyl group or a cyclic alkyl group.

具有取代基的伸芳基為以下所述之具有取代基的伸芳基。The extended aryl group having a substituent is a substituted aryl group having a substituent as described below.

可具有取代基的伸芳基為取代或非取代之伸芳基，為此等之伸芳基與氟伸烷基或環狀伸烷基之組合。The extended aryl group which may have a substituent is a substituted or unsubstituted extended aryl group, and for this purpose, a combination of a aryl group and a fluorine alkyl group or a cyclic alkyl group.

伸芳基，可舉例如伸苯基、萘基、或蒽基等，以伸苯基或萘基為佳。The aryl group may, for example, be a phenyl group, a naphthyl group or a fluorenyl group, and a phenyl or naphthyl group is preferred.

上述氟伸烷基可舉例如碳原子數1乃至10之氟伸烷基，其具體例，可舉例如氟亞甲基、氟伸乙基、氟-n-伸丙基、氟異伸丙基、氟丙烷-2,2-二基、氟-n-伸丁基、氟異伸丁基、氟-s-伸丁基、氟-t-伸丁基等。其中可舉例如全氟丙烷-2,2-二基等之碳原子數1乃至4之氟伸烷基。此等之氟伸烷基可使用完全氟化(全氟化)的伸烷基或一部份氟化的伸烷基(單氟化、二氟化等)。The fluorine alkyl group may, for example, be a fluorine alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a fluoromethylene group, a fluorine-extended ethyl group, a fluorine-n-propyl group, and a fluorine-iso-propyl group. , fluoropropane-2,2-diyl, fluoro-n-butylene, fluoroisobutylene, fluoro-s-butylene, fluoro-t-butylene, and the like. Among them, a fluorine alkyl group having 1 to 4 carbon atoms such as perfluoropropane-2,2-diyl may be mentioned. These fluorine alkyl groups may use a fully fluorinated (perfluorinated) alkylene group or a partially fluorinated alkylene group (monofluorinated, difluorinated, etc.).

環狀伸烷基，可舉例如碳原子數為3乃至30之環狀伸烷基，例如環伸丙基、環伸丁基、環伸己基、1-甲基-環伸戊基、2-甲基-環伸戊基、3-甲基-環伸戊基、1-乙基-環伸丁基、2-乙基-環伸丁基、3-乙基-環伸丁基、1,2-二甲基-環伸丁基、1,3-二甲基-環伸丁基、2,2-二甲基-環伸丁基、2,3-二甲基-環伸丁基、2,4-二甲基-環伸丁基、3,3-二甲基-環伸丁基、1-n-丙基-環伸丙基、2-n-丙基-環伸丙基、1-i-丙基-環伸丙基、2-i-丙基-環伸丙基、1,2,2-三甲基-環伸丙基、1,2,3-三甲基-環伸丙基、2,2,3-三甲基-環伸丙基、1-乙基-2-甲基-環伸丙基、2-乙基-1-甲基-環伸丙基、2-乙基-2-甲基-環伸丙基及2-乙基-3-甲基-環伸丙基等。又，可使用由金剛烷、降冰片烯所衍生的2價有機基。The cyclic alkyl group may, for example, be a cyclic alkyl group having 3 to 30 carbon atoms, such as a cyclic propyl group, a cyclobutyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, and 2 Methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1, 2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4-Dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclo Propyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2 -ethyl-2-methyl-cyclopropanyl and 2-ethyl-3-methyl-cyclopropyl. Further, a divalent organic group derived from adamantane or norbornene can be used.

本發明所使用的含式(1)所表示之單元構造的聚合物，T1為此等之官能基可單獨使用或複數組合使用。The polymer having a unit structure represented by the formula (1) used in the present invention, the functional group of T 1 or the like may be used singly or in combination.

上述聚合物可用作為重複單元構造為1種類所成之單獨聚合物或重複單元構造為2種類或其以上的共聚合物。The above polymer may be used as a repeating unit structure in a single polymer or a repeating unit structure of two or more kinds of copolymers.

在本發明，可含有含Ar1及Ar2可各自係式(2)所表示之基的上述式(1)所表示之單元構造的聚合物。In the present invention, a polymer having a unit structure represented by the above formula (1) in which Ar 1 and Ar 2 are each a group represented by the formula (2) may be contained.

式(2)中，R1為碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、羥基、烯丙基、烯丙氧基、胺基、氰基、硝基、醯基、醯基氧基、羧基、具有第3級碳構造的基、環狀烷基、或彼等之組合，n1為0乃至4之整數。In the formula (2), R 1 is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, a nitro group, A mercapto group, a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and n1 is an integer of 0 to 4.

式(2)中，作為表示R1之烷基為碳原子數1乃至10之烷基，例如甲基、乙基、n-丙基、i-丙基、n-丁基、i-丁基、s-丁基、t-丁基、n-戊基、1-甲基-n-丁基、2-甲基-n-丁基、3-甲基-n-丁基、1,1-二甲基-n-丙基、1,2-二甲基-n-丙基、2,2-二甲基-n-丙基、1-乙基-n-丙基、n-己基、1-甲基-n-戊基、2-甲基-n-戊基、3-甲基-n-戊基、4-甲基-n-戊基、1,1-二甲基-n-丁基、1,2-二甲基-n-丁基、1,3-二甲基-n-丁基、2,2-二甲基-n-丁基、2,3-二甲基-n-丁基、3,3-二甲基-n-丁基、1-乙基-n-丁基、2-乙基-n-丁基、1,1,2-三甲基-n-丙基、1,2,2-三甲基-n-丙基、1-乙基-1-甲基-n-丙基、1-乙基-2-甲基-n-丙基等。In the formula (2), the alkyl group representing R 1 is an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl. , s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1- Dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1 -methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl 1,1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n -butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl Base, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, and the like.

氟烷基，可舉例如碳原子數1乃至10之氟烷基，及碳原子數1乃至4之氟烷基。可舉例如氟甲基、氟乙基、氟-n-丙基、氟異丙基、氟-n-丁基、氟異丁基、氟-s-丁基、氟-t-丁基等。作為此等之氟烷基可使用完全氟化(全氟化)或一部份氟化的烷基。The fluoroalkyl group may, for example, be a fluoroalkyl group having 1 to 10 carbon atoms and a fluoroalkyl group having 1 to 4 carbon atoms. For example, a fluoromethyl group, a fluoroethyl group, a fluorine-n-propyl group, a fluoroisopropyl group, a fluorine-n-butyl group, a fluorine-isobutyl group, a fluorine-s-butyl group, a fluorine-t-butyl group, etc. are mentioned. As such a fluoroalkyl group, a fully fluorinated (perfluorinated) or partially fluorinated alkyl group can be used.

醯基，可舉例如碳原子數2乃至10之醯基，例如甲基羰基、乙基羰基、n-丙基羰基、i-丙基羰基、環丙基羰基、n-丁基羰基、i-丁基羰基、s-丁基羰基、t-丁基羰基、環丁基羰基、1-甲基-環丙基羰基、2-甲基-環丙基羰基、n-戊基羰基、1-甲基-n-丁基羰基、2-甲基-n-丁基羰基、3-甲基-n-丁基羰基、1,1-二甲基-n-丙基羰基、1,2-二甲基-n-丙基羰基、2,2-二甲基-n-丙基羰基、1-乙基-n-丙基羰基、環戊基羰基、1-甲基-環丁基羰基、2-甲基-環丁基羰基、3-甲基-環丁基羰基、1,2-二甲基-環丙基羰基、2,3-二甲基-環丙基羰基、1-乙基-環丙基羰基、2-乙基-環丙基羰基、n-己基羰基、1-甲基-n-戊基羰基、2-甲基-n-戊基羰基、3-甲基-n-戊基羰基、4-甲基-n-戊基羰基、1,1-二甲基-n-丁基羰基、1,2-二甲基-n-丁基羰基、1,3-二甲基-n-丁基羰基、2,2-二甲基-n-丁基羰基、2,3-二甲基-n-丁基羰基、3,3-二甲基-n-丁基羰基、1-乙基-n-丁基羰基、2-乙基-n-丁基羰基、1,1,2-三甲基-n-丙基羰基等。The mercapto group may, for example, be a fluorenyl group having 2 or 10 carbon atoms, such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl, cyclopropylcarbonyl, n-butylcarbonyl, i-. Butylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, cyclobutylcarbonyl, 1-methyl-cyclopropylcarbonyl, 2-methyl-cyclopropylcarbonyl, n-pentylcarbonyl, 1-methyl Base-n-butylcarbonyl, 2-methyl-n-butylcarbonyl, 3-methyl-n-butylcarbonyl, 1,1-dimethyl-n-propylcarbonyl, 1,2-dimethyl Base-n-propylcarbonyl, 2,2-dimethyl-n-propylcarbonyl, 1-ethyl-n-propylcarbonyl, cyclopentylcarbonyl, 1-methyl-cyclobutylcarbonyl, 2- Methyl-cyclobutylcarbonyl, 3-methyl-cyclobutylcarbonyl, 1,2-dimethyl-cyclopropylcarbonyl, 2,3-dimethyl-cyclopropylcarbonyl, 1-ethyl-cyclo Propylcarbonyl, 2-ethyl-cyclopropylcarbonyl, n-hexylcarbonyl, 1-methyl-n-pentylcarbonyl, 2-methyl-n-pentylcarbonyl, 3-methyl-n-pentyl Carbonyl, 4-methyl-n-pentylcarbonyl, 1,1-dimethyl-n-butylcarbonyl, 1,2-dimethyl-n-butylcarbonyl, 1,3-dimethyl-n -butylcarbonyl, 2,2-dimethyl-n-butylcarbonyl, 2,3-dimethyl-n-butylcarbonyl, 3,3-dimethyl -n- butyl carbonyl group, 1-ethyl -n- butyl carbonyl, ethyl carbonyl -n- butyl group, 1,1,2-trimethyl -n- propyl carbonyl group and the like.

作為醯基氧基可舉例如碳原子數2乃至10之醯基氧基，例如甲基羰基氧基、乙基羰基氧基、n-丙基羰基氧基、i-丙基羰基氧基、環丙基羰基氧基、n-丁基羰基氧基、i-丁基羰基氧基、s-丁基羰基氧基、t-丁基羰基氧基、環丁基羰基氧基、1-甲基-環丙基羰基氧基、2-甲基-環丙基羰基氧基、n-戊基羰基氧基、1-甲基-n-丁基羰基氧基、2-甲基-n-丁基羰基氧基、3-甲基-n-丁基羰基氧基、1,1-二甲基-n-丙基羰基氧基、1,2-二甲基-n-丙基羰基氧基、2,2-二甲基-n-丙基羰基氧基、1-乙基-n-丙基羰基氧基、環戊基羰基氧基、1-甲基-環丁基羰基氧基、2-甲基-環丁基羰基氧基、3-甲基-環丁基羰基氧基、1,2-二甲基-環丙基羰基氧基、2,3-二甲基-環丙基羰基氧基、1-乙基-環丙基羰基氧基、2-乙基-環丙基羰基氧基、n-己基羰基氧基、1-甲基-n-戊基羰基氧基、2-甲基-n-戊基羰基氧基、3-甲基-n-戊基羰基氧基、4-甲基-n-戊基羰基氧基、1,1-二甲基-n-丁基羰基氧基、1,2-二甲基-n-丁基羰基氧基、1,3-二甲基-n-丁基羰基氧基、2,2-二甲基-n-丁基羰基氧基、2,3-二甲基-n-丁基羰基氧基、3,3-二甲基-n-丁基羰基氧基、1-乙基-n-丁基羰基氧基、2-乙基-n-丁基羰基氧基、1,1,2-三甲基-n-丙基羰基氧基等。The mercaptooxy group may, for example, be a fluorenyloxy group having 2 or 10 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, or a ring. Propylcarbonyloxy, n-butylcarbonyloxy, i-butylcarbonyloxy, s-butylcarbonyloxy, t-butylcarbonyloxy, cyclobutylcarbonyloxy, 1-methyl- Cyclopropylcarbonyloxy, 2-methyl-cyclopropylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyl Oxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2, 2-Dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, cyclopentylcarbonyloxy, 1-methyl-cyclobutylcarbonyloxy, 2-methyl - cyclobutylcarbonyloxy, 3-methyl-cyclobutylcarbonyloxy, 1,2-dimethyl-cyclopropylcarbonyloxy, 2,3-dimethyl-cyclopropylcarbonyloxy, 1-ethyl-cyclopropylcarbonyloxy, 2-ethyl-cyclopropylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n -pentylcarbonyloxy, 3-methyl-n-pentyl Carbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1 , 3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3 - dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n -propylcarbonyloxy group and the like.

具有第3級碳構造的基較佳可使用第三丁基。A third butyl group is preferably used as the group having the third-order carbon structure.

環狀烷基，可舉例如碳原子數為3乃至30之環狀烷基，例如環丙基、環丁基、環己基、1-甲基-環戊基、2-甲基-環戊基、3-甲基-環戊基、1-乙基-環丁基、2-乙基-環丁基、3-乙基-環丁基、1,2-二甲基-環丁基、1,3-二甲基-環丁基、2,2-二甲基-環丁基、2,3-二甲基-環丁基、2,4-二甲基-環丁基、3,3-二甲基-環丁基、1-n-丙基-環丙基、2-n-丙基-環丙基、1-i-丙基-環丙基、2-i-丙基-環丙基、1,2,2-三甲基-環丙基、1,2,3-三甲基-環丙基、2,2,3-三甲基-環丙基、1-乙基-2-甲基-環丙基、2-乙基-1-甲基-環丙基、2-乙基-2-甲基-環丙基及2-乙基-3-甲基-環丙基等。又，可使用金剛烷、降冰片烯所衍生的1價有機基。The cyclic alkyl group may, for example, be a cyclic alkyl group having 3 to 30 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group or a 2-methyl-cyclopentyl group. , 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1 ,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3 - dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-ring Propyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl- 2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl Wait. Further, a monovalent organic group derived from adamantane or norbornene can be used.

本發明使用的聚合物與上述Ar1及Ar2之選擇不同，或與上述Ar1及Ar2之選擇同樣可含有含T1係式(3)所表示之基的上述式(1)所表示之單元構造、T1係式(4)所表示之基的上述式(1)所表示之單元構造、或彼等之單元構造之組合的聚合物。Used in the selection of the polymers of the present invention, Ar 1 and Ar 2 of the different selection or the above-described Ar 1 and Ar 2 may contain the same system of formula 1 having the formula T (3) represented by the group (1) represented by the unit cell structure is configured, the above-described formula T (4) a group represented by the Department of the formula (1) represented by the, or the polymer composition of their cell structure of the.

亦即，可使用含有Ar1及Ar2係式(2)所表示之基的上述式(1)所表示之單元構造、T1係式(3)所表示之基的上述式(1)所表示之單元構造、T1係式(4)所表示之基的上述式(1)所表示之單元構造、Ar1及Ar2係式(2)所表示之基且T1係式(3)所表示之基的上述式(1)所表示之單元構造、Ar1及Ar2係式(2)所表示之基且T1係式(4)所表示之基的上述式(1)所表示之單元構造、或此等之組合的聚合物。(1) represented by the unit configured i.e., may be used containing Ar and Ar 1 (2) 2 based group represented by the formula above formula, T (3) a group represented by the above formula based formula (1) unit construction unit configured represents the, T represented by the first system of formula (4) in the above formula (1) represented by the group, Ar 1 and Ar (2) represented by the group and T 1 lines of formula (3) 2-based formula The unit structure represented by the above formula (1), the group represented by the formula (1) of Ar 1 and Ar 2 , and the group represented by the formula (1) represented by the formula (4) of T 1 represented by the above formula (1) The unit structure, or a combination of such polymers.

式(3)及(4)中，R2、R3及R4各自為碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、羥基、烯丙基、烯丙氧基、胺基、氰基、硝基、醯基、醯基氧基、羧基、具有第3級碳構造的基、環狀烷基、或彼等之組合，n2、n3及n4各自為0乃至4之整數。T2為氟伸烷基、環狀伸烷基、或此等之組合。In the formulae (3) and (4), each of R 2 , R 3 and R 4 is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group or an allyloxy group. a group, an amine group, a cyano group, a nitro group, a decyl group, a decyloxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, wherein n2, n3 and n4 are each 0 or even An integer of 4. T 2 is a fluoroalkyl group, a cyclic alkyl group, or a combination thereof.

碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、具有第3級碳構造的基、環狀烷基、醯基、及醯基氧基可使用上述例示者。The above-exemplified examples can be used for the alkyl group having 1 to 10 carbon atoms, the fluoroalkyl group having 1 to 4 carbon atoms, the group having the third-order carbon structure, the cyclic alkyl group, the fluorenyl group, and the decyloxy group.

氟伸烷基及環狀伸烷基可使用上述例示者，此等可單獨使用或組合使用。As the fluoroalkylene group and the cyclic alkylene group, the above-exemplified ones can be used, and these can be used singly or in combination.

在式(3)，可使用R2至少含具有第3級碳構造的基，且n2為1乃至4之整數的單元構造。In the formula (3), it is possible to use a unit structure in which R 2 contains at least a group having a third-order carbon structure, and n2 is an integer of 1 to 4.

本發明除式(1)所表示之單元構造外，更可使用含式(5)所表示之單元構造的共聚合物。式(5)中，X為磺醯基或羰基，Ar3及Ar4各自為碳原子數6乃至30之伸芳基，T3為伸烷基、磺醯基、羰基、碳原子數6乃至30之伸芳基、或此等之組合。此等之伸芳基、伸烷基可使用上述例示者。In addition to the unit structure represented by the formula (1), the present invention can further use a copolymer having a unit structure represented by the formula (5). In the formula (5), X is a sulfonyl group or a carbonyl group, each of Ar 3 and Ar 4 is an exoaryl group having 6 to 30 carbon atoms, and T 3 is an alkylene group, a sulfonyl group, a carbonyl group, a carbon number of 6 or even 30 aryl, or a combination of these. The above-exemplified persons can be used for such exoaryl groups and alkylene groups.

式(5)中，伸芳基，可使用取代或者非取代之伸苯基、伸萘基、或伸蒽基。In the formula (5), a phenyl group, a substituted or unsubstituted phenyl group, a naphthyl group or a fluorenyl group may be used.

式(5)中，上述伸烷基，可舉例如碳原子數1乃至10之伸烷基，此等之伸烷基可舉例如亞甲基、伸乙基、伸丙基、異伸丙基、丙烷-2,2-二基、n-伸丁基、異伸丁基、s-伸丁基、t-伸丁基等。其中，可舉例如丙烷-2,2-二基等之碳原子數1乃至4之伸烷基。In the formula (5), the alkylene group may, for example, be an alkylene group having 1 to 10 carbon atoms, and the alkylene group may, for example, be a methylene group, an ethyl group, a propyl group or an exo-propyl group. , propane-2,2-diyl, n-butylene, isobutylene, s-butylene, t-butylene, and the like. Among them, an alkylene group having 1 to 4 carbon atoms such as a propane-2,2-diyl group can be mentioned.

式(5)中T3可使用式(6)所表示之基。式(6)中，R5及R6各自為碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、羥基、烯丙基、烯丙氧基、胺基、氰基、硝基、醯基、醯基氧基、羧基、具有第3級碳構造的基、環狀烷基、或彼等之組合，n5及n6各自為0乃至4之整數。T4為伸烷基、磺醯基、羰基、碳原子數6乃至30之伸芳基、或此等之組合。上述烷基、碳原子數1乃至4之氟烷基、醯基、醯基氧基、具有第3級碳構造的基、環狀烷基、伸烷基、及伸芳基可使用上述例示者。In the formula (5), the group represented by the formula (6) can be used for T 3 . In the formula (6), each of R 5 and R 6 is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group or a cyano group. And a nitro group, a mercapto group, a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and each of n5 and n6 is an integer of 0 to 4. T 4 is an alkylene group, a sulfonyl group, a carbonyl group, an extended aryl group having 6 to 30 carbon atoms, or a combination thereof. The above alkyl group, a fluoroalkyl group having 1 to 4 carbon atoms, a mercapto group, a mercaptooxy group, a group having a third-order carbon structure, a cyclic alkyl group, an alkylene group, and an extended aryl group can be used. .

本發明中，具有第3級碳構造的基為具有第3級碳構造之官能基。該官能基與碳原子上之氫原子做取代產生第4級碳。鍵結於該第3級碳構造的第3級碳原子之有機基，可舉例如甲基、乙基、丙基等之烷基或苯基等之芳基基，其中，甲基較宜使用。具有3個甲基的第三丁基可適用作為具有第3級碳構造的基。In the present invention, the group having the third-order carbon structure is a functional group having a third-order carbon structure. Substitution of this functional group with a hydrogen atom on a carbon atom produces a fourth-order carbon. The organic group bonded to the third-order carbon atom of the third-order carbon structure may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group or an aryl group such as a phenyl group, wherein a methyl group is preferably used. . A third butyl group having three methyl groups can be suitably used as the group having a third-order carbon structure.

本發明所使用的式(1)所表示之單元構造如以下所例示。The unit structure represented by the formula (1) used in the present invention is exemplified below.

【化6】【化6】

【化7】【化7】

含式(1)所表示之單元構造之上述聚合物為末端係羥基或鹵素基、或其羥基的氫原子或鹵素基以苯基等取代而封端者。該封端基如下述式(A)所表示之。The polymer having a unit structure represented by the formula (1) is a terminal hydroxyl group or a halogen group, or a hydrogen atom or a halogen group of a hydroxyl group thereof is substituted with a phenyl group or the like to block the terminal. This blocking group is represented by the following formula (A).

【化8】【化8】

上述式(A)中，Q1為上述烷基或鹵素原子(氟、氯、溴、碘)取代的上述烷基，k1為0乃至5之整數。In the above formula (A), Q 1 is the above alkyl group substituted with the above alkyl group or a halogen atom (fluorine, chlorine, bromine or iodine), and k1 is an integer of 0 to 5.

本發明中可使用交聯劑。該交聯劑雖無特別限制，但以具有可與聚合物之官能基反應的取代基2個以上、例如具有2乃至6個、或2乃至4個的交聯劑為佳。固形分中占有的交聯劑之比例可為0乃至50質量%、較佳為5乃至40質量%。A crosslinking agent can be used in the present invention. The crosslinking agent is not particularly limited, but is preferably a crosslinking agent having two or more substituents reactive with a functional group of the polymer, for example, 2 to 6 or 2 to 4 crosslinking agents. The proportion of the crosslinking agent which is contained in the solid content may be from 0 to 50% by mass, preferably from 5 to 40% by mass.

本發明所使用的交聯劑，可舉例如以羥基甲基或烷氧基甲基取代的具有氮原子之含氮化合物。例如以羥基甲基、甲氧基甲基、乙氧基甲基、丁氧基甲基、及己基氧基甲基等之基取代的具有氮原子之含氮化合物。又，可將含環氧基化合物、含環氧基聚合物、含烯丙基化合物、含烯丙基聚合物、含異氰酸酯基化合物、含異氰酸酯基聚合物用作為交聯劑。The crosslinking agent used in the present invention may, for example, be a nitrogen-containing compound having a nitrogen atom substituted with a hydroxymethyl group or an alkoxymethyl group. For example, a nitrogen-containing compound having a nitrogen atom substituted with a group such as a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group, or a hexyloxymethyl group. Further, an epoxy group-containing compound, an epoxy group-containing polymer, an allyl group-containing compound, an allyl group-containing polymer, an isocyanate group-containing compound, and an isocyanate group-containing polymer may be used as a crosslinking agent.

含氮化合物具體上可舉例如六甲氧基甲基三聚氰胺、四甲氧基甲基苯並三聚氰胺、1,3,4,6-肆(丁氧基甲基)乙炔脲、1,3,4,6-肆(羥基甲基)乙炔脲、1,3-雙(羥基甲基)尿素、1,1,3,3-肆(丁氧基甲基)尿素、1,1,3,3-肆(甲氧基甲基)尿素、1,3-雙(羥基甲基)-4,5-二羥基-2-四氫咪唑酮及1,3-雙(甲氧基甲基)-4,5-二甲氧基-2-四氫咪唑酮等之含氮化合物。Specific examples of the nitrogen-containing compound include hexamethoxymethyl melamine, tetramethoxymethyl benzo melamine, 1,3,4,6-fluorenyl (butoxymethyl) acetylene urea, 1, 3, 4, 6-fluorene (hydroxymethyl) acetylene urea, 1,3-bis(hydroxymethyl) urea, 1,1,3,3-indole (butoxymethyl) urea, 1,1,3,3-肆(methoxymethyl) urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-tetrahydroimidazolidone and 1,3-bis(methoxymethyl)-4,5 a nitrogen-containing compound such as dimethoxy-2-tetrahydroimidazolium.

交聯劑，可舉例如三井Cytec(股)製甲氧基甲基型三聚氰胺化合物(商品名Cyme1300、Cyme1301、Cyme1303、Cyme1350)、丁氧基甲基型三聚氰胺化合物(商品名MYCOAT 506、MYCOAT 508)、乙炔脲化合物(商品名Cyme11170、Powderlink1174)、甲基化尿素樹脂(商品名UFR65)、丁基化尿素樹脂(商品名UFR300、U-VAN10S60、U-VAN10R、U-VAN11HV)、大日本油墨化學工業(股)製尿素/甲醛系樹脂(高縮合型、商品名BECKAMINEJ-300S、BECKAMINEP-955、BECKAMINEN)等之市售的化合物。The crosslinking agent may, for example, be a methoxymethyl type melamine compound (trade name: Cyme 1300, Cyme 1301, Cyme 1303, Cyme 1350) manufactured by Mitsui Cytec Co., Ltd., or a butoxymethyl type melamine compound (trade name: MYCOAT 506, MYCOAT 508). , acetylene urea compound (trade name Cyme11170, Powderlink 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), Dainippon Ink Chemistry Commercially available compounds such as urea/formaldehyde resins (high condensation type, trade name BECKAMINEJ-300S, BECKAMINEP-955, BECKAMINEN) manufactured by the company.

又，交聯劑可為使胺基的氫原子經羥基甲基或烷氧基甲基取代的前述般三聚氰胺化合物、尿素化合物、乙炔脲化合物及苯並三聚氰胺化合物縮合而得的化合物。例如可使用美國專利6323310號記載的由三聚氰胺化合物(商品名Cymel303)與苯並三聚氰胺化合物(商品名Cymel1123)所製造之高分子量化合物作為交聯性化合物。Further, the crosslinking agent may be a compound obtained by condensing the above-described melamine compound, urea compound, acetylene urea compound, and benzoguanamine compound in which a hydrogen atom of an amine group is substituted with a hydroxymethyl group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound (trade name Cymel 303) and a benzoguanamine compound (trade name Cymel 1123) described in U.S. Patent No. 6,323,310 can be used as a crosslinkable compound.

又，交聯劑，可使用N-羥基甲基丙烯醯胺、N-甲氧基甲基甲基丙烯醯胺、N-乙氧基甲基丙烯醯胺及N-丁氧基甲基甲基丙烯醯胺等之經羥基甲基或烷氧基甲基取代的丙烯醯胺化合物或甲基丙烯醯胺化合物而製造之聚合物化合物。彼等聚合物化合物，可舉例如聚(N-丁氧基甲基丙烯醯胺)、N-丁氧基甲基丙烯醯胺與苯乙烯之共聚合物、N-羥基甲基甲基丙烯醯胺與甲基甲基丙烯酸酯之共聚合物、N-乙氧基甲基甲基丙烯醯胺與芐基甲基丙烯酸酯之共聚合物、及N-丁氧基甲基丙烯醯胺與芐基甲基丙烯酸酯與2-羥基丙基甲基丙烯酸酯之共聚合物等。Further, as the crosslinking agent, N-hydroxymethylpropenylamine, N-methoxymethylmethacrylamide, N-ethoxymethylpropenylamine and N-butoxymethylmethyl can be used. A polymer compound produced by a acrylamide or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as acrylamide. Examples of the polymer compound include poly(N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, and N-hydroxymethyl methacryl oxime. a copolymer of an amine and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and N-butoxymethyl acrylamide and benzyl A copolymer of a methacrylic acid ester and 2-hydroxypropyl methacrylate, and the like.

具有環氧基的交聯劑，可使用例如具有1個乃至6個、或2個乃至4個環氧環之化合物。具有環氧環的化合物，可舉例如由二醇化合物、三醇化合物、二羧酸化合物及三羧酸化合物等之具有2個以上羥基或羧基之化合物與表氯醇等之環氧丙基化合物製造的具有2個以上之環氧丙基醚構造或環氧丙基酯構造的化合物。例如1,4-丙二醇二環氧丙基醚、1,2-環氧-4-(環氧乙基)環己烷、丙三醇三環氧丙基醚、二乙二醇二環氧丙基醚、2,6-二環氧丙基苯基環氧丙基醚、1,1,3-參[p-(2,3-環氧丙氧基)苯基]丙烷、1,2-環己烷二羧酸二環氧丙基酯、4,4’-亞甲基雙(N,N-二環氧丙基苯胺)、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、三羥甲基乙烷三環氧丙基醚、三環氧丙基-p-胺基酚、四環氧丙基間二甲苯二胺、四環氧丙基二胺基二苯基甲烷、四環氧丙基-1,3-雙胺基甲基環己烷、雙酚-A-二環氧丙基醚、雙酚-S-二環氧丙基醚、季戊四醇四環氧丙基醚間苯二酚二環氧丙基醚、苯二甲酸二環氧丙基酯、新戊二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、四溴雙酚-A-二環氧丙基醚、雙酚六氟丙酮二環氧丙基醚、季戊四醇二環氧丙基醚、參-(2,3-環氧丙基)異氰脲酸酯、單烯丙基二環氧丙基異氰脲酸酯、二丙三醇聚二環氧丙基醚、季戊四醇聚環氧丙基醚、1,4-雙(2,3-環氧丙氧基全氟異丙基)環己烷、山梨醣醇聚環氧丙基醚、三羥甲基丙烷聚環氧丙基醚、間苯二酚二環氧丙基醚、1,6-己二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、苯基環氧丙基醚、p-第三丁基苯基環氧丙基醚、己二酸二環氧丙基醚、o-苯二甲酸二環氧丙基醚、二溴苯基環氧丙基醚、1,2,7,8-二環氧辛烷、1,6-二羥甲基全氟己烷二環氧丙基醚、4,4’-雙(2,3-環氧丙氧基全氟異丙基)二苯基醚、2,2-雙(4-環氧丙基氧基苯基)丙烷、3,4-環氧環己基甲基-3’,4’-環氧環己烷羧酸酯、3,4-環氧環己基環氧乙烷、2-(3,4-環氧環己基)-3’,4’-環氧-1,3-二噁烷-5-螺環己烷、1,2-伸乙基二氧基-雙(3,4-環氧環己基甲烷)、4’,5’-環氧-2’-甲基環己基甲基-4,5-環氧-2-甲基環己烷羧酸酯、乙二醇-雙(3,4-環氧環己烷羧酸酯)、雙-(3,4-環氧環己基甲基)己二酸、及雙(2,3-環氧環戊基)醚等。As the crosslinking agent having an epoxy group, for example, a compound having one to six, or two or even four epoxy rings can be used. The compound having an epoxy ring may, for example, be a compound having two or more hydroxyl groups or carboxyl groups such as a diol compound, a triol compound, a dicarboxylic acid compound or a tricarboxylic acid compound, and an epoxy propyl compound such as epichlorohydrin. A compound having two or more epoxypropyl ether structures or a glycidyl ester structure produced. For example, 1,4-propanediol diepoxypropyl ether, 1,2-epoxy-4-(oxiranyl)cyclohexane, glycerol triepoxypropyl ether, diethylene glycol diepoxypropyl Ether, 2,6-diepoxypropyl phenylepoxypropyl ether, 1,1,3-gin[p-(2,3-epoxypropoxy)phenyl]propane, 1,2- Dicyclopropyl propyl cyclohexanedicarboxylate, 4,4'-methylenebis(N,N-diepoxypropylaniline), 3,4-epoxycyclohexylmethyl-3,4- Epoxycyclohexane carboxylate, trimethylolethane triepoxypropyl ether, triepoxypropyl-p-aminophenol, tetraepoxypropylm-xylenediamine, tetra-epoxypropyl Diaminodiphenylmethane, tetraethoxypropyl-1,3-diaminomethylcyclohexane, bisphenol-A-diglycidyl ether, bisphenol-S-diglycidyl ether Pentaerythritol tetraepoxypropyl ether resorcinol diepoxypropyl ether, diepoxypropyl phthalate, neopentyl glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, four Bromobisphenol-A-diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diepoxypropyl ether, gins-(2,3-epoxypropyl)isocyanurate Monoallyl epoxypropyl isocyanurate, dipropyl Alcohol polydioxypropyl ether, pentaerythritol polyepoxypropyl ether, 1,4-bis(2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, sorbitol polyepoxypropyl Ether, trimethylolpropane polyepoxypropyl ether, resorcinol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, Phenylepoxypropyl ether, p-t-butylphenylepoxypropyl ether, diepoxypropyl ether of adipic acid, diepoxypropyl ether of o-phthalic acid, dibromophenyl epoxy Propyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylol perfluorohexane diepoxypropyl ether, 4,4'-bis(2,3-epoxy Propyloxyperfluoroisopropyl)diphenyl ether, 2,2-bis(4-epoxypropyloxyphenyl)propane, 3,4-epoxycyclohexylmethyl-3', 4'- Epoxycyclohexane carboxylate, 3,4-epoxycyclohexylethylene oxide, 2-(3,4-epoxycyclohexyl)-3',4'-epoxy-1,3-dioxin Alkan-5-spirocyclohexane, 1,2-extended ethylenedioxy-bis(3,4-epoxycyclohexylmethane), 4',5'-epoxy-2'-methylcyclohexyl Base-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis(3,4-epoxycyclohexanecarboxylate), bis-(3,4-epoxy ring) Yl methyl) adipate, and bis (2,3-epoxy cyclopentyl) ether and the like.

交聯劑可僅使用1種化合物、或2種以上之化合物組合使用。The crosslinking agent may be used alone or in combination of two or more compounds.

本發明之接著劑組成物可含交聯觸媒。藉由使用交聯觸媒促進交聯性化合物之反應。The adhesive composition of the present invention may contain a crosslinking catalyst. The reaction of the crosslinkable compound is promoted by using a crosslinking catalyst.

交聯觸媒，可使用p-甲苯磺酸、三氟甲烷磺酸、甲烷磺酸、吡啶鎓-p-甲苯磺酸、水楊酸、樟腦磺酸、磺水楊酸、檸檬酸、安息香酸、及羥基安息香酸等之酸化合物。For cross-linking catalyst, p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, pyridinium-p-toluenesulfonic acid, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, citric acid, benzoic acid can be used. And an acid compound such as hydroxybenzoic acid.

交聯觸媒可使用芳香族磺酸化合物。芳香族磺酸化合物之具體例，可舉例如p-甲苯磺酸、吡啶鎓-p-甲苯磺酸、磺水楊酸、4-氯苯磺酸、4-羥基苯磺酸、苯二磺酸、1-萘磺酸、及吡啶鎓-1-萘磺酸等。An aromatic sulfonic acid compound can be used for the crosslinking catalyst. Specific examples of the aromatic sulfonic acid compound include p-toluenesulfonic acid, pyridinium-p-toluenesulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, and benzenedisulfonic acid. , 1-naphthalenesulfonic acid, and pyridinium-1-naphthalenesulfonic acid, and the like.

使用具有環氧基之交聯劑的場合，交聯觸媒可使用酚樹脂、胺類、聚醯胺樹脂、咪唑類、聚硫醇、酸酐等。When a crosslinking agent having an epoxy group is used, a phenol resin, an amine, a polyamide resin, an imidazole, a polythiol, an acid anhydride or the like can be used as the crosslinking catalyst.

酚樹脂，可舉例如酚酚醛清漆樹脂、甲酚酚醛清漆樹脂等。Examples of the phenol resin include a phenol novolak resin and a cresol novolak resin.

胺類可舉例如哌啶、N,N-二甲基哌嗪、三伸乙基二胺、2,4,6-參(二甲基胺基甲基)酚、芐基二甲基胺、2-(二甲基胺基甲基)酚、二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、二乙基胺基丙基胺、N-胺基乙基哌嗪、二(1-甲基-2-胺基環己基)甲烷、孟烷二胺、異佛酮二胺、二胺基二環己基甲烷、1,3-二胺基甲基環己烷、苯二甲胺、間苯二胺、二胺基二苯基甲烷、二胺基二苯基碸等。此等之中以二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、二乙基胺基丙基胺、N-胺基乙基哌嗪、二(1-甲基-2-胺基環己基)甲烷、孟烷二胺、異佛酮二胺、二胺基二環己基甲烷等較宜使用。The amines may, for example, be piperidine, N,N-dimethylpiperazine, tri-ethylenediamine, 2,4,6-gin(dimethylaminomethyl)phenol, benzyldimethylamine, 2-(Dimethylaminomethyl)phenol, di-ethyltriamine, tri-ethyltetramine, tetraethylamamine, diethylaminopropylamine, N-aminoethylpiper Pyrazine, bis(1-methyl-2-aminocyclohexyl)methane, montanyl diamine, isophorone diamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, Xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylphosphonium, and the like. Among these, diethyltriamine, triethylamine, tetraethylamamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl) 2-Aminocyclohexyl)methane, montanyldiamine, isophoronediamine, diaminodicyclohexylmethane or the like is preferably used.

聚醯胺樹脂，可舉例如由二聚酸與聚胺之縮合而生成者，且分子中具有一級胺與二級胺之聚醯胺胺。The polyamine resin may, for example, be produced by condensation of a dimer acid and a polyamine, and a polyamine amine having a primary amine and a secondary amine in the molecule.

咪唑類，可舉例如2-甲基咪唑、2-乙基-4-甲基咪唑、1-氰基乙基-2-十一基咪唑鎓偏苯三酸、環氧咪唑加成物等。Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitic acid, and epoxy imidazole adducts.

聚硫醇，可舉例如聚丙二醇鏈的末端有硫醇基者或聚乙二醇鏈的末端有硫醇基者。The polythiol may, for example, be a thiol group at the terminal of the polypropylene glycol chain or a thiol group at the terminal of the polyethylene glycol chain.

酸酐以一分子中具有複數羧基的化合物之無水物為佳。此等之酸酐，可舉例如苯二甲酸酐、偏苯三酸酐、均苯四甲酸酐、二苯甲酮四羧酸酐、乙二醇雙偏苯三酸、丙三醇參偏苯三酸、馬來酸酐、四氫苯二甲酸酐、甲基四氫苯二甲酸酐、內亞甲基四氫苯二甲酸酐、甲基內亞甲基四氫苯二甲酸酐、甲基丁烯基四氫苯二甲酸酐、十二烯基琥珀酸酐、六氫苯二甲酸酐、甲基六氫苯二甲酸酐、琥珀酸酐、甲基環己烯二羧酸酐、六氯內亞甲四氫酞酐等。The anhydride is preferably an anhydride of a compound having a plurality of carboxyl groups in one molecule. Examples of such acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic acid, glycerol, trimellitic acid, and maleic anhydride. , tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrobenzene Formic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, hexachlorotetramethylene anhydride, and the like.

又，其他交聯觸媒，可舉例如三苯基膦或三丁基膦等之有機磷化合物、乙基三苯基鏻溴化物、四丁基鏻二硫磷酸二乙鹽等之第4級鏻鹽、1,8-二氮雜雙環(5，4，0)十一烷-7-烯、1,8-二氮雜雙環(5，4，0)十一烷-7-烯與辛酸之鹽、辛酸鋅、四丁基銨溴化物等之第4級銨鹽。Further, as another cross-linking catalyst, for example, an organophosphorus compound such as triphenylphosphine or tributylphosphine, ethyltriphenylphosphonium bromide or tetrabutylphosphonium dithiophosphate diethyl salt may be used. Onium salt, 1,8-diazabicyclo(5,4,0) undecane-7-ene, 1,8-diazabicyclo(5,4,0) undecane-7-ene and octanoic acid a fourth-order ammonium salt of a salt, zinc octoate, tetrabutylammonium bromide or the like.

在使用具有烯丙基之交聯劑的場合，硬化觸媒可使用例如自由基聚合起始劑及陽離子聚合起始劑。When a crosslinking agent having an allyl group is used, the curing catalyst may be, for example, a radical polymerization initiator and a cationic polymerization initiator.

自由基聚合起始劑，可舉例如咪唑化合物、重氮基化合物、雙咪唑化合物、N-芳基甘胺酸化合物、有機疊氮化合物、二茂鈦化合物、鋁酸鹽化合物、有機過酸化物、N-烷氧基吡啶鎓鹽化合物、及噻噸酮化合物等。The radical polymerization initiator may, for example, be an imidazole compound, a diazo compound, a diimidazole compound, an N-arylglycine compound, an organic azide compound, a titanocene compound, an aluminate compound, or an organic peracid compound. , an N-alkoxypyridinium salt compound, a thioxanthone compound, and the like.

有機疊氮化合物，可舉例如p-疊氮苯甲醛、p-疊氮苯乙酮、p-疊氮安息香酸、p-疊氮苯亞甲基苯乙酮、4,4’-二疊氮查耳酮、4,4’-二疊氮二苯基硫化物、及2,6-雙(4’-疊氮苯亞甲基)-4-甲基環己酮等。The organic azide compound may, for example, be p-azidaldehyde benzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzylidene acetophenone, 4,4'-diazide Chalcone, 4,4'-diazide diphenyl sulfide, and 2,6-bis(4'-azidobenzylidene)-4-methylcyclohexanone.

重氮基化合物，可舉例如1-重氮基-2,5-二乙氧基-4-p-甲苯基巰基苯硼氟化物、1-重氮基-4-N,N-二甲基胺基苯氯化物、及1-重氮基-4-N,N-二乙基胺基苯硼氟化物等。The diazo compound may, for example, be 1-diazo-2,5-diethoxy-4-p-tolylnonylbenzene boron fluoride, 1-diazo-4-N,N-dimethyl Amino phenyl chloride, and 1-diazo-4-N,N-diethylaminophenyl boron fluoride, and the like.

雙咪唑化合物，可舉例如2,2’-雙(o-氯苯基)-4,5,4’,5’-肆(3,4,5-三甲氧基苯基)1,2’-雙咪唑、及2,2’-雙(o-氯苯基)4,5,4’,5’-四苯基-1,2’-雙咪唑等。The biimidazole compound may, for example, be 2,2'-bis(o-chlorophenyl)-4,5,4',5'-fluorene (3,4,5-trimethoxyphenyl) 1,2'- Biimidazole and 2,2'-bis(o-chlorophenyl) 4,5,4',5'-tetraphenyl-1,2'-bisimidazole.

二茂鈦化合物，可舉例如二環戊二烯基-鈦-二氯化物、二環戊二烯基-鈦-雙苯基、二環戊二烯基-鈦-雙(2,3,4,5,6-五氟苯基)、二環戊二烯基-鈦-雙(2,3,5,6-四氟苯基)、二環戊二烯基-鈦-雙(2,4,6-三氟苯基)、二環戊二烯基-鈦-雙(2,6-二氟苯基)、二環戊二烯基-鈦-雙(2,4-二氟苯基)、雙(甲基環戊二烯基)-鈦-雙(2,3,4,5,6-五氟苯基)、雙(甲基環戊二烯基)-鈦-雙(2,3,5,6-四氟苯基)、雙(甲基環戊二烯基)-鈦-雙(2,6-二氟苯基)、及二環戊二烯基-鈦-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)等。The titanocene compound may, for example, be dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-diphenyl, dicyclopentadienyl-titanium-bis (2,3,4) ,5,6-pentafluorophenyl),dicyclopentadienyl-titanium-bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis (2,4 ,6-trifluorophenyl),dicyclopentadienyl-titanium-bis(2,6-difluorophenyl), dicyclopentadienyl-titanium-bis(2,4-difluorophenyl) , bis(methylcyclopentadienyl)-titanium-bis(2,3,4,5,6-pentafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis (2,3 ,5,6-tetrafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2,6-difluorophenyl), and dicyclopentadienyl-titanium-bis (2, 6-Difluoro-3-(1H-pyrrol-1-yl)-phenyl) and the like.

自由基聚合起始劑，可舉例如1,3-二(tert-丁基二氧基羰基)二苯甲酮、3,3’,4,4’-肆(tert-丁基二氧基羰基)二苯甲酮、3-苯基-5-異噁唑林酮、2-巰基苯咪唑、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羥基-環己基-苯基-酮、及2-芐基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮等。The radical polymerization initiator may, for example, be 1,3-bis(tert-butyldioxycarbonyl)benzophenone or 3,3',4,4'-fluorene (tert-butyldioxycarbonyl). Benzophenone, 3-phenyl-5-isoxazolinone, 2-mercaptobenazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- Hydroxy-cyclohexyl-phenyl-ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone and the like.

陽離子聚合起始劑，可舉例如磺酸酯、磺醯亞胺化合物、二磺醯基重氮基甲烷化合物、二烷基-4-羥基鋶鹽、芳基磺酸-p-硝基芐基酯、矽烷醇-鋁錯合物、(η6-苯)(η5-環戊二烯基)鐵(II)等。The cationic polymerization initiator may, for example, be a sulfonate, a sulfonimide compound, a disulfonyldiazomethane compound, a dialkyl-4-hydroxyindole salt, or an arylsulfonic acid-p-nitrobenzyl group. Ester, stanol-aluminum complex, (η6-benzene) (η5-cyclopentadienyl) iron (II), and the like.

磺醯亞胺化合物，可舉例如N-(三氟甲烷磺醯基氧基)琥珀醯亞胺、N-(九氟-正丁烷磺醯基氧基)琥珀醯亞胺、N-(樟腦磺醯基氧基)琥珀醯亞胺及N-(三氟甲烷磺醯基氧基)萘二甲醯亞胺等。The sulfonimide compound may, for example, be N-(trifluoromethanesulfonyloxy) succinimide, N-(nonafluoro-n-butanesulfonyloxy) succinimide, N-( camphor Sulfhydryloxy) succinimide and N-(trifluoromethanesulfonyloxy)naphthylimine.

二磺醯基重氮基甲烷化合物，可舉例如雙(三氟甲基磺醯基)重氮基甲烷、雙(環己基磺醯基)重氮基甲烷、雙(苯基磺醯基)重氮基甲烷、雙(p-甲苯磺醯基)重氮基甲烷、雙(2,4-二甲基苯磺醯基)重氮基甲烷、及甲基磺醯基-p-甲苯磺醯基重氮基甲烷等。The disulfonyldiazomethane compound may, for example, be bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane or bis(phenylsulfonyl) Nitrogen methane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl Diazomethane and the like.

陽離子聚合起始劑，可舉例如2-甲基-1-(4-甲基硫基苯基)-2-嗎啉基丙烷-1-酮。The cationic polymerization initiator may, for example, be 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one.

又，芳香族碘鎓鹽化合物、芳香族鋶鹽化合物、芳香族重氮鎓鹽化合物、芳香族鏻鹽化合物、三嗪化合物及鐵芳族烴錯合物化合物等可用作為自由基聚合起始劑或陽離子聚合起始劑。Further, an aromatic iodonium salt compound, an aromatic sulfonium salt compound, an aromatic diazonium salt compound, an aromatic sulfonium salt compound, a triazine compound, and an iron aromatic hydrocarbon compound compound can be used as a radical polymerization initiator. Or a cationic polymerization initiator.

芳香族碘鎓鹽化合物，可舉例如二苯基碘鎓六氟磷酸鹽、二苯基碘鎓三氟甲烷磺酸鹽、二苯基碘鎓九氟-正丁烷磺酸鹽、二苯基碘鎓全氟-正辛烷磺酸鹽、二苯基碘鎓樟腦磺酸鹽、雙(4-tert-丁基苯基)碘鎓樟腦磺酸鹽及雙(4-tert-丁基苯基)碘鎓三氟甲烷磺酸鹽等。The aromatic iodonium salt compound may, for example, be diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate or diphenyl. Iodine perfluoro-n-octane sulfonate, diphenyl iodonium sulfonate, bis(4-tert-butylphenyl) iodonium sulfonate and bis(4-tert-butylphenyl) Iodine trifluoromethanesulfonate and the like.

芳香族鋶鹽化合物，可舉例如三苯基鋶六氟銻酸鹽、三苯基鋶九氟正丁烷磺酸鹽、三苯基鋶樟腦磺酸鹽及三苯基鋶三氟甲烷磺酸鹽等。The aromatic onium salt compound may, for example, be triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluorobutanesulfonate, triphenyl camphorsulfonate or triphenylsulfonium trifluoromethanesulfonate. Salt and so on.

交聯觸媒可僅使用1種或2種以上組合使用。The cross-linking catalyst may be used singly or in combination of two or more kinds.

交聯觸媒相對聚合物而言，可以0乃至10質量份、或0.01乃至10質量份、或0.05乃至8質量份、或0.1乃至5質量份、或0.3乃至3質量份、或0.5乃至1質量份來使用。The cross-linking catalyst may be 0 to 10 parts by mass, or 0.01 to 10 parts by mass, or 0.05 to 8 parts by mass, or 0.1 to 5 parts by mass, or 0.3 to 3 parts by mass, or 0.5 to 1 mass, relative to the polymer. Use it.

又，本發明所使用的被接著物，可舉例如矽基板、玻璃基板、樹脂基板、及陶瓷基板。此等基板可用作為本發明之層合物的支持體。Moreover, examples of the object to be used in the present invention include a ruthenium substrate, a glass substrate, a resin substrate, and a ceramic substrate. These substrates can be used as a support for the laminate of the present invention.

本發明所使用的被接著物可舉例如矽、氧化矽、玻璃、氮化矽等之無機材料、鋁、銅等之金屬材料、聚醯胺樹脂、聚醯亞胺樹脂、環氧樹脂、聚丙烯酸樹脂、聚甲基丙烯酸樹脂、聚苯並噁唑樹脂、聚羥基苯乙烯樹脂、苯並環丁烯樹脂等之樹脂材料等。The material to be used in the present invention may, for example, be an inorganic material such as ruthenium, iridium oxide, glass or tantalum nitride, a metal material such as aluminum or copper, a polyamide resin, a polyimide resin, an epoxy resin or a poly A resin material such as an acrylic resin, a polymethacrylic resin, a polybenzoxazole resin, a polyhydroxystyrene resin, or a benzocyclobutene resin.

接著劑組成物為了旋轉塗佈而可使用有機溶劑將其溶解。聚合物溶解於有機溶劑、該溶液黏度在0.001乃至5000Pa‧s之黏度範圍，可將該聚合物溶液作為具旋轉塗佈性之塗佈液。The subsequent composition can be dissolved by an organic solvent for spin coating. The polymer is dissolved in an organic solvent, and the viscosity of the solution is in the range of 0.001 to 5000 Pa s. The polymer solution can be used as a coating liquid having spin coating properties.

上述有機溶劑，為可在其他半導體步驟使用的溶劑即可，並無特別限制，以使用環己酮、甲基異戊基酮、2-庚酮等之酮類；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基醚、單乙基醚、單丙基醚、單丁基醚或單苯基醚等之多元醇類及其衍生物；二噁烷等之環式醚類；以及乳酸甲酯、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、乙氧基丙酸乙酯等之酯類為佳。此等可單獨使用或2種以上混合使用。The organic solvent is not particularly limited as long as it can be used in another semiconductor step, and a ketone such as cyclohexanone, methyl isoamyl ketone or 2-heptanone; ethylene glycol or ethylene glycol; Monomethyl ether, monoethyl ether, monopropyl, monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate Polyols such as ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid Esters such as ester, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate and the like are preferred. These may be used singly or in combination of two or more.

本實施形態的接著劑組成物中，在不損及本發明本質特性範圍，可再添加具混合性的添加劑，例如改良接著劑性能用的加成的樹脂、黏著賦予劑、可塑劑、接著助劑、安定劑、著色劑、界面活性劑等之慣用者。In the adhesive composition of the present embodiment, a mixed additive such as an additive resin for improving the performance of the adhesive, an adhesive imparting agent, a plasticizer, and the like may be further added without impairing the essential characteristics of the present invention. Conventional agents such as agents, stabilizers, colorants, surfactants, and the like.

作為改良接著劑性能用之加成的樹脂(聚合物)，可使用聚酯、聚苯乙烯、聚醯亞胺、丙烯基聚合物、甲基丙烯基聚合物、聚乙烯基醚、酚酚醛清漆、萘酚酚醛清漆、聚醚、聚醯胺、及聚碳酸酯等之加成聚合聚合物或縮聚合聚合物。以苯環、萘環、蒽環、三嗪環、喹啉環、及喹喔啉環等之具芳香環構造的聚合物較宜使用。As the resin (polymer) to be used for improving the performance of the adhesive, polyester, polystyrene, polyimide, propylene-based polymer, methacryl-based polymer, polyvinyl ether, phenol novolac can be used. An addition polymerized polymer or a polycondensation polymer of a naphthol novolac, a polyether, a polyamide, and a polycarbonate. A polymer having an aromatic ring structure such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, or a quinoxaline ring is preferably used.

如此之加成的樹脂(聚合物)，可舉例如含有以芐基丙烯酸酯、芐基甲基丙烯酸酯、苯基丙烯酸酯、萘基丙烯酸酯、蒽基甲基丙烯酸酯、蒽基甲基甲基丙烯酸酯、苯乙烯、羥基苯乙烯、芐基乙烯基醚、及N-苯基馬來醯亞胺等之加成聚合性單體作為其構造單元的加成聚合聚合物或酚酚醛清漆、及萘酚酚醛清漆等之縮聚合聚合物。The resin (polymer) thus added may, for example, be a benzyl acrylate, a benzyl methacrylate, a phenyl acrylate, a naphthyl acrylate, a decyl methacrylate or a decyl methyl group. Addition polymerizable monomer such as acrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as an addition polymerization polymer or phenol novolac of its structural unit, And a polycondensation polymer such as naphthol novolac.

又，加成的樹脂(聚合物)可使用無芳香環構造之聚合物。如此之聚合物，可舉例如僅含有以烷基丙烯酸酯、烷基甲基丙烯酸酯、乙烯基醚、烷基乙烯基醚、丙烯腈、馬來醯亞胺、N-烷基馬來醯亞胺、及馬來酸酐等之不具芳香環構造的加成聚合性單體作為其構造單元的加成聚合聚合物。Further, as the added resin (polymer), a polymer having no aromatic ring structure can be used. Such a polymer may, for example, contain only alkyl acrylate, alkyl methacrylate, vinyl ether, alkyl vinyl ether, acrylonitrile, maleimide, N-alkyl malayan An addition polymerizable monomer having no aromatic ring structure such as an amine or maleic anhydride as an addition polymerizable polymer of the structural unit thereof.

加成的樹脂(聚合物)使用加成聚合聚合物之場合，該聚合物可為單獨聚合物或共聚合物。在加成聚合系聚合物之製造時使用加成聚合性單體。如此之加成聚合性單體，可舉例如丙烯酸、甲基丙烯酸、丙烯酸酯化合物、甲基丙烯酸酯化合物、丙烯醯胺化合物、甲基丙烯醯胺化合物、乙烯基化合物、苯乙烯化合物、馬來醯亞胺化合物、馬來酸酐、及丙烯腈等。Where the addition resin (polymer) is an addition polymerized polymer, the polymer may be a single polymer or a copolymer. An addition polymerizable monomer is used in the production of the addition polymerization polymer. Examples of the addition polymerizable monomer include acrylic acid, methacrylic acid, acrylate compound, methacrylate compound, acrylamide compound, methacrylamide compound, vinyl compound, styrene compound, and Malay. An imine compound, maleic anhydride, acrylonitrile, and the like.

丙烯酸酯化合物，可舉例如甲基丙烯酸酯、乙基丙烯酸酯、正己基丙烯酸酯、異丙基丙烯酸酯、環己基丙烯酸酯、芐基丙烯酸酯、苯基丙烯酸酯、蒽基甲基丙烯酸酯、2-羥基乙基丙烯酸酯、3-氯-2-羥基丙基丙烯酸酯、2-羥基丙基丙烯酸酯、2,2,2-三氟乙基丙烯酸酯、2,2,2-三氯乙基丙烯酸酯、2-溴乙基丙烯酸酯、4-羥基丁基丙烯酸酯、2-甲氧基乙基丙烯酸酯、四氫糠基丙烯酸酯、2-甲基-2-金剛烷基丙烯酸酯、5-丙烯醯氧基-6-羥基降冰片烯-2-羧酸-6-內酯、3-丙烯醯氧基丙基三乙氧基矽烷、及環氧丙基丙烯酸酯等。Examples of the acrylate compound include methacrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, mercapto methacrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloro Acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-propenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 3-propenyloxypropyltriethoxydecane, and epoxypropyl acrylate.

甲基丙烯酸酯化合物，可舉例如甲基甲基丙烯酸酯、乙基甲基丙烯酸酯、正己基甲基丙烯酸酯、異丙基甲基丙烯酸酯、環己基甲基丙烯酸酯、芐基甲基丙烯酸酯、苯基甲基丙烯酸酯、蒽基甲基甲基丙烯酸酯、2-羥基乙基甲基丙烯酸酯、2-羥基丙基甲基丙烯酸酯、2,2,2-三氟乙基甲基丙烯酸酯、2,2,2-三氯乙基甲基丙烯酸酯、2-溴乙基甲基丙烯酸酯、4-羥基丁基甲基丙烯酸酯、2-甲氧基乙基甲基丙烯酸酯、四氫糠基甲基丙烯酸酯、2-甲基-2-金剛烷基甲基丙烯酸酯、5-甲基丙烯醯基氧基-6-羥基降冰片烯-2-羧酸-6-內酯、3-甲基丙烯醯氧基丙基三乙氧基矽烷、環氧丙基甲基丙烯酸酯、2-苯基乙基甲基丙烯酸酯、羥基苯基甲基丙烯酸酯、及溴苯基甲基丙烯酸酯等。Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylic acid. Ester, phenyl methacrylate, mercaptomethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethylmethyl Acrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrogen Mercapto methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methylpropenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 3 -Methyl propylene methoxy propyl triethoxy decane, epoxy propyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate Ester and the like.

丙烯醯胺化合物，可舉例如丙烯醯胺、N-甲基丙烯醯胺、N-乙基丙烯醯胺、N-芐基丙烯醯胺、N-苯基丙烯醯胺、N,N-二甲基丙烯醯胺、及N-蒽基丙烯醯胺等。The acrylamide compound may, for example, be acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-benzyl acrylamide, N-phenyl acrylamide, N, N-dimethyl Acrylamide, and N-mercaptopropenylamine.

甲基丙烯醯胺化合物，可舉例如甲基丙烯醯胺、N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺、N-芐基甲基丙烯醯胺、N-苯基甲基丙烯醯胺、N,N-二甲基甲基丙烯醯胺、及N-蒽基丙烯醯胺等。The methacrylamide compound may, for example, be methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenyl. Methyl acrylamide, N,N-dimethyl methacrylamide, and N-mercapto acrylamide.

乙烯基化合物，可舉例如乙烯基醇、2-羥基乙基乙烯基醚、甲基乙烯基醚、乙基乙烯基醚、芐基乙烯基醚、乙烯基乙酸、乙烯基三甲氧基矽烷、2-氯乙基乙烯基醚、2-甲氧基乙基乙烯基醚、乙烯基萘、及乙烯基蒽等。The vinyl compound may, for example, be vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxy decane, 2 -Chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

苯乙烯化合物，可舉例如苯乙烯、羥基苯乙烯、氯苯乙烯、溴苯乙烯、甲氧基苯乙烯、氰基苯乙烯、及乙醯基苯乙烯等。Examples of the styrene compound include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and ethyl styrene styrene.

馬來醯亞胺化合物，可舉例如馬來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-芐基馬來醯亞胺、及N-羥基乙基馬來醯亞胺等。The maleidin compound may, for example, be maleimine, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl Maleic imine, and N-hydroxyethyl maleimide, and the like.

本發明之接著劑組成物使用的加成的樹脂(聚合物)之分子量，以重量平均分子量計例如為1000乃至1000000、或3000乃至300000、又，例如5000乃至200000、或10000乃至100000。The molecular weight of the addition resin (polymer) used in the adhesive composition of the present invention is, for example, 1000 to 1,000,000, or 3,000 to 300,000, and further, for example, 5,000 to 200,000, or 10,000 to 100,000, by weight average molecular weight.

本發明之接著劑組成物含有加成的樹脂(聚合物)之場合，其含量為固形分中，例如0乃至40質量%、或0乃至20質量%、或1乃至19質量%。When the adhesive composition of the present invention contains an added resin (polymer), the content thereof is, for example, 0 to 40% by mass, or 0 to 20% by mass, or 1 to 19% by mass in the solid content.

黏著賦予劑係為了接著層之彈性率、黏性控制、表面狀態控制而添加。該黏著賦予劑之種類以考量接著層的黏性而定為佳，但具體上可舉例如脂肪族系石油樹脂、芳香族系石油樹脂、脂肪族‧芳香族共聚合系石油樹脂、脂環族系氫化石油樹脂、烷基酚樹脂、二甲苯樹脂、香豆酮茚樹脂、萜烯樹脂、萜烯酚樹脂、芳香族改性萜烯樹脂、氫化萜烯樹脂、松香系樹脂、氫化松香系樹脂、不均化松香系樹脂、二量化松香系樹脂、酯化松香系樹脂等之1種單獨或2種以上之組合。黏著賦予劑相對接著劑組成物之主成分的聚醚100重量份而言可含有0乃至100重量份之比例。The adhesion imparting agent is added for the elastic modulus, viscosity control, and surface state control of the adhesive layer. The type of the adhesion-imparting agent is preferably determined in consideration of the adhesiveness of the adhesive layer, and specific examples thereof include an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic ‧ aromatic copolymerized petroleum resin, and an alicyclic group. Hydrogenated petroleum resin, alkylphenol resin, xylene resin, coumarone oxime resin, terpene resin, terpene phenol resin, aromatic modified terpene resin, hydrogenated terpene resin, rosin resin, hydrogenated rosin resin One type or a combination of two or more types of the rosin-based resin, the second-quantized rosin-based resin, and the esterified rosin-based resin. The adhesion-imparting agent may contain a ratio of 0 to 100 parts by weight based on 100 parts by weight of the polyether as a main component of the adhesive composition.

因此，以使該黏著賦予劑的添加量在0乃至100重量份的範圍內之值更佳、為0乃至50重量份的範圍內之值又更佳。Therefore, the value of the addition amount of the adhesion-imparting agent is preferably in the range of 0 to 100 parts by weight, more preferably in the range of 0 to 50 parts by weight.

又，本發明係關於含有至少2個的被接著物、與此等被接著物間設置的本發明之接著劑組成物所形成之接著層的層合物。Further, the present invention relates to a laminate of an adhesive layer comprising at least two binders and an adhesive composition of the present invention provided between the binders.

本發明藉由含有於第1被接著物上將本發明之接著劑組成物以旋轉塗佈進行塗佈並在50乃至300℃進行燒成以形成接著層的步驟、透過形成的接著層將第2被接著物接著至第1被接著物的步驟之方法，可得到被接著物之層合物。進一步，可含將層合物的被接著物層加工的步驟。In the present invention, the adhesive composition of the present invention is applied by spin coating on the first adherend, and is fired at 50 to 300 ° C to form an adhesive layer, and the formed adhesive layer is formed. 2 A method in which the substrate is followed by the step of the first substrate to obtain a substrate. Further, a step of processing the layer of the layer of the laminate may be included.

又，進而重複於第2被接著物上形成接著層之步驟、透過形成的接著層使第3被接著物接著於第2被接著物之步驟、及因應需要將經接著而得的被接著物層加工的步驟，亦可形成由複數被接著物及其間所形成的接著層所成之層合物。Further, the step of forming a subsequent layer on the second object to be repeated, the step of passing the formed subsequent layer to form the third object to be attached to the second object, and the subsequent article to be formed as needed The step of layer processing may also form a laminate of a plurality of substrates to be bonded and an adhesive layer formed therebetween.

在本發明，在半導體晶圓以旋轉塗佈塗佈的接著劑的厚度可為0.1μm以上200μm以下。厚度比0.1μm薄則不能貼合表面凹凸而在接著時有產生孔洞的可能性，比200μm厚則有接著層產生龜裂的可能性。更佳為接著層的厚度在1μm乃至50μm。In the present invention, the thickness of the adhesive applied by spin coating on the semiconductor wafer may be 0.1 μm or more and 200 μm or less. When the thickness is less than 0.1 μm, the surface unevenness cannot be bonded, and there is a possibility that a hole is formed in the subsequent case, and if it is thicker than 200 μm, there is a possibility that cracks may occur in the adhesive layer. More preferably, the thickness of the adhesive layer is from 1 μm to 50 μm.

[實施例][Examples]

以下，說明確認本發明接著劑組成物之特性的實施例。Hereinafter, examples of confirming the characteristics of the adhesive composition of the present invention will be described.

但本發明不限於該等實施例。However, the invention is not limited to the embodiments.

以下記載的合成例所得高分子化合物之GPC分析係使用下述裝置，並用下述測定條件。The GPC analysis of the polymer compound obtained in the synthesis example described below was carried out using the following apparatus, and the following measurement conditions were used.

裝置：一體型高速GPC系統HLC-8220GPC東曹股份公司製Device: Integrated high-speed GPC system HLC-8220GPC made by Tosoh Corporation

管柱：KF-G、KF804LColumn: KF-G, KF804L

管柱溫度：40℃Column temperature: 40 ° C

溶劑：THFSolvent: THF

流量：1.0mL/分鐘Flow rate: 1.0mL/min

標準試料：聚苯乙烯Standard sample: polystyrene

偵測器：R1Detector: R1

合成例1Synthesis Example 1

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氯二苯基-碸20.10g、2,2-雙(4-羥基苯基)六氟丙烷24.77g、碳酸鉀29.02g、N-甲基-2-吡咯烷酮369.50g。之後將燒瓶內進行氮取代後，加熱至160℃、進行20h反應。使合成的芳香族聚醚醚碸冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與1mol/l鹽酸之體積比為90：10之混合液30ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 24.10 g of 4,4'-dichlorodiphenyl-anthracene and 24.77 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. Potassium carbonate 29.02 g, N-methyl-2-pyrrolidone 369.50 g. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 1 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到本發明使用的芳香族聚醚醚碸(相當式(1-1))。使得到的芳香族聚醚進行GPC分析，以標準聚苯乙烯換算重量平均分子量為18600。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum dried at 85 ° C for 1 day to obtain an aromatic polyether ether oxime (equivalent formula (1-1)) used in the present invention. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 18,600.

合成例2Synthesis Example 2

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氯二苯基-碸68.20g、2,2-雙(4-羥基苯基)六氟丙烷84.06g、碳酸鉀103.68g、N-甲基-2-吡咯烷酮456.98g。之後將燒瓶內進行氮取代後，加熱至160℃、進行20h反應。之後滴下作為封端劑的4-氟苯三氟化物32.83g溶於N-甲基-2-吡咯烷酮160.48g的樣本，再進行20h攪拌。使合成的芳香族聚醚醚碸冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液100ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 4,4'-dichlorodiphenyl-anthracene 68.20 g, 2,2-bis(4-hydroxyphenyl)hexafluoropropane 84.06 g, 103.68 g of potassium carbonate and 456.98 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, 32.83 g of 4-fluorobenzene trifluoride as a blocking agent was dropped, and a sample of 160.48 g of N-methyl-2-pyrrolidone was added thereto, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 100 ml of a mixed solution of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到使本發明所使用的芳香族聚醚以取代基封端者。使得到的芳香族聚醚醚碸(相當式(1-1))進行GPC分析，以標準聚苯乙烯換算重量平均分子量為17000。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-1)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 17,000.

合成例3Synthesis Example 3

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氯二苯基-碸16.37g、tert-丁基對苯二酚9.97g、碳酸鉀24.90g、N-甲基-2-吡咯烷酮79.04g。之後將燒瓶內進行氮取代後，加熱至160℃、進行20h反應。之後滴下作為封端劑的4-氟苯三氟化物7.90g溶於N-甲基-2-吡咯烷酮28.94g的樣本，再進行20h攪拌。使合成的芳香族聚醚醚碸冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液30ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 16.37 g of 4,4'-dichlorodiphenyl-anthracene, 9.97 g of tert-butyl hydroquinone, and 24.90 g of potassium carbonate, N- were placed. Methyl-2-pyrrolidone 79.04 g. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, 7.90 g of 4-fluorobenzene trifluoride as a blocking agent was added dropwise to a sample of 28.94 g of N-methyl-2-pyrrolidone, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到使本發明所使用的芳香族聚醚以取代基封端者。使得到的芳香族聚醚醚碸(相當式(1-2))進行GPC分析，以標準聚苯乙烯換算重量平均分子量為14800。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-2)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 14,800.

合成例4Synthesis Example 4

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氯二苯基-碸13.64g、1,1-雙(4-羥基苯基)環己烷13.42g、碳酸鉀20.78g、N-甲基-2-吡咯烷酮81.23g。之後將燒瓶內進行氮取代後，加熱至160℃、進行20h反應。之後滴下使4-氟苯三氟化物6.55g溶於N-甲基-2-吡咯烷酮28.75g的樣本，再進行20h攪拌。使合成的芳香族聚醚醚碸冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液30ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 13.4 g of 4,4'-dichlorodiphenyl-anthracene and 13.42 g of 1,1-bis(4-hydroxyphenyl)cyclohexane were placed. 20.78 g of potassium carbonate and 81.23 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, a sample of 6.55 g of 4-fluorobenzene trifluoride dissolved in N-methyl-2-pyrrolidone (28.75 g) was added dropwise thereto, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到將本發明使用的芳香族聚醚以取代基封端者。使得到的芳香族聚醚醚碸(相當式(1-3))進行GPC分析，以標準聚苯乙烯換算重量平均分子量為14600。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a block in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-3)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 14,600.

合成例5Synthesis Example 5

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氯二苯基-碸13.64g、2,2-雙(4-羥基苯基)六氟丙烷8.41g、2,2-雙(4-羥基苯基)丙烷5.71g、碳酸鉀34.56g、N-甲基-2-吡咯烷酮83.44g。之後將燒瓶內進行氮取代後，加熱至160℃、進行20h反應。之後滴下使4-氟苯三氟化物6.56g溶於N-甲基-2-吡咯烷酮29.56g的樣本，再進行20h攪拌。使合成的芳香族聚醚醚碸冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液30ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 14.4 g of 4,4'-dichlorodiphenyl-anthracene and 8.41 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. 5.71 g of 2,2-bis(4-hydroxyphenyl)propane, 34.56 g of potassium carbonate, and 83.44 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, a sample of 6.56 g of 4-fluorobenzene trifluoride dissolved in N-methyl-2-pyrrolidone (29.56 g) was added dropwise thereto, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到使本發明所使用的芳香族聚醚以取代基封端者。使得到的芳香族聚醚醚碸(相當式(1-4))進行GPC分析，以標準聚苯乙烯換算重量平均分子量為17700。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-4)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 17,700.

合成例6Synthesis Example 6

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氯二苯基-碸13.64g、2,2-雙(4-羥基苯基)六氟丙烷8.41g、tert-丁基對苯二酚4.16g、碳酸鉀34.55g、N-甲基-2-吡咯烷酮78.95g。之後將燒瓶內進行氮取代後，加熱至160℃、進行20h反應。之後滴下使4-氟苯三氟化物6.56g溶於N-甲基-2-吡咯烷酮28.06g的樣本，再進行20h攪拌。使合成的芳香族聚醚醚碸冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液30ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 14.4 g of 4,4'-dichlorodiphenyl-anthracene and 8.41 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. Tert-butyl hydroquinone 4.16 g, potassium carbonate 34.55 g, and N-methyl-2-pyrrolidone 78.95 g. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, a sample of 6.56 g of 4-fluorobenzene trifluoride dissolved in N-methyl-2-pyrrolidone 28.06 g was added dropwise, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到使本發明所使用的芳香族聚醚以取代基封端者。使得到的芳香族聚醚醚碸(相當式(1-5))進行GPC分析，以標準聚苯乙烯換算之重量平均分子量為17300。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-5)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 17,300.

合成例7Synthesis Example 7

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氟二苯甲酮94.26g、tert-丁基對苯二酚44.88g、甲基對苯二酚33.52g、碳酸鉀82.10g、N-甲基-2-吡咯烷酮764.27g。之後將燒瓶內進行氮取代後，加熱至140℃並進行20h反應。使合成的芳香族聚醚醚酮冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液30ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 94.26 g of 4,4'-difluorobenzophenone, 44.88 g of tert-butyl hydroquinone, and 33.52 g of methyl hydroquinone were placed. 82.10 g of potassium carbonate and 764.27 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was subjected to nitrogen substitution, and then heated to 140 ° C and reacted for 20 hours. After cooling the synthesized aromatic polyetheretherketone to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到使本發明所使用的芳香族聚醚以取代基封端者。使得到的芳香族聚醚醚酮(相當式(1-6))進行GPC分析，以標準聚苯乙烯換算之重量平均分子量為15200。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyetheretherketone (equivalent formula (1-6)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 15,200.

合成例8Synthesis Example 8

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氯二苯基碸14.07g、1,1-雙(4-羥基苯基)六氟丙烷8.40g、1,1-雙(4-羥基苯基)環己烷6.71g、碳酸鉀20.75g、N-甲基-2-吡咯烷酮87.68g。之後將燒瓶內進行氮取代後，加熱至160℃、進行20h反應。使合成的芳香族聚醚醚碸冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液30ml混合。之後將混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 14.07 g of 4,4'-dichlorodiphenyl fluorene and 1.40 g of 1,1-bis(4-hydroxyphenyl)hexafluoropropane were placed. There were 6.71 g of 1-bis(4-hydroxyphenyl)cyclohexane, 20.75 g of potassium carbonate, and 87.68 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was poured into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到本發明使用的芳香族聚醚醚碸(相當式(1-7))。使得到的芳香族聚醚進行GPC分析，以標準聚苯乙烯換算之重量平均分子量為43000。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum dried at 85 ° C for 1 day to obtain an aromatic polyether ether oxime (equivalent formula (1-7)) used in the present invention. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 43,000.

合成例9Synthesis Example 9

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氟二苯甲酮74.19g、2,2-雙(4-羥基苯基)六氟丙烷94.14g、三甲基對苯二酚18.26g、碳酸鉀60.81g、N-甲基-2-吡咯烷酮742.22g。之後將燒瓶內進行氮取代後，加熱至140℃並進行20h反應。使合成的芳香族聚醚醚酮冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液30ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 74.19 g of 4,4'-difluorobenzophenone and 94.14 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. 18.26 g of methyl hydroquinone, 60.81 g of potassium carbonate, and 742.22 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was subjected to nitrogen substitution, and then heated to 140 ° C and reacted for 20 hours. After cooling the synthesized aromatic polyetheretherketone to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到本發明使用的芳香族聚醚醚酮(相當式(1-8))。使得到的芳香族聚醚進行GPC分析，以標準聚苯乙烯換算之重量平均分子量為24700。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum dried at 85 ° C for 1 day to obtain an aromatic polyether ether ketone (equivalent formula (1-8)) used in the present invention. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 24,700.

合成例10Synthesis Example 10

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氟二苯甲酮40.42g、2,2-雙(4-羥基苯基)六氟丙烷73.97g、2,2-雙(4-羥基-3,5-二羥基甲基苯基)丙烷4.03g、碳酸鉀32.01g、N-甲基-2-吡咯烷酮752.16g。之後將燒瓶內進行氮取代後，加熱至140℃並進行20h反應。使合成的芳香族聚醚醚酮冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液30ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 40.42 g of 4,4'-difluorobenzophenone and 73.97 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. 4-(4-hydroxy-3,5-dihydroxymethylphenyl)propane 4.03 g, potassium carbonate 32.01 g, and N-methyl-2-pyrrolidone 752.16 g. Thereafter, the inside of the flask was subjected to nitrogen substitution, and then heated to 140 ° C and reacted for 20 hours. After cooling the synthesized aromatic polyetheretherketone to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到本發明使用的芳香族聚醚醚酮(相當式(1-9))。使得到的芳香族聚醚進行GPC分析，以標準聚苯乙烯換算之重量平均分子量為19000。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum dried at 85 ° C for 1 day to obtain an aromatic polyether ether ketone (equivalent formula (1-9)) used in the present invention. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 19,000.

比較合成例1Comparative Synthesis Example 1

在具備攪拌裝置、迴流器、溫度計、滴下槽的燒瓶，置入4,4’-二氯二苯基-碸15.00g、2,2-雙(4-羥基苯基)丙烷12.56g、碳酸鉀8.37g、N-甲基-2-吡咯烷酮82.61g，之後將燒瓶內進行氮取代後，加熱至160℃、進行20h反應。使合成的芳香族聚醚醚碸冷卻至室溫後，過濾後回收濾液，與N-甲基-2-吡咯烷酮與2mol/l鹽酸之體積比為90：10之混合液30ml混合。之後使該混合溶液投入甲醇進行再沈澱精製。In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 15.00 g of 4,4'-dichlorodiphenyl-fluorene, 12.56 g of 2,2-bis(4-hydroxyphenyl)propane, and potassium carbonate were placed. 8.37 g of 82.61 g of N-methyl-2-pyrrolidone, and then the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

之後將得到的沈澱以甲醇與水洗淨，在85℃進行1日真空乾燥，得到比較例1使用的芳香族聚醚醚碸(相當式(2-1))。使得到的芳香族聚醚進行GPC分析，以標準聚苯乙烯換算之重量平均分子量為16700。Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain an aromatic polyether ether oxime (Comparative Formula (2-1)) used in Comparative Example 1. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 16,700.

【化9】【化9】

比較合成例2Comparative Synthesis Example 2

準備以市售品合成的丙烯酸樹脂之聚甲基丙烯酸甲酯(和光純藥工業股份公司製)。Polymethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) of an acrylic resin synthesized in a commercial product was prepared.

(溶劑溶解性評估)(solvent solubility evaluation)

相對合成例1乃至10及比較合成例1所得到的芳香族聚醚及比較合成例2的丙烯酸樹脂5質量份，將作為各溶劑的(1)丙二醇單甲基醚(PGME)、(2)丙二醇單甲基醚乙酸酯(PGMEA)、(3)乳酸乙酯(EL)、(4)環己酮(Cy)、(5)N-甲基-2-吡咯烷酮(NMP)、(6)二甲基乙醯醯胺(DMAC)、(7)4-甲基2-戊酮(MIBK)、(8)5-甲基-2-己酮(MIAK)、(9)乙醯乙酸乙酯(EAA)、(10)γ丁基內酯(GBL)、(11)環戊酮(Cp)以95質量份之比例加入，評估溶解性。With respect to the aromatic polyether obtained in Synthesis Example 1 to 10 and Comparative Synthesis Example 1 and 5 parts by mass of the acrylic resin of Comparative Synthesis Example 2, (1) propylene glycol monomethyl ether (PGME) and (2) were used as the respective solvents. Propylene glycol monomethyl ether acetate (PGMEA), (3) ethyl lactate (EL), (4) cyclohexanone (Cy), (5) N-methyl-2-pyrrolidone (NMP), (6) Dimethylacetamide (DMAC), (7) 4-methyl 2-pentanone (MIBK), (8) 5-methyl-2-hexanone (MIAK), (9) ethyl acetate (EAA), (10) γ-butyl lactone (GBL), and (11) cyclopentanone (Cp) were added in a ratio of 95 parts by mass to evaluate solubility.

結果如表1。○為溶解、△為微溶、×為不溶。The results are shown in Table 1. ○ is dissolved, Δ is slightly soluble, and × is insoluble.

由合成例1乃至10得到的芳香族聚醚與作為比較合成例2使用的丙烯酸樹脂具同樣溶解性，而比比較合成例1得到的聚碸具更高溶解性。The aromatic polyether obtained in Synthesis Example 1 to 10 had the same solubility as the acrylic resin used in Comparative Synthesis Example 2, and was more soluble than the polyhydrazine obtained in Comparative Synthesis Example 1.

(耐熱性評估)(heat resistance evaluation)

關於由合成例1乃至10及比較合成例1得到的芳香族聚醚以及作為比較合成例2使用的聚甲基丙烯酸甲酯的耐熱性使用TG-DTA(BrukerAXS股份公司製、TG/DTA2010SR)以10℃/分鐘昇溫產生減少5質量%的溫度來評估。結果如表2。TG-DTA (manufactured by Bruker AXS Co., Ltd., TG/DTA2010SR) was used for the heat resistance of the aromatic polyether obtained in Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 and the polymethyl methacrylate used in Comparative Synthesis Example 2 The temperature rise of 10 ° C / min produced a temperature reduction of 5% by mass. The results are shown in Table 2.

本發明所使用的合成例1乃至10之芳香族聚醚與比較合成例1的芳香族聚醚同樣，減少5質量%重量的溫度皆在450℃以上，與比較合成例2的丙烯酸樹脂比較具高耐熱性。The aromatic polyether of Synthesis Example 1 to 10 used in the present invention is similar to the aromatic polyether of Comparative Synthesis Example 1 in that the temperature at which the mass by 5% by weight is reduced to 450 ° C or higher, which is comparable to the acrylic resin of Comparative Synthesis Example 2. High heat resistance.

(接著劑組成物之調整)(adjustment of the composition of the adhesive)

使用由合成例1乃至10及比較合成例1得到的芳香族聚醚以及比較合成例2的丙烯酸樹脂，各自使用下述組成調製接著劑組成物。The aromatic polyether obtained in Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 and the acrylic resin in Comparative Synthesis Example 2 were used, and each of the following compositions was used to prepare an adhesive composition.

實施例1Example 1

將由合成例1得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 1 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

實施例2Example 2

將合成例2所得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 2 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

實施例3Example 3

將合成例3所得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 3 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

實施例4Example 4

將合成例4所得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 4 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

實施例5Example 5

將合成例5所得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 5 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

實施例6Example 6

將合成例6所得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 6 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

實施例7Example 7

將合成例7所得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 7 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

實施例8Example 8

將合成例8所得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 8 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

實施例9Example 9

將合成例9所得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 9 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

實施例10Example 10

將合成例10所得到的芳香族聚醚溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The aromatic polyether obtained in Synthesis Example 10 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

實施例11Example 11

將相對由合成例10得到的芳香族聚醚為5質量%之Cymel303(交聯劑)溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The Cymel 303 (crosslinking agent) having a 5% by mass of the aromatic polyether obtained in Synthesis Example 10 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

實施例12Example 12

將相對合成例7所得到的芳香族聚醚為5質量%之Pine crystal KE100(可塑劑、荒川化學工業股份公司製、商品名、成分為酯化松香樹脂)溶於環己酮中，調製含有20質量%固形分的接著劑組成物。Pine crystal KE100 (plasticizer, manufactured by Arakawa Chemical Industries Co., Ltd., trade name, and esterified rosin resin) was dissolved in cyclohexanone in an amount of 5% by mass of the aromatic polyether obtained in Synthesis Example 7. 20% by mass of the solid component of the adhesive composition.

比較例1Comparative example 1

將由比較合成例1所得到的芳香族聚醚溶於N-甲基-2-吡咯烷酮中，調製含有10質量%固形分的接著劑組成物。The aromatic polyether obtained in Comparative Synthesis Example 1 was dissolved in N - methyl - 2-pyrrolidone to prepare an adhesive composition containing 10% by mass of a solid content.

比較例2Comparative example 2

將比較合成例2的聚甲基丙烯酸甲酯溶於環己酮中，調製含有20質量%固形分的接著劑組成物。The polymethyl methacrylate of Comparative Example 2 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

(塗佈性評估)(coating evaluation)

將實施例1乃至12、比較例1及比較例2所得到的接著劑組成物各自以塗佈條件1000rpm、30秒鐘在矽晶圓上進行旋轉塗佈，對各自在100℃及250℃各自進行2分鐘烘烤而形成的膜進行評估。結果如表3所示。Each of the adhesive compositions obtained in Examples 1 to 12, Comparative Example 1 and Comparative Example 2 was spin-coated on a ruthenium wafer at a coating condition of 1000 rpm for 30 seconds, and each was applied at 100 ° C and 250 ° C for each. The film formed by baking for 2 minutes was evaluated. The results are shown in Table 3.

相對於在比較例1調整的接著劑組成物產生塗佈不良、且無法形成均勻的膜，在本發明之實施例1乃至12調整的芳香族聚醚之接著劑組成物與作為比較合成例2使用的丙烯酸樹脂之接著劑組成物皆可形成1μm以上之均勻的膜。The adhesive composition of the aromatic polyether adjusted in Examples 1 to 12 of the present invention was compared with the adhesive composition adjusted in Comparative Example 1, and a coating film was not formed, and a uniform film could not be formed. The adhesive composition of the acrylic resin to be used can form a uniform film of 1 μm or more.

(接著性評估)(subsequent assessment)

將實施例1乃至12、比較例1及2所得到的接著劑組成物在矽晶圓上以1000rpm、30秒鐘的塗佈條件進行塗佈後，在100℃及250℃各自進行2分鐘的烘烤而在矽晶圓上各自形成塗佈膜。將該矽晶圓切取2cm方形，在270℃的加熱板上、預先靜置的玻璃晶圓上使塗佈面向下放置而由上進行壓黏，並評估接著性。結果如表4所示。將由玻璃晶圓面所見狀態而無孔洞(孔)被接著的場合評估為良好。The adhesive compositions obtained in Examples 1 to 12 and Comparative Examples 1 and 2 were applied on a ruthenium wafer at a coating condition of 1000 rpm and 30 seconds, and then each was carried out at 100 ° C and 250 ° C for 2 minutes. Baking and forming a coating film on each of the germanium wafers. The tantalum wafer was cut into a 2 cm square, and the coating was placed face down on a preheated glass wafer on a hot plate of 270 ° C to be pressure-bonded from above, and the adhesion was evaluated. The results are shown in Table 4. It was evaluated that the state of the glass wafer surface was observed and no holes (holes) were followed.

相對於比較例1所得到的接著劑組成物產生接著不良、且無法均勻地接著，本發明之實施例1乃至12的接著劑組成物、比較例2的接著劑組成物具有良好的接著性。The adhesive composition obtained in Comparative Example 1 was defective in adhesion and could not be uniformly followed. The adhesive compositions of Examples 1 to 12 of the present invention and the adhesive composition of Comparative Example 2 had good adhesion.

(接著力評估樣本的製作)(Follow the force evaluation sample production)

將合成例7及合成例9所調整的芳香族聚醚、以及比較合成例2的丙烯酸樹脂之接著力評估樣本用下述方法製作。The adhesion test samples of the aromatic polyether adjusted in Synthesis Example 7 and Synthesis Example 9 and the acrylic resin of Comparative Synthesis Example 2 were produced by the following method.

實施例13Example 13

使合成例7所得到的芳香族聚醚溶於環己酮中，調製含有27質量%固形分的接著劑組成物。使得到接著劑組成物以塗佈條件1500rpm、60秒鐘在4吋矽晶圓上進行旋轉塗佈，並各自在100℃及230℃進行2分鐘烘烤，形成膜厚為5.5μm之膜。之後，使用黏合裝置(Ayumi工業股份公司製、VJ-300)，在真空度10Pa以下、溫度250℃、黏合壓力300Kg之條件下將矽晶圓透過膜與4吋玻璃晶圓接著。將該晶圓以切割裝置(DISCO股份公司製、DAD321)切斷為1cm方形，以製做樣本。The aromatic polyether obtained in Synthesis Example 7 was dissolved in cyclohexanone to prepare an adhesive composition containing 27% by mass of a solid component. The adhesive composition was spin-coated on a 4 Å wafer at a coating condition of 1500 rpm for 60 seconds, and each was baked at 100 ° C and 230 ° C for 2 minutes to form a film having a film thickness of 5.5 μm. Thereafter, using a bonding apparatus (manufactured by Ayumi Industries Co., Ltd., VJ-300), the ruthenium wafer permeable film was bonded to a 4 Å glass wafer under the conditions of a vacuum of 10 Pa or less, a temperature of 250 ° C, and a bonding pressure of 300 kg. The wafer was cut into a 1 cm square by a cutting device (manufactured by DISCO Corporation, DAD321) to prepare a sample.

實施例14Example 14

將合成例9所得到的芳香族聚醚溶於環己酮中，調製含有27質量%固形分的接著劑組成物。使得到接著劑組成物以塗佈條件1500rpm、60秒鐘在4吋矽晶圓上進行旋轉塗佈，各自在100℃及230℃進行2分鐘烘烤，形成膜厚為4.9μm之膜。之後，使用黏合裝置(Ayumi工業股份公司製、VJ-300)，在真空度10Pa以下、溫度270℃、黏合壓力300Kg之條件下使矽晶圓透過膜與4吋玻璃晶圓接著。將該晶圓以切割裝置(DISCO股份公司製、DAD321)切斷為1cm方形，製作樣本。The aromatic polyether obtained in Synthesis Example 9 was dissolved in cyclohexanone to prepare an adhesive composition containing 27% by mass of a solid component. The adhesive composition was spin-coated on a 4 Å wafer at a coating condition of 1500 rpm for 60 seconds, and baked at 100 ° C and 230 ° C for 2 minutes to form a film having a film thickness of 4.9 μm. Thereafter, using a bonding apparatus (manufactured by Ayumi Industries Co., Ltd., VJ-300), the ruthenium wafer permeable film was bonded to the 4 Å glass wafer under the conditions of a vacuum of 10 Pa or less, a temperature of 270 ° C, and a bonding pressure of 300 kg. The wafer was cut into a 1 cm square by a cutting device (manufactured by DISCO Corporation, DAD321) to prepare a sample.

比較例3Comparative example 3

使比較合成例2的丙烯酸樹脂溶於環己酮中，調製含有20質量%固形分的接著劑組成物。使得到接著劑組成物以塗佈條件1300rpm、60秒鐘在4吋矽晶圓上進行旋轉塗佈，各自在100℃及200℃進行2分鐘的烘烤，形成膜厚為5.0μm之膜。之後，使用黏合裝置(Ayumi工業股份公司製、VJ-300)，在真空度10Pa以下、溫度270℃、黏合壓力400Kg之條件下使矽晶圓透過膜與4吋玻璃晶圓接著。使該晶圓以切割裝置(股份公司DISCO製、DAD321)切斷為1cm方形，以製作樣本。The acrylic resin of Comparative Synthesis Example 2 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content. The adhesive composition was spin-coated on a 4 Å wafer at a coating condition of 1300 rpm for 60 seconds, and baked at 100 ° C and 200 ° C for 2 minutes to form a film having a film thickness of 5.0 μm. Thereafter, using a bonding apparatus (manufactured by Ayumi Industries Co., Ltd., VJ-300), the ruthenium wafer permeable film was bonded to the 4 Å glass wafer under the conditions of a vacuum of 10 Pa or less, a temperature of 270 ° C, and a bonding pressure of 400 Kg. The wafer was cut into a 1 cm square by a cutting device (manufactured by the company DISCO, DAD321) to prepare a sample.

(接著力評估1)(Continue to force evaluation 1)

在實施例13及實施例14以及比較例3所得到的接著力評估樣本之兩面塗佈ARALDITE2014(Huntsman Advanced Materials股份公司製、商品名)，在接著力(剪斷)測定用專用夾具使兩面接著後，以萬能材料試驗機(股份公司島津製作所製、萬能材料試驗機AGS-100NX)評估接著力(剪斷)。接著力以1mm/分鐘之拉伸速度進行測定。結果如表5所示。ARALDITE 2014 (manufactured by Huntsman Advanced Materials Co., Ltd., trade name) was applied to both surfaces of the adhesion evaluation samples obtained in Example 13 and Example 14 and Comparative Example 3, and the special jig for the measurement of the force (shear) was applied to both sides. After that, the adhesion force (cutting) was evaluated by a universal material testing machine (manufactured by Shimadzu Corporation, a universal material testing machine AGS-100NX). Then, the force was measured at a tensile speed of 1 mm/min. The results are shown in Table 5.

表5中，接著力之值在1000N以上係指上述接著力測定機的測定界限以上。In Table 5, the value of the subsequent force is 1000 N or more and is equal to or higher than the measurement limit of the above-described adhesion measuring machine.

在實施例13及實施例14得到的樣本比在比較例3得到的樣本具有高接著力。The samples obtained in Examples 13 and 14 had higher adhesion than the samples obtained in Comparative Example 3.

(接著力評估2)(Continue to force evaluation 2)

將實施例13及實施例14以及比較例3所得到的接著力評估樣本置於350℃的加熱板上1小時，在靜置後樣本之兩面塗佈ARALDITE2014(Huntsman Advanced Materials股份公司製、商品名)，在接著剪斷力測定用專用夾具將兩面接著後，以萬能材料試驗機(股份公司島津製作所製、萬能材料試驗機AGS-100NX)評估接著力(剪斷)。接著力以1mm/分鐘的拉伸速度進行測定。結果如表6所示。The adhesion evaluation samples obtained in Example 13 and Example 14 and Comparative Example 3 were placed on a hot plate at 350 ° C for 1 hour, and ARALDITE 2014 (manufactured by Huntsman Advanced Materials Co., Ltd., trade name) was applied to both sides of the sample after standing. After the two sides of the cutting force measurement tester were used, the adhesive force (shearing) was evaluated by a universal material testing machine (manufactured by Shimadzu Corporation, a universal material testing machine AGS-100NX). Then, the force was measured at a tensile speed of 1 mm/min. The results are shown in Table 6.

表6中，接著力之值在1000N以上係指在上述接著力測定機的測定界限以上。In Table 6, the value of the subsequent force is 1000 N or more, which means that it is more than the measurement limit of the above-mentioned adhesion measuring machine.

對於在實施例13及實施例14得到的樣本維持高接著力，而比較例3得到的樣本接著力降低。The high adhesion was maintained for the samples obtained in Example 13 and Example 14, and the sample obtained in Comparative Example 3 had a lower adhesion force.

[產業上之利用性][Industrial use]

可做成易溶於種種有機溶劑而塗佈性佳、可形成足夠厚度的接著層，且該接著層在金屬凸塊接合、CVD、離子擴散步驟等之高溫製程中熱重量減少極少、密著性良好的高耐熱性接著劑組成物。It can be made into an adhesive layer which is easily soluble in various organic solvents and has good coatability and can form a sufficient thickness, and the adhesive layer has little thermal weight reduction and adhesion in a high-temperature process such as metal bump bonding, CVD, ion diffusion step and the like. A highly heat resistant adhesive composition having good properties.

Claims (16)

一種接著劑組成物，其特徵係含有含以下述式(1)： (式中，X為磺醯基或羰基，Ar1及Ar2各自為碳原子數6乃至30之伸芳基，T1為氟伸烷基、環狀伸烷基、具有碳原子數1乃至10之烷基之伸芳基、或可具有取代基的伸芳基與氟伸烷基或者環狀伸烷基之組合)所表示之單元構造的聚合物與溶劑，且由該組成物除去溶劑的固形分，相對接著劑組成物，為0.1乃至80質量%之比例。 An adhesive composition characterized by containing the following formula (1): (wherein X is a sulfonyl group or a carbonyl group, each of Ar 1 and Ar 2 is an exoaryl group having 6 to 30 carbon atoms, and T 1 is a fluoroalkyl group, a cyclic alkyl group, having a carbon number of 1 or even a polymer and a solvent of a unit structure represented by an alkyl group of 10, or a combination of a aryl group which may have a substituent and a fluorine alkyl group or a cyclic alkyl group, and the solvent is removed from the composition The solid content is a ratio of 0.1 to 80% by mass relative to the composition of the adhesive. 如請求項1記載之接著劑組成物，其中，前述伸芳基為伸苯基、伸萘基、或伸蒽基。 The adhesive composition according to claim 1, wherein the exoaryl group is a phenylene group, a naphthyl group, or a fluorenyl group. 如請求項1或請求項2記載之接著劑組成物，其中，前述聚合物為具有1種類單元構造之單獨聚合物。 The adhesive composition according to claim 1 or claim 2, wherein the polymer is a single polymer having one type of unit structure. 如請求項1或請求項2記載之接著劑組成物，其中，前述聚合物為具有至少2種類單元構造之共聚合物。 The adhesive composition according to claim 1 or claim 2, wherein the polymer is a copolymer having at least two types of unit structures. 如請求項1或請求項2記載之接著劑組成物，其特徵係含有含前述Ar1及Ar2各自係下述式(2)： (式中，R1為碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、羥基、烯丙基、烯丙氧基、胺基、氰基、硝基、醯基、醯基氧基、羧基、具有第3級碳構造的基、環狀烷基、或彼等之組合，n1為0乃至4之整數)所表示之基的上述式(1)所表示之單元構造的聚合物。 The adhesive composition according to claim 1 or claim 2, characterized in that each of Ar 1 and Ar 2 is contained in the following formula (2): (wherein R 1 is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, a nitro group or a fluorenyl group; a unit represented by the above formula (1), which is a group represented by a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and n1 is an integer of 0 to 4) Constructed polymer. 如請求項1或請求項2記載之接著劑組成物，其係含有含前述T1為下述式(3)所表示之基的上述式(1)所表示之單元構造、前述T1為下述式(4)所表示之基的上述式(1)所表示之單元構造、或彼等之單元構造的組合的聚合物， (式中，R2、R3及R4各自為碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、羥基、烯丙基、烯丙氧基、胺基、氰基、硝基、醯基、醯基氧基、羧基、具有第3級碳構造的基、環狀烷基、或彼等之組合，n2、n3及n4各自為0乃至4之整數，T2為氟伸烷基、環狀伸烷基、或此等之組合)。 The requested item described in item 1 or 2 requests the adhesive composition, which system contains containing T 1 is the cell structure (1) represented by the above formula (3) the group represented by the following formula, T 1 is the next a polymer having a unit structure represented by the above formula (1) represented by the formula (4) or a combination of unit structures thereof, (wherein R 2 , R 3 and R 4 are each an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, and a cyanogen group; a group, a nitro group, a fluorenyl group, a decyloxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and each of n2, n3 and n4 is an integer of 0 to 4, T 2 It is a fluoroalkyl group, a cyclic alkyl group, or a combination thereof. 如請求項6記載之接著劑組成物，其中，前述式(3)中，R2為第三丁基，且n2為1乃至4之整數。 The adhesive composition according to claim 6, wherein, in the above formula (3), R 2 is a third butyl group, and n 2 is an integer of 1 to 4. 如請求項1或請求項2記載之接著劑組成物，其中除式(1)所表示之單位構造外，再含有含式(5)： (式中，X為磺醯基或羰基，Ar3及Ar4各自為碳原子數6乃至30之伸芳基，T3為伸烷基、磺醯基、羰基、碳原子數6乃至30之伸芳基、或此等之組合)所表示之單元構造的共聚合物。 The adhesive composition according to claim 1 or claim 2, which further comprises the formula (5) in addition to the unit structure represented by the formula (1): (wherein X is a sulfonyl group or a carbonyl group, each of Ar 3 and Ar 4 is an exoaryl group having 6 to 30 carbon atoms, and T 3 is an alkylene group, a sulfonyl group, a carbonyl group, or a carbon number of 6 or 30. A copolymer of a unit structure represented by an aryl group or a combination thereof. 如請求項8記載之接著劑組成物，其中，前述伸芳基為伸苯基、伸萘基、或伸蒽基。 The adhesive composition according to claim 8, wherein the exoaryl group is a phenylene group, a naphthyl group, or a fluorenyl group. 如請求項8記載之接著劑組成物，其中，前述T3係式(6)： (式中，R5及R6各自為碳原子數1乃至10之烷基、碳原子數1乃至4之氟烷基、羥基、烯丙基、烯丙氧基、胺基、氰基、硝基、醯基、醯基氧基、羧基、具有第3級碳構造的基、環狀烷基、或彼等之組合，n5及n6各自為0乃至4之整數，T4為伸烷基、磺醯基、羰基、碳原子數6 乃至30之伸芳基、或此等之組合)所表示之基。 The adhesive composition according to claim 8, wherein the T 3 formula (6): (wherein R 5 and R 6 are each an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, and a nitrate a group, a mercapto group, a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, each of n5 and n6 is an integer of 0 to 4, and T 4 is an alkylene group, a group represented by a sulfonyl group, a carbonyl group, a aryl group having 6 or 30 carbon atoms, or a combination thereof. 如請求項1或請求項2記載之接著劑組成物，其中，前述具有第3級碳構造的基為第三丁基。 The adhesive composition according to claim 1 or claim 2, wherein the group having the third-order carbon structure is a third butyl group. 如請求項1或請求項2記載之接著劑組成物，其中，前述聚合物之重量平均分子量為500乃至5000000。 The adhesive composition according to claim 1 or claim 2, wherein the polymer has a weight average molecular weight of 500 to 5,000,000. 如請求項1或請求項2記載之接著劑組成物，其中再含有交聯劑。 The adhesive composition according to claim 1 or claim 2, which further contains a crosslinking agent. 如請求項1或請求項2記載之接著劑組成物，其具有0.001乃至5000Pa．s之黏度。 The adhesive composition as claimed in claim 1 or claim 2, which has a 0.001 to 5000 Pa. s viscosity. 一種層合物，其特徵係含有至少2個的被接著物、與在該被接著物間所設置的由請求項1或請求項2記載之接著劑組成物所形成的0.1μm乃至200μm之接著層。 A laminate comprising at least two adherends, and 0.1 μm or even 200 μm formed of the adhesive composition described in claim 1 or claim 2 disposed between the substrates Floor. 如請求項15記載之層合物，其中，前述被接著物各自係選自矽基板、玻璃基板、樹脂基板、或陶瓷基板所成之組群。 The laminate according to claim 15, wherein each of the substrates to be bonded is selected from the group consisting of a ruthenium substrate, a glass substrate, a resin substrate, or a ceramic substrate.
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