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TW202436454A - Adhesive film, temporary fixing material, hardened material, laminate, and method for manufacturing electronic component - Google Patents

Adhesive film, temporary fixing material, hardened material, laminate, and method for manufacturing electronic component Download PDF

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Publication number
TW202436454A
TW202436454A TW113101756A TW113101756A TW202436454A TW 202436454 A TW202436454 A TW 202436454A TW 113101756 A TW113101756 A TW 113101756A TW 113101756 A TW113101756 A TW 113101756A TW 202436454 A TW202436454 A TW 202436454A
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Taiwan
Prior art keywords
light
wavelength
temporary fixing
fixing material
adhesive
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TW113101756A
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Chinese (zh)
Inventor
大同和泉
岡山久敏
髙橋駿夫
七里徳重
林聡史
星野文香
坂本雄治
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日商積水化學工業股份有限公司
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Publication of TW202436454A publication Critical patent/TW202436454A/en

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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides an adhesive film that allows for efficient removal of a support body even when irradiated with low-energy laser light, and also has excellent adherend removability even when high-temperature processing is performed. The present invention is also able to provide a cured product of the adhesive film. The present invention furthermore provides a laminate comprising a support body, the adhesive film, and a semiconductor, in the stated order. In addition, the present invention provides a method of producing an electronic component using the laminate and comprising a step that allows for efficient removal of a support body even when irradiated with low-energy laser light, and a step making it easy to remove an adherend even when high-temperature processing is performed. The present invention also provides a temporary fixing material that has excellent anti-laser processing performance and allows for efficient removal of a support body even when irradiated with low-energy laser light after curing. The present invention additionally provides a cured product of the temporary fixing material. The present invention furthermore provides a laminate comprising the cured product. In addition, the present invention provides a method of producing an electronic component including a step that allows for efficient removal of a support body even when irradiated with low-energy laser light. The present invention is an adhesive film comprising an adhesive layer containing a curable adhesive, wherein: the curable adhesive is a photocurable adhesive; the adhesive layer, after being irradiated with light in the wavelength 405 nm so as to reach a cumulative light intensity of 20000 mJ/cm2, has a gel fraction of 65 mass% or higher, and the adhesive layer, after being irradiated with light in the wavelength 405 nm so as to reach a cumulative light intensity of 20000 mJ/cm2, has an extinction coefficient, to light in the wavelength 308 nm, of 1.0 * 10-4 or higher.

Description

接著膜、暫時固定材、硬化物、積層體、及電子零件之製造方法Adhesive film, temporary fixing material, hardened material, laminate, and method for manufacturing electronic component

本發明係關於一種接著膜。又，本發明係關於一種該接著膜之硬化物。進而，本發明係關於一種具有該接著膜之積層體。並且，本發明係關於一種使用該積層體之電子零件之製造方法。 又，本發明係關於一種暫時固定材。又，本發明係關於一種該暫時固定材之硬化物。進而，本發明係關於一種具有該硬化物之積層體。並且，本發明係關於一種電子零件之製造方法。 The present invention relates to a bonding film. Furthermore, the present invention relates to a cured product of the bonding film. Furthermore, the present invention relates to a laminate having the bonding film. Furthermore, the present invention relates to a method for manufacturing an electronic component using the laminate. Furthermore, the present invention relates to a temporary fixing material. Furthermore, the present invention relates to a cured product of the temporary fixing material. Furthermore, the present invention relates to a laminate having the cured product. Furthermore, the present invention relates to a method for manufacturing an electronic component.

於半導體等電子零件之加工時，為了使電子零件之操作容易且不會破損，經由黏著劑組合物或由黏著劑組合物構成之暫時固定材將電子零件接著於支持體而暫時固定，或將具有黏著劑層之帶狀之暫時固定材或黏著膜等接著膜貼附接著於電子零件以保護該電子零件。例如，於將自高純度之矽單晶等切取之厚膜晶圓研削至規定厚度而製成薄膜晶圓之情形時，經由黏著劑組合物或暫時固定材將厚膜晶圓接著於支持體。When processing electronic parts such as semiconductors, in order to make the electronic parts easy to handle and not to damage, the electronic parts are temporarily fixed to a support body through an adhesive composition or a temporary fixing material composed of an adhesive composition, or a temporary fixing material in the form of a strip with an adhesive layer or an adhesive film is attached to the electronic parts to protect the electronic parts. For example, when a thick film wafer cut from a high-purity silicon single crystal is ground to a specified thickness to produce a thin film wafer, the thick film wafer is connected to a support body through an adhesive composition or a temporary fixing material.

對如此用於電子零件之黏著劑組合物或黏著膜、用於電子零件之暫時固定之暫時固定材，要求於加工步驟中僅可牢固地固定電子零件之高接著性，以及於步驟結束後能夠不損傷電子零件而將其剝離（以下，亦稱為「高接著易剝離」）。 作為高接著易剝離之實現手段，例如於專利文獻1中揭示有如下黏著片，其使用於聚合物之側鏈或主鏈鍵結有具有放射線聚合性官能基之多官能性單體或低聚物之黏著劑。藉由具有放射線聚合性官能基而藉由紫外線照射使聚合物硬化，利用上述情況，剝離時能夠藉由照射紫外線而使黏著力降低，從而能夠無糊劑殘留地剝離。 [先前技術文獻] [專利文獻] For such adhesive compositions or adhesive films used for electronic components, and temporary fixing materials used for temporary fixing of electronic components, it is required to have high adhesion that can firmly fix the electronic components during the processing steps, and to be able to peel off the electronic components without damaging them after the steps are completed (hereinafter also referred to as "high adhesion and easy peeling"). As a means of realizing high adhesion and easy peeling, for example, Patent Document 1 discloses an adhesive sheet used for an adhesive in which a multifunctional monomer or oligomer having a radiation-polymerizable functional group is bonded to the side chain or main chain of a polymer. By having a radiation polymerizable functional group and curing the polymer by ultraviolet irradiation, the above situation can be utilized to reduce the adhesive force by ultraviolet irradiation during peeling, thereby enabling peeling without leaving any paste residue. [Prior art literature] [Patent literature]

專利文獻1：日本特開平5-32946號公報Patent document 1: Japanese Patent Application Publication No. 5-32946

[發明所欲解決之課題][The problem that the invention wants to solve]

近年來，為了應對半導體之高積體化，採用藉由支持體與暫時固定材或接著膜支持較薄之晶圓來製造半導體之TBDB（Temporary bonding/de-bonding）製程。存在於TBDB製程中，包括對支持體之整個表面照射雷射光而將支持體剝離之步驟的情形，作為所照射之雷射光，使用固體雷射光、氣體雷射光等各種雷射光，為了促進光分解，使用紫外區域之波長之雷射光。其中，使用波長308 nm以上355 nm以下之準分子雷射光之情況亦較多。In recent years, in order to cope with the high integration of semiconductors, the TBDB (Temporary bonding/de-bonding) process is used to manufacture semiconductors by supporting thin wafers with a support and a temporary fixing material or bonding film. In the TBDB process, there is a step of irradiating the entire surface of the support with laser light to peel off the support. As the irradiated laser light, various laser lights such as solid laser light and gas laser light are used. In order to promote photolysis, laser light with a wavelength in the ultraviolet region is used. Among them, excimer laser light with a wavelength of more than 308 nm and less than 355 nm is also used more often.

然而，於使用先前之黏著膜等接著膜或帶狀之暫時固定材等暫時固定材並藉由照射雷射光將支持體剝離之情形時，若長時間持續照射能夠將支持體剝離之雷射光，則有時會導致雷射光照射裝置之裝置能力及加工能力降低，或者接著膜或暫時固定材碳化、支持體損傷、接著膜或暫時固定材及支持體受到污染、以及支持體之剝離性能惡化等所伴隨之電子零件的製造品質降低。However, when using a bonding film such as an adhesive film or a temporary fixing material such as a tape and peeling the support by irradiating laser light, if the laser light capable of peeling the support is continuously irradiated for a long time, it may sometimes lead to a decrease in the device capacity and processing capacity of the laser light irradiation device, or carbonization of the bonding film or the temporary fixing material, damage to the support, contamination of the bonding film or the temporary fixing material and the support, and deterioration of the peeling performance of the support, resulting in a decrease in the manufacturing quality of electronic parts.

又，於半導體之製造中，有時藉由熱壓接接合（TCB）將半導體集成於基盤，故要求於實施加熱處理或伴有發熱之處理之高溫加工處理後容易將黏著膜自被黏著體剝離。然而，先前之接著膜於高溫加工處理中會產生與被黏著體之接著亢進，剝離時黏著力不會充分降低，有時會產生糊劑殘留。In addition, in the manufacture of semiconductors, semiconductors are sometimes integrated onto substrates by thermal compression bonding (TCB), so it is required that the adhesive film can be easily peeled off from the adherend after a high-temperature process such as heat treatment or a process that generates heat. However, the adhesive film previously produced an excessive adhesion to the adherend during the high-temperature process, and the adhesive force was not sufficiently reduced during the peeling process, and sometimes a paste residue was produced.

本發明之目的在於提供一種接著膜，其即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離，進而，即便於進行高溫加工處理之情形時，對被黏著體之剝離性亦優異。又，本發明之目的在於提供一種該接著膜之硬化物。進而，本發明之目的在於提供一種依序具有支持體、該接著膜、及半導體之積層體。進而，本發明之目的在於提供一種電子零件之製造方法，其具有：使用該積層體，即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離之步驟；及即便於進行高溫加工處理之情形時，亦能夠容易地將被黏著體剝離之步驟。 又，本發明之目的在於提供一種暫時固定材，其即便於硬化後照射低能量之雷射光之情形時，對雷射加工性能亦優異，從而能夠效率良好地將支持體剝離。又，本發明之目的在於提供一種該暫時固定材之硬化物。進而，本發明之目的在於提供一種具有該硬化物之積層體。進而，本發明之目的在於提供一種電子零件之製造方法，其具有即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離之步驟。 [解決課題之技術手段] The object of the present invention is to provide a bonding film which can efficiently peel off a support even when irradiated with low-energy laser light, and has excellent peeling properties for an adherend even when subjected to high-temperature processing. Another object of the present invention is to provide a cured product of the bonding film. Furthermore, the object of the present invention is to provide a laminate having a support, the bonding film, and a semiconductor in sequence. Furthermore, the purpose of the present invention is to provide a method for manufacturing electronic components, which has: using the laminate, even when irradiated with low-energy laser light, the step of efficiently peeling off the support body; and even when subjected to high-temperature processing, the step of easily peeling off the adhered body. Furthermore, the purpose of the present invention is to provide a temporary fixing material, which has excellent laser processing performance even when irradiated with low-energy laser light after curing, so that the support body can be peeled off efficiently. Furthermore, the purpose of the present invention is to provide a cured product of the temporary fixing material. Furthermore, the purpose of the present invention is to provide a laminate having the cured product. Furthermore, the purpose of the present invention is to provide a method for manufacturing electronic components, which has a step of efficiently peeling off the support even when irradiated with low-energy laser light. [Technical means for solving the problem]

本發明1係一種接著膜，其包含含有硬化型接著劑之接著層，該硬化型接著劑為光硬化型接著劑，該接著層以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後的凝膠分率為65質量%以上，該接著層以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後對波長308 nm之光的消光係數為1.0×10 -4以上。 本發明2係一種接著膜，其包含含有硬化型接著劑之接著層，該硬化型接著劑為光硬化型接著劑，該接著層照射光後之凝膠分率為65質量%以上，該接著層照射光後對波長308 nm之光之消光係數為1.0×10 -4以上。 本發明3係如本發明1或2之接著膜，其中，該硬化型接著劑含有硬化性樹脂及光聚合起始劑。 本發明4係如本發明3之接著膜，其中，該硬化性樹脂含有雙馬來醯亞胺化合物。 本發明5係如本發明3或4之接著膜，其中，該光聚合起始劑於波長405 nm之吸光係數為10 ml/（g・cm）以上。 本發明6係如本發明3、4或5之接著膜，其中，該光聚合起始劑之含量相對於該硬化性樹脂100質量份，為0.1質量份以上10質量份以下。 本發明7係如本發明3、4、5或6之接著膜，其中，該硬化型接著劑進而含有紫外線吸收劑。 本發明8係如本發明7之接著膜，其中，該紫外線吸收劑包含三系紫外線吸收劑。 本發明9係如本發明7或8之接著膜，其中，該紫外線吸收劑之含量相對於該硬化性樹脂100質量份為，1質量份以上30質量份以下。 本發明10係如本發明3、4、5、6、7、8或9之接著膜，其中，該硬化型接著劑進而含有離型劑。 本發明11係如本發明10之接著膜，其中，該離型劑包含選自由聚矽氧系離型劑及丙烯酸系離型劑所組成之群中之至少1種。 本發明12係如本發明10或11之接著膜，其中，該離型劑之含量相對於該硬化性樹脂100質量份，為0.1質量份以上20質量份以下。 本發明13係如本發明1、2、3、4、5、6、7、8、9、10、11或12之接著膜，其中，該接著層照射光之前的凝膠分率為60質量%以下。 本發明14係如本發明1、2、3、4、5、6、7、8、9、10、11、12或13之接著膜，其中，該接著層照射光之前對波長308 nm之光的消光係數為1.0×10 -4以上。 本發明15係如本發明1、2、3、4、5、6、7、8、9、10、11、12、13或14之接著膜，其具有基材。 本發明16係如本發明1、2、3、4、5、6、7、8、9、10、11、12、13、14或15之接著膜，其以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後，於氮氣環境下，經以升溫速度10℃/min加熱之情形時之5%重量減少溫度為300℃以上。 本發明17係如本發明1、2、3、4、5、6、7、8、9、10、11、12、13、14、15或16之接著膜，其用於電子零件之暫時固定。 本發明18係一種硬化物，其係使本發明1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16或17之接著膜硬化而成，且經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上。 本發明19係一種積層體，其依序具有支持體、本發明1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16或17之接著膜及半導體裝置。 本發明20係一種電子零件之製造方法，其使用本發明19之積層體，並具有下述步驟：光照射步驟：自該支持體側對該積層體照射光；高溫加工處理步驟：對該積層體實施加熱處理或伴有發熱之處理；支持體剝離步驟：自該支持體側對該積層體照射波長200 nm以上355 nm以下之雷射光，而將該支持體自該接著膜剝離；及接著膜剝離步驟：將該接著膜自該半導體裝置剝離。 本發明21係一種暫時固定材，其含有硬化型接著劑，該硬化型接著劑為光硬化型接著劑，藉由以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光而硬化後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上。 本發明22係一種暫時固定材，其含有硬化型接著劑，其於硬化後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上。 本發明23係如本發明21或22之暫時固定材，其中，於該硬化後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為1.0 μm以下。 本發明24係如本發明21、22或23之暫時固定材，其中，於該硬化後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度為1.0 μm以下。 本發明25係如本發明21、22、23或24之暫時固定材，其中，該硬化型接著劑含有硬化性樹脂，該硬化性樹脂包含在主鏈之重複單元具有醯亞胺骨架之樹脂。 本發明26係如本發明25之暫時固定材，其中，於該硬化性樹脂100質量份中，該在主鏈之重複單元具有醯亞胺骨架之樹脂的含量為65質量份以上。 本發明27係如本發明21、22、23、24、25或26之暫時固定材，其中，該硬化型接著劑含有紫外線吸收劑或紫外線散射劑。 本發明28係如本發明27之暫時固定材，其中，上述紫外線吸收劑或該紫外線散射劑包含三系紫外線吸收劑或氧化鈦。 本發明29係如本發明21、22、23、24、25、26、27或28之暫時固定材，其中，該硬化型接著劑含有光聚合起始劑。 本發明30係如本發明21、22、23、24、25、26、27、28或29之暫時固定材，其於硬化後，於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率為7%以下。 本發明31係一種硬化物，其係使本發明21、22、23、24、25、26、27、28、29或30之暫時固定材硬化而成。 本發明32係一種積層體，其依序具有支持體、本發明31之硬化物、及半導體裝置，該支持體之波長300 nm以上400 nm以下之光的穿透率為50%以上。 本發明33係一種電子零件之製造方法，其具有支持體剝離步驟：對依序含有支持體、暫時固定材之硬化物及半導體裝置之積層體自該支持體側脈衝照射波長308 nm以上355 nm以下、脈衝寬度100 nsec以下、照射能量密度500 mJ/cm 2以下之雷射光，藉此，將該支持體自該積層體剝離。 以下，對本發明進行詳細說明。 The present invention 1 is an adhesive film, which includes an adhesive layer containing a curable adhesive, wherein the curable adhesive is a photocurable adhesive, and the gel fraction of the adhesive layer after irradiating light with a wavelength of 405 nm in a manner such that the cumulative light amount becomes 20,000 mJ/ cm2 is 65% by mass or more, and the extinction coefficient of the adhesive layer for light with a wavelength of 308 nm after irradiating light with a wavelength of 405 nm in a manner such that the cumulative light amount becomes 20,000 mJ/ cm2 is 1.0× 10-4 or more. Invention 2 is an adhesive film, which includes an adhesive layer containing a curable adhesive, wherein the curable adhesive is a photocurable adhesive, the gel fraction of the adhesive layer after irradiation with light is 65 mass % or more, and the extinction coefficient of the adhesive layer for light with a wavelength of 308 nm after irradiation with light is 1.0×10 -4 or more. Invention 3 is an adhesive film as in invention 1 or 2, wherein the curable adhesive contains a curable resin and a photopolymerization initiator. Invention 4 is an adhesive film as in invention 3, wherein the curable resin contains a dimaleimide compound. Invention 5 is an adhesive film as in invention 3 or 4, wherein the light absorption coefficient of the photopolymerization initiator at a wavelength of 405 nm is 10 ml/(g・cm) or more. Invention 6 is an adhesive film as in invention 3, 4 or 5, wherein the content of the photopolymerization initiator is 0.1 to 10 parts by mass relative to 100 parts by mass of the curable resin. Invention 7 is an adhesive film as in invention 3, 4, 5 or 6, wherein the curable adhesive further contains an ultraviolet absorber. Invention 8 is an adhesive film as in invention 7, wherein the ultraviolet absorber contains three The present invention 9 is an adhesive film as in the present invention 7 or 8, wherein the content of the ultraviolet absorber is 1 part by mass or more and 30 parts by mass or less relative to 100 parts by mass of the curable resin. The present invention 10 is an adhesive film as in the present invention 3, 4, 5, 6, 7, 8 or 9, wherein the curable adhesive further contains a release agent. The present invention 11 is an adhesive film as in the present invention 10, wherein the release agent includes at least one selected from the group consisting of a silicone release agent and an acrylic release agent. The present invention 12 is an adhesive film as in the present invention 10 or 11, wherein the content of the release agent is 0.1 part by mass or more and 20 parts by mass or less relative to 100 parts by mass of the curable resin. The thirteenth invention is a bonding film as in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, or twenty-first inventions, wherein the gel fraction of the bonding layer before irradiation with light is 60 mass % or less. The fourteenth invention is a bonding film as in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, or twenty-first inventions, wherein the extinction coefficient of the bonding layer for light of a wavelength of 308 nm before irradiation with light is 1.0×10 -4 or more. The fifteenth invention is a bonding film as in the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, or twenty-first inventions, wherein the bonding layer has a substrate. Invention 16 is an adhesive film as in invention 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, wherein after irradiation with light of wavelength 405 nm in a manner that the accumulated light quantity becomes 20000 mJ/ cm2 , the 5% weight loss temperature when heated at a temperature increase rate of 10°C/min in a nitrogen environment is 300°C or above. Invention 17 is an adhesive film as in invention 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, which is used for temporary fixing of electronic components. The present invention 18 is a cured product, which is obtained by curing the bonding film of the present invention 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, and the laser processing depth is 0.10 μm or more when pulse irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/ cm2 . The present invention 19 is a laminate, which has a support, the bonding film of the present invention 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, and a semiconductor device in order. The present invention 20 is a method for manufacturing electronic components, which uses the laminate of the present invention 19 and has the following steps: a light irradiation step: irradiating the laminate with light from the support side; a high temperature processing step: applying heat treatment or a treatment accompanied by heating to the laminate; a support peeling step: irradiating the laminate with laser light with a wavelength of not less than 200 nm and not more than 355 nm from the support side to peel the support from the bonding film; and a bonding film peeling step: peeling the bonding film from the semiconductor device. The present invention 21 is a temporary fixing material, which contains a curable adhesive, and the curable adhesive is a light curable adhesive. After curing by irradiating light with a wavelength of 365 nm in a manner that the cumulative light amount becomes 20,000 mJ/ cm2 , the laser processing depth when irradiating with laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 is 0.10 μm or more. The present invention 22 is a temporary fixing material, which contains a curable adhesive. After curing, the laser processing depth when irradiating with laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 is 0.10 μm or more. The present invention 23 is a temporary fixing material as in the present invention 21 or 22, wherein after the curing, the laser processing depth when irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/ cm2 by pulse is 1.0 μm or less. The present invention 24 is a temporary fixing material as in the present invention 21, 22, or 23, wherein after the curing, the laser processing depth when irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 400 mJ/ cm2 by pulse is 1.0 μm or less. The present invention 25 is a temporary fixing material as described in the present invention 21, 22, 23 or 24, wherein the curable adhesive contains a curable resin, and the curable resin contains a resin having an imide skeleton in a repeating unit of the main chain. The present invention 26 is a temporary fixing material as described in the present invention 25, wherein the content of the resin having an imide skeleton in a repeating unit of the main chain is 65 parts by mass or more in 100 parts by mass of the curable resin. The present invention 27 is a temporary fixing material as described in the present invention 21, 22, 23, 24, 25 or 26, wherein the curable adhesive contains an ultraviolet absorber or an ultraviolet scatterer. The present invention 28 is a temporary fixing material as in the present invention 27, wherein the ultraviolet absorber or the ultraviolet scatterer comprises three is an ultraviolet absorber or titanium oxide. Invention 29 is a temporary fixing material as in invention 21, 22, 23, 24, 25, 26, 27 or 28, wherein the curing adhesive contains a photopolymerization initiator. Invention 30 is a temporary fixing material as in invention 21, 22, 23, 24, 25, 26, 27, 28 or 29, wherein after curing, the weight loss rate of the temporary fixing material when heated at 290° C. for 30 minutes in a nitrogen environment is 7% or less. Invention 31 is a cured product, which is obtained by curing the temporary fixing material of invention 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. The present invention 32 is a laminate, which sequentially comprises a support, a hardened material of the present invention 31, and a semiconductor device, wherein the transmittance of the support for light having a wavelength of 300 nm to 400 nm is 50% or more. The present invention 33 is a method for manufacturing an electronic component, which comprises a support stripping step: the laminate, which sequentially comprises a support, a hardened material of a temporary fixing material, and a semiconductor device, is pulsed with laser light having a wavelength of 308 nm to 355 nm, a pulse width of 100 nsec or less, and an irradiation energy density of 500 mJ/cm 2 or less from the side of the support, thereby stripping the support from the laminate. The present invention is described in detail below.

本發明者等人著眼於在近年來所需之高耐熱性之電子零件之製造中，用以將支持體剝離而照射之雷射光為高能量，對獲得如下接著膜或暫時固定材進行了研究，該接著膜或暫時固定材即便於照射能夠抑制損傷裝置、支持體、暫時固定材等之低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離。 本發明者等人使用包含含有硬化型接著劑之接著層之接著膜，對關於進行光照射後之接著膜，將接著層之凝膠分率及接著層對特定波長之光的消光係數調整為特定範圍內進行了研究。結果發現，能夠獲得如下接著膜，其即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離，進而，即便於進行高溫加工處理之情形時，對被黏著體之剝離性亦優異，從而完成了本發明之接著膜。 又，本發明者等人對使含有硬化型接著劑之暫時固定材硬化，並對經硬化之暫時固定材脈衝照射雷射光時之加工深度進行了研究，發現若使用成為特定加工狀態之暫時固定材，則能夠效率良好地將支持體剝離，從而完成了本發明之暫時固定材。 The inventors of the present invention have focused on the fact that in the manufacture of electronic components with high heat resistance, which has been required in recent years, the laser light used for irradiation to peel off the support is high energy, and have studied the following adhesive film or temporary fixing material, which can efficiently peel off the support even when irradiated with low energy laser light that can suppress damage to the device, support, temporary fixing material, etc. The inventors of the present invention used an adhesive film including an adhesive layer containing a curing adhesive, and studied adjusting the gel fraction of the adhesive layer and the extinction coefficient of the adhesive layer to light of a specific wavelength within a specific range for the adhesive film after light irradiation. As a result, it was found that the following adhesive film can be obtained, which can efficiently peel off the support even when irradiated with low-energy laser light, and further, even when subjected to high-temperature processing, the peeling property of the adherend is excellent, thereby completing the adhesive film of the present invention. In addition, the inventors of the present invention and others studied the processing depth when the temporary fixing material containing a curing adhesive was hardened and the hardened temporary fixing material was pulse-irradiated with laser light, and found that if a temporary fixing material in a specific processing state is used, the support can be efficiently peeled off, thereby completing the temporary fixing material of the present invention.

本發明之接著膜包含含有硬化型接著劑之接著層。上述硬化型接著劑為光硬化型接著劑。藉由使本發明之接著膜包含含有光硬化型接著劑之接著層，能夠藉由光進行硬化，從而能夠抑制高溫加工處理中之所獲得之接著膜對被黏著體之接著亢進。結果，所獲得之接著膜對被黏著體之剝離性提高，從而能夠防止與被黏著體剝離時產生糊劑殘留。 作為藉由光使本發明之接著膜硬化之方法，例如可舉使用超高壓水銀燈以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光的方法等。 The adhesive film of the present invention includes an adhesive layer containing a curable adhesive. The curable adhesive is a photocurable adhesive. By making the adhesive film of the present invention include an adhesive layer containing a photocurable adhesive, it can be cured by light, thereby suppressing the hyperadhesion of the adhesive film obtained during high-temperature processing to the adherend. As a result, the peelability of the obtained adhesive film to the adherend is improved, thereby preventing the generation of paste residues when peeling from the adherend. As a method for curing the adhesive film of the present invention by light, for example, a method of irradiating light with a wavelength of 405 nm in a manner such that the cumulative light amount becomes 20,000 mJ/ cm2 using an ultra-high pressure mercury lamp can be cited.

本發明2之接著膜之上述接著層照射光後之凝膠分率的下限為65質量%。藉由使上述接著層之照射光後之凝膠分率為65質量%以上，所獲得之接著膜對被黏著體之剝離性優異。上述接著層照射光後之凝膠分率的較佳下限為70質量%，更佳下限為75質量%。 又，就提高上述接著層之硬化性之觀點而言，鑒於使用不會被組入至交聯中之光聚合起始劑，上述接著層照射光後之凝膠分率的較佳上限為99.9質量%，更佳上限為99質量%。 作為上述接著層照射光後之凝膠分率中之光的照射條件，例如可舉以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光等。 The lower limit of the gel fraction of the above-mentioned bonding layer of the bonding film of the present invention 2 after being irradiated with light is 65% by mass. By making the gel fraction of the above-mentioned bonding layer after being irradiated with light be 65% by mass or more, the obtained bonding film has excellent releasability to the adherend. The preferred lower limit of the gel fraction of the above-mentioned bonding layer after being irradiated with light is 70% by mass, and the more preferred lower limit is 75% by mass. In addition, from the perspective of improving the curability of the above-mentioned bonding layer, in view of the use of a photopolymerization initiator that will not be incorporated into the crosslinking, the preferred upper limit of the gel fraction of the above-mentioned bonding layer after being irradiated with light is 99.9% by mass, and the more preferred upper limit is 99% by mass. As the light irradiation conditions in the gel fraction after the above-mentioned next layer is irradiated with light, for example, irradiation with light having a wavelength of 405 nm can be given so that the accumulated light amount becomes 20000 mJ/ cm2 .

本發明1之接著膜之上述接著層以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後之凝膠分率（以下，亦有時僅表示為「接著層照射波長405 nm之光後之凝膠分率」）的下限為65質量%。藉由使上述接著層照射波長405 nm之光後的凝膠分率為65質量%以上，所獲得之接著膜對被黏著體之剝離性優異。上述接著層照射波長405 nm之光後之凝膠分率的較佳下限為70質量%，更佳下限為75質量%。 又，就提高上述接著層之硬化性之觀點而言，鑒於使用不會被組入至交聯中之光聚合起始劑，上述接著層照射波長405 nm之光後之凝膠分率的較佳上限為99.9質量%，更佳上限為99質量%。 再者，上述接著層照射波長405 nm之光後的凝膠分率例如係藉由以下方法測定。 即，針對接著膜，以累計光量成為20000 mJ/cm 2之方式對接著層照射波長405 nm之光後，採集質量W 0（g）之照射光後之接著層，將所採集之接著層於23℃於甲苯中浸漬24小時。浸漬後，使用金屬網（網眼＃200目，質量：W 1（g））對吸收了甲苯而已膨潤之接著層進行過濾，使分離後之接著層於110℃之條件下乾燥1小時。繼而，測定乾燥後之接著層之質量W 2（g），並使用下述式算出凝膠分率等，藉此，能夠測定上述接著層照射波長405 nm之光後的凝膠分率。 凝膠分率（質量%）＝100×（W 2－W 1）/W 0（W 0：初始接著層之質量、W 1：金屬網之初始質量、W 2：乾燥後之含有金屬網之接著層的質量） The lower limit of the gel fraction of the bonding layer of the bonding film of the present invention 1 after irradiation with light of a wavelength of 405 nm in such a manner that the cumulative light amount becomes 20000 mJ/ cm2 (hereinafter, sometimes simply expressed as "the gel fraction of the bonding layer after irradiation with light of a wavelength of 405 nm") is 65% by mass. By making the gel fraction of the bonding layer after irradiation with light of a wavelength of 405 nm 65% by mass or more, the bonding film obtained has excellent releasability from the adherend. The preferred lower limit of the gel fraction of the bonding layer after irradiation with light of a wavelength of 405 nm is 70% by mass, and the more preferred lower limit is 75% by mass. In addition, from the viewpoint of improving the curability of the above-mentioned bonding layer, in view of the use of a photopolymerization initiator that is not incorporated into the crosslinking, the preferred upper limit of the gel fraction of the above-mentioned bonding layer after irradiation with light of a wavelength of 405 nm is 99.9 mass%, and the more preferred upper limit is 99 mass%. Furthermore, the gel fraction of the above-mentioned bonding layer after irradiation with light of a wavelength of 405 nm is measured, for example, by the following method. That is, after irradiating the bonding layer with light of a wavelength of 405 nm in a manner such that the cumulative light amount becomes 20000 mJ/ cm2 , the bonding layer after irradiation with a mass of W0 (g) is collected, and the collected bonding layer is immersed in toluene at 23°C for 24 hours. After immersion, the adhesive layer that has absorbed toluene and swelled is filtered using a metal mesh (mesh size #200, mass: W1 (g)), and the separated adhesive layer is dried at 110°C for 1 hour. Then, the mass W2 (g) of the dried adhesive layer is measured, and the gel fraction is calculated using the following formula, thereby measuring the gel fraction of the adhesive layer after irradiation with light of a wavelength of 405 nm. Gel fraction (mass %) = 100×( W2 - W1 )/ W0 ( W0 : mass of initial adhesive layer, W1 : initial mass of metal mesh, W2 : mass of adhesive layer containing metal mesh after drying)

上述接著層照射光前之凝膠分率（以下，亦有時僅表示為「接著層照射光前之凝膠分率」）之較佳上限為60質量%。藉由使上述接著層照射光前之凝膠分率為60質量%以下，所獲得之接著膜之接著性更優異。上述接著層照射光前之凝膠分率的更佳上限為50質量%，進而較佳上限為40質量%。 又，上述接著層照射光前之凝膠分率的下限雖可為0質量%，但就上述接著層對被黏著體之偏移或變形之耐久性、及所獲得之接著膜對被黏著體之密接性之觀點而言，上述接著層照射光前之凝膠分率的較佳下限為0.5質量%，更佳下限為1質量%。 再者，上述接著層照射光前之凝膠分率，例如可藉由如下方式進行測定，即，不進行光照射而實施以上所述之該接著層照射光後之凝膠分率的測定方法。 The preferred upper limit of the gel fraction of the bonding layer before irradiation (hereinafter, sometimes simply expressed as "gel fraction of the bonding layer before irradiation") is 60% by mass. By making the gel fraction of the bonding layer before irradiation below 60% by mass, the bonding property of the bonding film obtained is better. The preferred upper limit of the gel fraction of the bonding layer before irradiation is 50% by mass, and further preferably 40% by mass. Furthermore, although the lower limit of the gel fraction of the bonding layer before irradiation with light may be 0 mass%, from the viewpoint of the durability of the bonding layer to the offset or deformation of the adherend and the close adhesion of the obtained bonding film to the adherend, the preferred lower limit of the gel fraction of the bonding layer before irradiation with light is 0.5 mass%, and the more preferred lower limit is 1 mass%. Furthermore, the gel fraction of the bonding layer before irradiation with light can be measured, for example, by the following method, that is, without irradiation with light, the method for measuring the gel fraction of the bonding layer after irradiation with light described above is implemented.

作為將上述接著層照射光後之凝膠分率、及上述接著層照射光前之凝膠分率調整為上述範圍的方法，較佳為變更上述光硬化型接著劑之組成之方法（例如，調整不會進行光硬化之成分之量、藉由添加光聚合起始劑而提高光硬化性等）。As a method for adjusting the gel fraction of the above-mentioned bonding layer after irradiation with light and the gel fraction of the above-mentioned bonding layer before irradiation with light to the above-mentioned range, it is better to change the composition of the above-mentioned photocurable adhesive (for example, adjusting the amount of components that will not be photocured, improving photocurability by adding a photopolymerization initiator, etc.).

本發明2之接著膜之上述接著層照射光後對波長308 nm之光的消光係數的下限為1.0×10 -4。藉由使上述接著層照射光後對波長308 nm之光的消光係數為1.0×10 -4以上，即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離。上述接著層照射光後對波長308 nm之光的消光係數之較佳下限為1.0×10 -3，更佳下限為5.0×10 -2，進而較佳下限為1.0×10 -1。 又，上述接著層照射光後對波長308 nm之光的消光係數之較佳上限為50。藉由使上述接著層照射光後對波長308 nm之光的消光係數為50以下，即便於照射低能量之雷射光之情形時，亦能夠將上述接著層加工至更充分之深度為止，故能夠更效率良好地將支持體剝離。上述接著層照射光後之對波長308 nm之光的消光係數之更佳上限為20，進而較佳上限為10，進而更佳上限為5.0。 作為上述接著層照射光後之消光係數中之光的照射條件，例如可舉以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光等。 The lower limit of the extinction coefficient of the bonding layer of the bonding film of the present invention 2 to light of a wavelength of 308 nm after being irradiated with light is 1.0×10 -4 . By making the extinction coefficient of the bonding layer to light of a wavelength of 308 nm after being irradiated with light be 1.0×10 -4 or more, the support can be efficiently peeled off even when irradiated with low-energy laser light. The preferred lower limit of the extinction coefficient of the bonding layer to light of a wavelength of 308 nm after being irradiated with light is 1.0×10 -3 , the more preferred lower limit is 5.0×10 -2 , and the further preferred lower limit is 1.0×10 -1 . In addition, the preferred upper limit of the extinction coefficient of the bonding layer to light of a wavelength of 308 nm after being irradiated with light is 50. By making the extinction coefficient of the bonding layer to light of wavelength 308 nm after irradiation of light 50 or less, the bonding layer can be processed to a more sufficient depth even when irradiated with low-energy laser light, so the support can be peeled off more efficiently. The upper limit of the extinction coefficient of the bonding layer to light of wavelength 308 nm after irradiation of light is more preferably 20, more preferably 10, and more preferably 5.0. As the irradiation condition of the light in the extinction coefficient after irradiation of light of the bonding layer, for example, irradiation with light of wavelength 405 nm can be cited in a manner that the cumulative light amount becomes 20000 mJ/ cm2 .

本發明1之接著膜之上述接著層以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後對波長308 nm之光之消光係數（以下，亦有時僅表示為「接著層照射波長405 nm之光後對波長308 nm之光之消光係數」）的下限為1.0×10 -4。藉由使上述接著層照射波長405 nm之光後對波長308 nm之光的消光係數為1.0×10 -4以上，即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離。上述接著層照射波長405 nm之光後對波長308 nm之光之消光係數的較佳下限為1.0×10 -3，更佳下限為1.0×10 -2，進而較佳下限為5.0×10 -2，進而更佳下限為1.0×10 -1。 又，上述接著層照射波長405 nm之光後對波長308 nm之光之消光係數的較佳上限為50。藉由使上述接著層照射波長405 nm之光後對波長308 nm之光之消光係數為50以下，即便於照射低能量之雷射光之情形時，亦能夠將上述接著層加工至更充分之深度為止，故能夠更效率良好地將支持體剝離。上述接著層照射波長405 nm之光後對波長308 nm之光之消光係數的更佳上限為20，進而較佳上限為10，進而更佳上限為5.0。 再者，上述接著層照射波長405 nm之光後對波長308 nm之光的消光係數，例如可藉由以下方法進行測定。 即，針對以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後的接著層，藉由分光光度計（日本分光公司製造，「V-670」等）測定穿透率與反射率，藉由厚度計（MITUTOYO公司製造，「Digimatic Indicator ID-H」等）測定厚度。使用所獲得之穿透率、反射率、及厚度之測定結果，並利用光譜橢偏儀解析軟體進行解析等，藉此，能夠測定出本發明之接著層照射光後對波長308 nm之光的消光係數。再者，於本發明之接著膜具有基材之情形時，可藉由如下方式獲得：將接著層與基材分離，針對已分離之接著層進行穿透率、反射率、厚度之測定，使用所獲得之穿透率、反射率、厚度之測定結果並利用光譜橢偏儀解析軟體進行解析。 再者，存在穿透率成為1%以下之波長無法根據上述解析導出消光係數之準確值之情形。因此，於波長308 nm之穿透率為1%以下之情形時，假定使用穿透率大於1%之長波長區域之消光係數近似成指數函數，藉由最小平方法求出近似曲線之式（y＝A（常數）×e ＾（B（常數）×x），y：消光係數，x：波長（nm）），並根據所獲得之近似曲線之式算出波長308 nm的消光係數k。於穿透率成為1%以下之波長短於波長308 nm之情形時，能夠根據上述解析結果求出波長308 nm之消光係數k。 The lower limit of the extinction coefficient of the bonding layer of the bonding film of the present invention 1 to the light of 308 nm after irradiation with the light of 405 nm in a manner that the cumulative light amount becomes 20000 mJ/ cm2 (hereinafter, sometimes simply expressed as "the extinction coefficient of the bonding layer to the light of 308 nm after irradiation with the light of 405 nm") is 1.0× 10-4 . By making the extinction coefficient of the bonding layer to the light of 308 nm after irradiation with the light of 405 nm be 1.0× 10-4 or more, even when irradiated with low-energy laser light, the support can be efficiently peeled off. The preferred lower limit of the extinction coefficient of the bonding layer to the light of wavelength 308 nm after irradiation with light of wavelength 405 nm is 1.0×10 -3 , more preferably 1.0×10 -2 , further preferably 5.0×10 -2 , further more preferably 1.0×10 -1 . Moreover, the preferred upper limit of the extinction coefficient of the bonding layer to the light of wavelength 308 nm after irradiation with light of wavelength 405 nm is 50. By making the extinction coefficient of the bonding layer to the light of wavelength 308 nm after irradiation with light of wavelength 405 nm be 50 or less, the bonding layer can be processed to a more sufficient depth even when irradiated with low-energy laser light, so the support can be peeled off more efficiently. The upper limit of the extinction coefficient of the bonding layer for light of wavelength 308 nm after irradiation with light of wavelength 405 nm is preferably 20, further preferably 10, and further preferably 5.0. Furthermore, the extinction coefficient of the bonding layer for light of wavelength 308 nm after irradiation with light of wavelength 405 nm can be measured, for example, by the following method. That is, the bonding layer irradiated with light of wavelength 405 nm in such a manner that the accumulated light amount becomes 20000 mJ/ cm2 is measured for transmittance and reflectance by a spectrophotometer (manufactured by JASCO Corporation, "V-670", etc.), and the thickness is measured by a thickness meter (manufactured by MITUTOYO, "Digimatic Indicator ID-H", etc.). By using the obtained transmittance, reflectance, and thickness measurement results and analyzing them using the spectral ellipsometer analysis software, the extinction coefficient of the bonding layer of the present invention to light of a wavelength of 308 nm after being irradiated with light can be measured. Furthermore, when the bonding film of the present invention has a substrate, it can be obtained by the following method: separating the bonding layer from the substrate, measuring the transmittance, reflectance, and thickness of the separated bonding layer, and using the obtained transmittance, reflectance, and thickness measurement results and analyzing them using the spectral ellipsometer analysis software. Furthermore, there is a situation where the wavelength at which the transmittance becomes less than 1% cannot derive an accurate value of the extinction coefficient according to the above analysis. Therefore, when the transmittance at a wavelength of 308 nm is less than 1%, it is assumed that the extinction coefficient in the long wavelength region with a transmittance greater than 1% is approximated as an exponential function, and the formula of the approximate curve is obtained by the least square method (y＝A(constant)×e ＾ (B(constant)×x), y: extinction coefficient, x: wavelength (nm)), and the extinction coefficient k at a wavelength of 308 nm is calculated based on the obtained approximate curve formula. When the wavelength shorter than 308 nm where the transmittance becomes less than 1%, the extinction coefficient k at a wavelength of 308 nm can be obtained based on the above analytical results.

上述接著層照射光前對波長308 nm之光之消光係數（以下，亦有時僅表示為「接著層之光照射前對波長308 nm之光的消光係數」）的較佳下限為1.0×10 -4。藉由使上述接著層照射光前對波長308 nm之光的消光係數為1.0×10 -4以上，能夠更容易地將上述接著層照射光後對波長308 nm之光的消光係數調節為上述範圍。上述接著層照射光前對波長308 nm之光的消光係數之更佳下限為1.0×10 -3，進而較佳下限為1.0×10 -2，進而更佳下限為5.0×10 -2。 又，上述接著層照射光前對波長308 nm之光的消光係數之較佳上限為50。藉由使上述接著層照射光前對波長308 nm之光的消光係數為50以下，即便於照射低能量之雷射光之情形時，亦能夠將上述接著層加工至更充分之深度為止，故能夠更效率良好地將支持體剝離。上述接著層照射光前對波長308 nm之光的消光係數之更佳上限為20，進而較佳上限為10。 再者，上述接著層照射光前對波長308 nm之光的消光係數，例如可藉由如下方式進行測定：針對測定前之上述接著層，不進行光照射而實施對上述接著層照射光後對波長308 nm之光的消光係數之測定。 The preferred lower limit of the extinction coefficient of the above-mentioned connecting layer to light of a wavelength of 308 nm before being irradiated with light (hereinafter, sometimes simply expressed as "extinction coefficient of the above-mentioned connecting layer to light of a wavelength of 308 nm before being irradiated with light") is 1.0×10 -4 . By making the extinction coefficient of the above-mentioned connecting layer to light of a wavelength of 308 nm before being irradiated with light be 1.0×10 -4 or more, it is possible to more easily adjust the extinction coefficient of the above-mentioned connecting layer to light of a wavelength of 308 nm after being irradiated with light to the above-mentioned range. The preferred lower limit of the extinction coefficient of the above-mentioned connecting layer to light of a wavelength of 308 nm before being irradiated with light is 1.0×10 -3 , further preferred lower limit is 1.0×10 -2 , and further preferred lower limit is 5.0×10 -2 . Furthermore, the upper limit of the extinction coefficient of the bonding layer to the light of wavelength 308 nm before irradiation is preferably 50. By making the extinction coefficient of the bonding layer to the light of wavelength 308 nm before irradiation be 50 or less, the bonding layer can be processed to a more sufficient depth even when irradiated with low-energy laser light, so the support can be peeled off more efficiently. The upper limit of the extinction coefficient of the bonding layer to the light of wavelength 308 nm before irradiation is more preferably 20, and further preferably 10. Furthermore, the extinction coefficient of the bonding layer to light of a wavelength of 308 nm before irradiation can be measured, for example, by measuring the extinction coefficient of the bonding layer to light of a wavelength of 308 nm after irradiation without irradiating the bonding layer before measurement.

作為將上述接著層照射光後對波長308 nm之光的消光係數、及上述接著層照射光前對波長308 nm之光的消光係數調整為上述範圍之方法，較佳為變更上述硬化型接著劑之組成（例如下述紫外線吸收劑等）之種類或含量之方法。As a method for adjusting the extinction coefficient of the above-mentioned bonding layer to light of a wavelength of 308 nm after irradiation with light and the extinction coefficient of the above-mentioned bonding layer to light of a wavelength of 308 nm before irradiation with light to the above-mentioned range, it is preferable to change the type or content of the composition of the above-mentioned curable adhesive (for example, the ultraviolet absorber described below).

含有硬化型接著劑，使上述硬化型接著劑硬化後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上的暫時固定材亦為本發明之一。 本發明之暫時固定材即便於硬化後照射低能量之雷射光之情形時，對雷射加工性能亦優異，而能夠效率良好地將支持體剝離。 再者，於本說明書中，「雷射加工深度」係指將雷射光脈衝照射至已硬化之上述暫時固定材後，自硬化後之上述暫時固定材之雷射光照射側之表面觀測到的已硬化之上述暫時固定材被去除之深度。 A temporary fixing material containing a curable adhesive, which after curing the curable adhesive, has a laser processing depth of 0.10 μm or more when pulsed with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 is also one of the present invention. The temporary fixing material of the present invention has excellent laser processing performance even when irradiated with low-energy laser light after curing, and can efficiently peel off the support. Furthermore, in this specification, "laser processing depth" refers to the depth of the cured temporary fixing material removed from the surface of the laser light irradiated side of the cured temporary fixing material after irradiating the laser light pulse to the cured temporary fixing material.

上述硬化型接著劑可為藉由光之照射而硬化之光硬化型接著劑，亦可為藉由高溫環境下之加熱而硬化之熱硬化型接著劑。其中，就加熱後之剝離性之觀點而言，較佳為光硬化型接著劑。The curable adhesive may be a light curable adhesive that is cured by irradiation with light, or a heat curable adhesive that is cured by heating in a high temperature environment. Of these, light curable adhesives are preferred from the perspective of peelability after heating.

作為使上述光硬化型接著劑硬化之方法，例如可舉以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光之方法、以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光之方法等。 作為以累計光量成為20000 mJ/cm 2之方式照射上述波長365 nm之光之方法中的光源，例如可舉超高壓水銀燈、LED、金屬鹵化物型燈等。 含有光硬化型接著劑，以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上之暫時固定材亦為本發明之一。 Examples of methods for curing the photocurable adhesive include irradiating with light having a wavelength of 365 nm so that the cumulative light quantity becomes 20,000 mJ/ cm2 , irradiating with light having a wavelength of 405 nm so that the cumulative light quantity becomes 20,000 mJ/ cm2 , etc. Examples of the light source in the method of irradiating with light having a wavelength of 365 nm so that the cumulative light quantity becomes 20,000 mJ/ cm2 include ultra-high pressure mercury lamps, LEDs, metal halide lamps, etc. The present invention also provides a temporary fixing material containing a photocurable adhesive, which is irradiated with light of a wavelength of 365 nm in such a manner that the cumulative light amount becomes 20,000 mJ/cm 2 , and then pulsed with laser light of a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2, and has a laser processing depth of 0.10 μm or more.

作為使上述熱硬化型接著劑硬化之方法，例如可舉於氮氣環境下以290℃加熱30分鐘之方法、於氧氣環境下於150℃加熱30分鐘之方法等。As a method for curing the above-mentioned heat-curing adhesive, for example, there can be cited a method of heating at 290° C. for 30 minutes in a nitrogen environment, a method of heating at 150° C. for 30 minutes in an oxygen environment, and the like.

本發明22之暫時固定材硬化後經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之下限為0.10 μm。經脈衝照射上述波長308 nm、藉由使脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上，即便於照射低能量之雷射光之情形時，亦能夠效率良好地將硬化後之上述暫時固定材自支持體剝離。上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之較佳下限為0.15 μm，更佳下限為0.20 μm。 又，上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之較佳上限為1.0 μm。若上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為1.0 μm以下，則硬化後之上述暫時固定材之對雷射加工性能進一步提高，能夠更效率良好地將支持體剝離。上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的更佳上限為0.80 μm，進而較佳上限為0.60 μm。 再者，於本發明之暫時固定材並非液狀或糊狀之情形時，上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之下限只要於已硬化之暫時固定材之至少一面滿足上述範圍即可，但較佳為於已硬化之暫時固定材之兩面滿足上述範圍。又，於本發明之暫時固定材並非為液狀或糊狀之情形時，上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之上限較佳為於已硬化之暫時固定材的至少一面滿足上述範圍，更佳為於已硬化之暫時固定材之兩面滿足上述範圍。 又，本說明書中之雷射加工深度例如可藉由如下方式進行測定：將雷射光脈衝照射至已硬化之上述暫時固定材後，使用雷射顯微鏡對硬化後之上述暫時固定材之雷射光照射側之表面進行階差測定。作為上述雷射顯微鏡，例如可舉OLS4100-SAT（Olympus公司製造，波長405 nm）等。 After the temporary fixing material of the present invention 22 is hardened, the lower limit of the laser processing depth when the pulse irradiation is performed with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 is 0.10 μm. By setting the laser processing depth to be 0.10 μm or more when the pulse irradiation is performed with the above-mentioned wavelength of 308 nm, the pulse width of 10 nsec, and the irradiation energy density of 300 mJ/cm 2, the hardened temporary fixing material can be efficiently peeled off from the support body even when irradiating with low-energy laser light. The preferred lower limit of the laser processing depth when the laser light with a pulse irradiation wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm2 is 0.15 μm, and the more preferred lower limit is 0.20 μm. In addition, the preferred upper limit of the laser processing depth when the laser light with a pulse irradiation wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 is 1.0 μm. If the laser processing depth when the above-mentioned pulse irradiation laser light has a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 is less than 1.0 μm, the laser processing performance of the above-mentioned temporary fixing material after hardening is further improved, and the support body can be peeled off more efficiently. The upper limit of the laser processing depth when the above-mentioned pulse irradiation laser light has a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm2 is more preferably 0.80 μm, and the further preferred upper limit is 0.60 μm. Furthermore, when the temporary fixing material of the present invention is not in liquid or paste form, the lower limit of the laser processing depth when the pulsed laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 is irradiated is sufficient as long as at least one side of the hardened temporary fixing material meets the above range, but it is better that both sides of the hardened temporary fixing material meet the above range. Furthermore, when the temporary fixing material of the present invention is not in a liquid or paste state, the upper limit of the laser processing depth when the pulse irradiation is performed with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 is preferably such that at least one side of the hardened temporary fixing material satisfies the above range, and more preferably such that both sides of the hardened temporary fixing material satisfy the above range. Furthermore, the laser processing depth in this specification can be measured, for example, by irradiating the hardened temporary fixing material with a laser light pulse, and then using a laser microscope to perform step measurement on the surface of the hardened temporary fixing material on the laser light irradiation side. Examples of the laser microscope include OLS4100-SAT (manufactured by Olympus Corporation, wavelength 405 nm).

本發明21之暫時固定材以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的下限為0.10 μm。 藉由使以累計光量成為20000 mJ/cm 2之方式照射上述波長365 nm之光後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上，即便於照射低能量之雷射光之情形時，亦能夠效率良好地將硬化後之上述暫時固定材自支持體剝離。上述以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的較佳下限為0.15 μm，更佳下限為0.20 μm。 又，上述以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的較佳上限為1.0 μm。若上述以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為1.0 μm以下，則硬化後之上述暫時固定材之對雷射加工性能進一步提高，能夠更效率良好地將支持體剝離。上述以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的更佳上限為0.80 μm，進而較佳上限為0.60 μm。 再者，於本發明之暫時固定材並非為液狀或糊狀之情形時，上述以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之下限只要於已硬化之暫時固定材的至少一面滿足上述範圍即可，但較佳為於已硬化之暫時固定材之兩面滿足上述範圍。又，於本發明之暫時固定材並非為液狀或糊狀之情形時，上述以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之上限較佳為於已硬化之暫時固定材的至少一面滿足上述範圍，更佳為於已硬化之暫時固定材之兩面滿足上述範圍。 The temporary fixing material of the present invention 21 is irradiated with light of a wavelength of 365 nm in such a manner that the cumulative light amount becomes 20000 mJ/cm 2 , and then the laser light of a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 is pulsed, and the lower limit of the laser processing depth is 0.10 μm. By making the laser processing depth of the temporary fixing material of the present invention 21 not less than 0.10 μm when the laser light of a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 is pulsed after the irradiation with the above-mentioned light of a wavelength of 365 nm in such a manner that the cumulative light amount becomes 20000 mJ/cm 2, even when the laser light of low energy is irradiated, the hardened temporary fixing material can be efficiently peeled off from the supporting body. After irradiating with light of a wavelength of 365 nm in such a manner that the accumulated light amount becomes 20000 mJ/cm 2 , the preferred lower limit of the laser processing depth when irradiating with laser light of a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 by pulse is 0.15 μm, and the more preferred lower limit is 0.20 μm. In addition, after irradiating with light of a wavelength of 365 nm in such a manner that the accumulated light amount becomes 20000 mJ/cm 2 , the preferred upper limit of the laser processing depth when irradiating with laser light of a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 by pulse is 1.0 μm. If the laser processing depth is 1.0 μm or less when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/cm 2 is pulsed after irradiating the light with a wavelength of 365 nm in a manner such that the cumulative light amount becomes 20000 mJ/cm 2 , the laser processing performance of the temporary fixing material after hardening is further improved, and the support body can be peeled off more efficiently. The upper limit of the laser processing depth when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/cm 2 is 0.80 μm, and the further upper limit is 0.60 μm. Furthermore, when the temporary fixing material of the present invention is not in liquid or paste form, after irradiating with light of a wavelength of 365 nm in a manner in which the accumulated light amount becomes 20,000 mJ/cm 2 , the lower limit of the laser processing depth when pulsed with laser light of a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 is sufficient as long as at least one side of the hardened temporary fixing material satisfies the above range, but it is preferred that both sides of the hardened temporary fixing material satisfy the above range. Furthermore, when the temporary fixing material of the present invention is not in liquid or paste form, after irradiating with light of a wavelength of 365 nm in a manner such that the accumulated light amount becomes 20,000 mJ/cm 2 , the upper limit of the laser processing depth when pulsed with laser light of a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 is preferably such that at least one side of the hardened temporary fixing material satisfies the above range, and more preferably, both sides of the hardened temporary fixing material satisfy the above range.

上述暫時固定材硬化後經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度之較佳上限為1.0 μm。若上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度為1.0 μm以下，則已硬化之上述暫時固定材之對雷射加工性能進一步提高，能夠更效率良好地將支持體剝離。上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度的更佳上限為0.80 μm，進而較佳上限為0.60 μm。 又，上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度的較佳下限為0.10 μm。若上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上，則已硬化之上述暫時固定材之對雷射加工性能進一步提高，能夠更效率良好地將支持體剝離。上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度的更佳下限為0.15 μm，進而較佳下限為0.20 μm。 再者，於本發明之暫時固定材並非為液狀或糊狀之情形時，上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度較佳為於已硬化之暫時固定材的至少一面滿足上述範圍，更佳為於已硬化之暫時固定材之兩面滿足上述範圍。 After the temporary fixing material is hardened, the upper limit of the laser processing depth when the pulse irradiation is performed with laser light of wavelength 308 nm, pulse width 10 nsec, and energy density 400 mJ/cm 2 is preferably 1.0 μm. If the laser processing depth when the pulse irradiation is performed with laser light of wavelength 308 nm, pulse width 10 nsec, and energy density 400 mJ/cm 2 is less than 1.0 μm, the laser processing performance of the hardened temporary fixing material is further improved, and the support body can be peeled off more efficiently. The upper limit of the laser processing depth when the laser light with a pulse irradiation wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ/ cm2 is preferably 0.80 μm, and the further upper limit is preferably 0.60 μm. Moreover, the lower limit of the laser processing depth when the laser light with a pulse irradiation wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ/cm2 is preferably 0.10 μm. If the laser processing depth when the laser light with a pulse wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 400 mJ/ cm2 is irradiated is 0.10 μm or more, the laser processing performance of the hardened temporary fixing material is further improved, and the support body can be peeled off more efficiently. The lower limit of the laser processing depth when the laser light with a pulse wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 400 mJ/ cm2 is 0.15 μm, and the lower limit is 0.20 μm. Furthermore, when the temporary fixing material of the present invention is not in liquid or paste form, the laser processing depth when the pulsed irradiation laser light has a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ/ cm2 is preferably such that at least one side of the hardened temporary fixing material satisfies the above range, and more preferably, both sides of the hardened temporary fixing material satisfy the above range.

作為調整上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度、及上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度之方法，可舉調整硬化型接著劑之組成之方法等。又，於將上述暫時固定材用於下述積層體之情形時，亦能夠利用使用波長308 nm之光之穿透率較高之支持體的方法進行調整。 As a method for adjusting the laser processing depth when the laser light with a pulse wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/cm2 is irradiated, and the laser processing depth when the laser light with a pulse wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 400 mJ/ cm2 is irradiated, there can be cited a method of adjusting the composition of the curing adhesive, etc. In addition, when the temporary fixing material is used for the following laminate, it can also be adjusted by using a support having a higher transmittance of light with a wavelength of 308 nm.

上述硬化型接著劑較佳為含有硬化性樹脂。 上述硬化性樹脂較佳為包含在主鏈之重複單元具有醯亞胺骨架之樹脂。藉由使上述硬化型接著劑含有上述主鏈之重複單元具有醯亞胺骨架之樹脂，上述接著層、及已硬化之上述暫時固定材之紫外區域之光的吸收性進一步提高，故即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述主鏈之重複單元具有醯亞胺骨架之樹脂具有醯亞胺骨架，藉此，耐熱性極優異，即便於進行300℃以上之高溫加工處理之情形時，亦不易產生主鏈之分解。因此，藉由使上述光硬化型接著劑含有主鏈之重複單元具有醯亞胺骨架之樹脂，能夠進一步抑制上述接著膜、及上述暫時固定材於高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制上述接著膜、及上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 The curable adhesive preferably contains a curable resin. The curable resin preferably contains a resin having an imide skeleton in the repeating unit of the main chain. By making the curable adhesive contain a resin having an imide skeleton in the repeating unit of the main chain, the absorption of the light in the ultraviolet region of the bonding layer and the cured temporary fixing material is further improved, so that even when irradiated with low-energy laser light, the support can be more efficiently peeled off. In addition, the bonding layer and the temporary fixing material are more easily cured by irradiation with light, so that the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the peelability of the adhesive film and the hardened temporary fixing material from the adherend is further improved, thereby further preventing the generation of paste residues when peeling from the adherend. In addition, the resin having an imide skeleton in the repeating unit of the main chain has an imide skeleton, thereby having extremely excellent heat resistance, and the main chain is not easily decomposed even when subjected to high-temperature processing at more than 300°C. Therefore, by making the above-mentioned light-curing adhesive contain a resin having an imide skeleton in the repeating unit of the main chain, the generation of gaps and bulges between the above-mentioned adhesive film and the temporary fixing material and the support during high-temperature processing can be further suppressed. In addition, the adhesion of the above-mentioned adhesive film and the above-mentioned temporary fixing material to the adherend during high-temperature processing can be further suppressed, so the releasability to the adherend is further improved, thereby further preventing the generation of paste residues when peeling off the adherend.

上述在主鏈之重複單元具有醯亞胺骨架之樹脂較佳為具有下述式（1）所表示之結構單元。The above-mentioned resin having an imide skeleton in the repeating unit of the main chain preferably has a structural unit represented by the following formula (1).

上述式（1）中，P 1較佳為碳數5以上50以下之芳香族基。藉由使上述P 1為碳數5以上50以下之芳香族基，上述接著層、及已硬化之上述暫時固定材之紫外區域之光之吸收性進一步提高，故即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 In the above formula (1), P1 is preferably an aromatic group having a carbon number of 5 to 50. By making the above P1 an aromatic group having a carbon number of 5 to 50, the absorption of the above bonding layer and the above hardened temporary fixing material in the ultraviolet region is further improved, so that even when irradiated with low-energy laser light, the support can be peeled off more efficiently. In addition, the above bonding layer and the above temporary fixing material are more easily hardened by irradiation light, so the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the releasability of the above bonding film and the above hardened temporary fixing material to the adherend is further improved, thereby further preventing the generation of paste residues when peeling from the adherend. Furthermore, the heat resistance of the adhesive film and the hardened temporary fixing material is better. That is, the gap and bulge between the adhesive film and the support can be further suppressed during the high-temperature processing. Furthermore, the adhesion of the adhesive film and the hardened temporary fixing material to the adherend can be further suppressed during the high-temperature processing, so the peeling property of the adherend is further improved, thereby further preventing the generation of paste residues when peeling from the adherend.

上述式（1）中，Q 1較佳為經取代或未經取代之直鏈狀、支鏈狀或環狀之碳數2以上100以下之脂肪族基。藉由使上述Q 1為經取代或未經取代之直鏈狀、支鏈狀或環狀之碳數2以上100以下之脂肪族基，上述接著膜、及上述暫時固定材之柔軟性更優異，能夠對具有凹凸之被黏著體發揮高追隨性，並且剝離時能夠更容易地剝離。 又，上述Q 1較佳為源自二胺化合物之脂肪族基。其中，就柔軟性、及上述在主鏈之重複單元具有醯亞胺骨架之樹脂與溶劑或其他成分之相容性之觀點而言，上述Q 1較佳為源自二聚二胺之脂肪族基。 上述二聚二胺係對作為不飽和脂肪酸之二聚物而獲得之環式及非環式二聚酸進行還原、胺基化而獲得之二胺化合物，例如可舉直鏈型、單環型、多環型等二聚二胺。上述二聚二胺可含有碳-碳雙鍵，亦可為加成有氫之氫化物。 In the above formula (1), Q1 is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. By making Q1 a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms, the above adhesive film and the above temporary fixing material have better flexibility, can exhibit high tracking properties to an adherend having uneven surfaces, and can be more easily peeled off. In addition, Q1 is preferably an aliphatic group derived from a diamine compound. Among them, from the viewpoint of flexibility and compatibility of the resin having an imide skeleton in the main chain repeating unit with a solvent or other components, the above Q1 is preferably an aliphatic group derived from a dimer diamine. The above dimer diamine is a diamine compound obtained by reducing and aminating a cyclic and non-cyclic dimer acid obtained as a dimer of an unsaturated fatty acid, and examples thereof include straight chain type, monocyclic type, polycyclic type, etc. dimer diamine. The above dimer diamine may contain a carbon-carbon double bond, and may also be a hydride with hydrogen added.

作為源自上述二聚二胺之脂肪族基，例如較佳為選自由下述式（2-1）所表示之基、下述式（2-2）所表示之基、下述式（2-3）所表示之基、及下述式（2-4）所表示之基所組成之群中之至少1種基。其中，更佳為下述式（2-2）所表示之基。The aliphatic group derived from the dimerized diamine is preferably at least one group selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4). Among them, a group represented by the following formula (2-2) is more preferred.

上述式（2-1）～（2-4）中，R 1～R 16分別獨立地表示直鏈狀或支鏈狀之烴基，*表示鍵結鍵。鍵結鍵*與上述式（1）中之N鍵結。 In the above formulae (2-1) to (2-4), R 1 to R 16 each independently represent a linear or branched alkyl group, and * represents a bonding bond. The bonding bond * is bonded to N in the above formula (1).

上述式（2-1）～（2-4）中，R 1～R 16所表示之烴基可為飽和烴基，亦可為不飽和烴基。其中，較佳為R 1與R 2、R 3與R 4、R 5與R 6、R 7與R 8、R 9與R 10、R 11與R 12、R 13與R 14、及R 15與R 16之合計碳數為7以上50以下。藉由使上述合計碳數為上述範圍內，上述在主鏈之重複單元具有醯亞胺骨架之樹脂與溶劑或其他成分之相容性更優異，且上述接著膜、及上述暫時固定材之柔軟性更優異。上述合計碳數更佳為9以上，進而較佳為12以上，進而更佳為14以上。上述合計碳數更佳為35以下，進而較佳為25以下，進而更佳為18以下。 In the above formulae (2-1) to (2-4), the alkyl groups represented by R 1 to R 16 may be saturated alkyl groups or unsaturated alkyl groups. Preferably, the total carbon number of R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 9 and R 10 , R 11 and R 12 , R 13 and R 14 , and R 15 and R 16 is 7 or more and 50 or less. By making the total carbon number within the above range, the compatibility of the resin having an imide skeleton in the repeating unit of the main chain with the solvent or other components is further improved, and the flexibility of the above adhesive film and the above temporary fixing material is further improved. The total carbon number is more preferably 9 or more, further preferably 12 or more, further preferably 14 or more. The total carbon number is more preferably 35 or less, further preferably 25 or less, further preferably 18 or less.

於上述式（2-1）所表示之基、上述式（2-2）所表示之基、上述式（2-3）所表示之基、及上述式（2-4）所表示之基中，光學異構性並無特別限定，包含任一光學異構性。In the group represented by the above formula (2-1), the group represented by the above formula (2-2), the group represented by the above formula (2-3), and the group represented by the above formula (2-4), the optical isomerism is not particularly limited, and includes any optical isomerism.

上述硬化性樹脂100質量份中，上述在主鏈之重複單元具有醯亞胺骨架之樹脂之含量之較佳下限為40質量份，較佳上限為100質量份。 藉由使上述在主鏈之重複單元具有醯亞胺骨架之樹脂之含量為該範圍內，上述接著層、及已硬化之上述暫時固定材之紫外區域之光之吸收性進一步提高，故即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制高溫加工處理中之上述接著膜、及已硬化之上述暫時固定材對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 The preferred lower limit of the content of the resin having an imide skeleton in the repeating unit of the main chain in 100 parts by mass of the curable resin is 40 parts by mass, and the preferred upper limit is 100 parts by mass. By making the content of the resin having an imide skeleton in the repeating unit of the main chain within this range, the absorption of the light in the ultraviolet region of the bonding layer and the cured temporary fixing material is further improved, so that even when irradiated with low-energy laser light, the support can be more efficiently peeled off. In addition, the bonding layer and the temporary fixing material are more easily cured by irradiation with light, so that the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured have a further improved releasability to the adherend, thereby further preventing the generation of paste residues when peeling off the adherend. In addition, the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured have better heat resistance. That is, it is possible to further suppress the generation of gaps and bulges between the support body during high-temperature processing. In addition, it is possible to further suppress the hyperadhesion of the above-mentioned adhesive film and the above-mentioned temporary fixing material to the adherend during high-temperature processing, so the releasability to the adherend is further improved, thereby further preventing the generation of paste residues when peeling off the adherend.

上述在主鏈之重複單元具有醯亞胺骨架之樹脂較佳為含有不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂。 再者，芳香環中所含有之碳-碳雙鍵不視為上述具有碳-碳雙鍵之官能基之該碳-碳雙鍵。 The above-mentioned resin having an imide skeleton in the repeating unit of the main chain is preferably a resin having an imide skeleton in the repeating unit of the main chain and containing no functional group containing a carbon-carbon double bond. Furthermore, the carbon-carbon double bond contained in the aromatic ring is not regarded as the carbon-carbon double bond of the above-mentioned functional group having a carbon-carbon double bond.

上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之重量平均分子量的較佳下限為2萬，較佳上限為200萬。藉由使上述不具有含有碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之重量平均分子量為2萬以上，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 藉由使上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之重量平均分子量為200萬以下，上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂與溶劑或其他成分之相容性更優異。上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之重量平均分子量之更佳下限為4萬，更佳上限為60萬。 再者，於本說明書中，上述重量平均分子量係藉由凝膠滲透層析（GPC）法以聚苯乙烯換算分子量之形式測定。具體而言，例如使用APC系統（Waters公司製造），於流動相THF、流量1.0 ml/min、管柱溫度40℃、樣品濃度0.2質量%、RI・PDA檢測器之條件下進行測定。作為上述管柱，可使用HR-MB-M 6.0×150 mm（Waters公司製造）等。 The preferred lower limit of the weight average molecular weight of the resin having no functional group containing carbon-carbon double bonds and having an imide skeleton in the repeating unit of the main chain is 20,000, and the preferred upper limit is 2 million. By making the weight average molecular weight of the resin having no functional group containing carbon-carbon double bonds and having an imide skeleton in the repeating unit of the main chain more than 20,000, the heat resistance of the bonding film and the hardened temporary fixing material is better. That is, the generation of gaps and bulges between the bonding film and the hardened temporary fixing material and the support during high-temperature processing can be further suppressed. In addition, the adhesion of the adhesive film and the hardened temporary fixing material to the adherend during the high temperature processing can be further suppressed, so the peeling property of the adherend is further improved, thereby further preventing the generation of paste residues when peeling from the adherend. By making the weight average molecular weight of the resin having no functional group containing carbon-carbon double bonds and having an imide skeleton in the repeating units of the main chain less than 2 million, the compatibility of the resin having no functional group containing carbon-carbon double bonds and having an imide skeleton in the repeating units of the main chain with solvents or other components is more excellent. The weight average molecular weight of the resin having no functional group containing carbon-carbon double bonds and having an imide skeleton in the repeating unit of the main chain has a better lower limit of 40,000 and a better upper limit of 600,000. Furthermore, in this specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) in the form of polystyrene conversion molecular weight. Specifically, for example, the measurement is performed using an APC system (manufactured by Waters) under the conditions of mobile phase THF, flow rate 1.0 ml/min, column temperature 40°C, sample concentration 0.2 mass%, and RI・PDA detector. As the above-mentioned column, HR-MB-M 6.0×150 mm (manufactured by Waters) and the like can be used.

作為上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂，具體而言，例如可舉具有上述式（1）所表示之結構單元且兩末端具有不含碳-碳雙鍵之官能基之樹脂等。Specific examples of the resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain include a resin having a structural unit represented by the above formula (1) and having a functional group containing no carbon-carbon double bond at both ends.

具有上述式（1）所表示之結構單元且兩末端具有不含碳-碳雙鍵之官能基之樹脂亦可具有下述式（3）所表示之結構單元。The resin having the structural unit represented by the above formula (1) and having functional groups having no carbon-carbon double bond at both ends may also have the structural unit represented by the following formula (3).

上述式（3）中，P 2表示芳香族基，Q 2表示經取代或未經取代之具有芳香族結構之基。 In the above formula (3), P2 represents an aromatic group, and Q2 represents a substituted or unsubstituted group having an aromatic structure.

上述式（3）中，P 2較佳為碳數5以上50以下之芳香族基。藉由使上述P 2為碳數5以上50以下之芳香族基，上述接著層、及已硬化之上述暫時固定材之紫外區域之光之吸收性進一步提高，故即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 In the above formula (3), P2 is preferably an aromatic group having a carbon number of 5 or more and 50 or less. By making the above P2 an aromatic group having a carbon number of 5 or more and 50 or less, the absorption of the above bonding layer and the above hardened temporary fixing material in the ultraviolet region is further improved, so that even when irradiated with low-energy laser light, the support can be more efficiently peeled off. In addition, the above bonding layer and the above temporary fixing material are more easily hardened by irradiation light, so the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the releasability of the above bonding film and the above hardened temporary fixing material to the adherend is further improved, thereby further preventing the generation of paste residues when peeling from the adherend. Furthermore, the heat resistance of the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured is more excellent. That is, it is possible to further suppress the generation of gaps and bulges between the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured and the support during high-temperature processing. Furthermore, it is possible to further suppress the hyperadhesion of the above-mentioned adhesive film and the above-mentioned temporary fixing material to the adherend during high-temperature processing, so the peeling property of the adherend is further improved, thereby further preventing the generation of paste residues when peeling from the adherend.

上述式（3）中，Q 2較佳為經取代或未經取代之碳數5以上50以下之具有芳香族結構之基。藉由使上述Q 2為經取代或未經取代之碳數5以上50以下之具有芳香族結構之基，上述接著層、及已硬化之上述暫時固定材之紫外區域之光之吸收性進一步提高，故即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 In the above formula (3), Q2 is preferably a substituted or unsubstituted group having an aromatic structure with a carbon number of 5 or more and 50 or less. By making the above Q2 a substituted or unsubstituted group having an aromatic structure with a carbon number of 5 or more and 50 or less, the absorption of the light in the ultraviolet region of the above bonding layer and the above hardened temporary fixing material is further improved, so that even when irradiated with low-energy laser light, the support body can be more efficiently peeled off. In addition, the above bonding layer and the above temporary fixing material are more easily hardened by irradiation with light, so that the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured have a further improved releasability to the adherend, thereby further preventing the generation of paste residues when peeling off the adherend. In addition, the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured have better heat resistance. That is, it is possible to further suppress the generation of gaps and bulges between the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured and the support during high-temperature processing. In addition, it is possible to further suppress the hyperadhesion of the above-mentioned adhesive film and the above-mentioned temporary fixing material to the adherend during high-temperature processing, so the releasability to the adherend is further improved, thereby further preventing the generation of paste residues when peeling off the adherend.

作為上述不具有碳-碳雙鍵之官能基，例如可舉脂肪族基、脂環式基、芳香族基、酸酐基、胺基等。具體而言，可舉成為上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之原料的酸酐或二胺化合物之未反應的單末端構成基等。 具有上述式（1）所表示之結構單元且兩末端具有不含碳-碳雙鍵之官能基之樹脂於兩末端所具有之不含碳-碳雙鍵之官能基可相同，亦可不同。 Examples of the functional group not having a carbon-carbon double bond include aliphatic groups, alicyclic groups, aromatic groups, acid anhydride groups, and amine groups. Specifically, examples include unreacted single-terminal constituent groups of an acid anhydride or diamine compound that is a raw material for the resin not having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain. The resin having the structural unit represented by the above formula (1) and having a functional group not having a carbon-carbon double bond at both ends may have the same or different functional groups not having a carbon-carbon double bond at both ends.

具有上述式（1）所表示之結構單元且兩末端具有不含碳-碳雙鍵之官能基之樹脂中的上述式（1）所表示之結構單元之含有比率較佳為30莫耳%以上，更佳為50莫耳%以上，較佳為90莫耳%以下，更佳為80莫耳%以下。 於具有上述式（1）所表示之結構單元且兩末端具有不含碳-碳雙鍵之官能基之樹脂具有上述式（3）所表示之結構單元之情形時，上述式（3）所表示之結構單元之含有比率較佳為5莫耳%以上，更佳為10莫耳%以上，進而較佳為20莫耳%以上，較佳為50莫耳%以下，更佳為30莫耳%以下。 於上述式（1）所表示之結構單元及上述式（3）所表示之結構單元中，藉由使各結構單元之含量為上述範圍內，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中與支持體之間產生空隙及隆起，又，與被黏著體剝離時能夠更容易地剝離。 再者，上述式（1）所表示之結構單元及上述式（3）所表示之結構單元可具有各結構單元連續排列之由嵌段成分構成之嵌段結構，亦可具有各結構單元無規排列之無規結構。 The content ratio of the structural unit represented by the above formula (1) in the resin having the structural unit represented by the above formula (1) and having functional groups without carbon-carbon double bonds at both ends is preferably 30 mol% or more, more preferably 50 mol% or more, preferably 90 mol% or less, and more preferably 80 mol% or less. In the case where the resin having the structural unit represented by the above formula (1) and having functional groups without carbon-carbon double bonds at both ends has the structural unit represented by the above formula (3), the content ratio of the structural unit represented by the above formula (3) is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, preferably 50 mol% or less, and more preferably 30 mol% or less. In the structural unit represented by the above formula (1) and the structural unit represented by the above formula (3), by making the content of each structural unit within the above range, it is possible to further suppress the generation of gaps and bulges between the above adhesive film and the above hardened temporary fixing material and the support during high temperature processing, and it is possible to more easily peel off the adherend. Furthermore, the structural unit represented by the above formula (1) and the structural unit represented by the above formula (3) may have a block structure composed of block components in which each structural unit is continuously arranged, or may have a random structure in which each structural unit is randomly arranged.

作為製造上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂的方法，例如可舉使二胺化合物與芳香族酸酐反應之方法等。As a method for producing the above-mentioned resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain, for example, a method of reacting a diamine compound with an aromatic acid anhydride can be cited.

作為上述二胺化合物，可使用脂肪族二胺化合物或芳香族二胺化合物之任一者。 藉由使用脂肪族二胺化合物作為上述二胺化合物，上述接著層、及上述暫時固定材之柔軟性更優異，能夠對具有凹凸之被黏著體發揮較高之追隨性，並且剝離時能夠更容易地剝離。 又，藉由使用芳香族二胺化合物作為上述二胺化合物，上述接著膜、及已硬化之上述暫時固定材之紫外區域之光之吸收性進一步提高，故即便於照射低能量之雷射光之情形時，能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。 上述二胺化合物可單獨使用，亦可將2種以上組合使用。 As the above-mentioned diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used. By using an aliphatic diamine compound as the above-mentioned diamine compound, the above-mentioned bonding layer and the above-mentioned temporary fixing material have better flexibility, can exhibit higher tracking properties to the adherend with unevenness, and can be peeled off more easily when peeled off. In addition, by using an aromatic diamine compound as the above-mentioned diamine compound, the absorption of the above-mentioned bonding film and the cured above-mentioned temporary fixing material in the ultraviolet region is further improved, so even when irradiated with low-energy laser light, the support can be peeled off more efficiently. Furthermore, the above-mentioned adhesive layer and the above-mentioned temporary fixing material are more easily cured by irradiation with light, so that the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the above-mentioned adhesive film and the above-mentioned temporary fixing material that have been cured have further improved releasability from the adherend, thereby further preventing the generation of paste residues when peeling from the adherend. Furthermore, the above-mentioned adhesive film and the above-mentioned temporary fixing material that have been cured have better heat resistance. The above-mentioned diamine compound can be used alone or in combination of two or more.

作為上述脂肪族二胺化合物，例如可舉1,10-二胺基癸烷、1,12-二胺基十二烷、二聚二胺、1,2-二胺基-2-甲基丙烷、1,2-二胺基環己烷、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,7-二胺基庚烷、1,8-二胺基薄荷烷、1,8-二胺基辛烷、1,9-二胺基壬烷、3,3'-二胺基-N-甲基二丙基胺、二胺順丁烯二腈、1,3-二胺基戊烷、雙(4-胺基-3-甲基環己基)甲烷、1,2-雙(2-胺基乙氧基)乙烷、3(4),8(9)-雙(胺基甲基)三環(5.2.1.02,6)癸烷等。Examples of the aliphatic diamine compound include 1,10-diaminodecane, 1,12-diaminododecane, diaminodiamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminopentane, diaminooctane, 1,8-diaminooctane, 1,9-diaminononane, 3,3'-diamino-N-methyldipropylamine, diaminobutene dinitrile, 1,3-diaminopentane, bis(4-amino-3-methylcyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane, 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane, etc.

上述脂肪族二胺化合物之中，就柔軟性、及上述不具有含碳-碳雙鍵之官能基且主鏈之重複單元具有醯亞胺骨架之樹脂與溶劑或其他成分之相容性之觀點而言，較佳為二聚二胺。作為上述二聚二胺，具體而言，例如可舉能夠構成選自由上述式（2-1）所表示之基、式（2-2）所表示之基、式（2-3）所表示之基、及式（2-4）所表示之基所組成之群中之至少1種基之二聚二胺等。Among the above-mentioned aliphatic diamine compounds, dimerized diamine is preferred from the viewpoint of flexibility and compatibility with the above-mentioned resin having no functional group containing a carbon-carbon double bond and having an imide skeleton as a main chain repeating unit, and solvents or other components. As the above-mentioned dimerized diamine, for example, dimerized diamine that can constitute at least one group selected from the group consisting of the group represented by the above-mentioned formula (2-1), the group represented by the formula (2-2), the group represented by the formula (2-3), and the group represented by the formula (2-4) can be cited.

作為上述芳香族二胺化合物，例如可舉9,10-二胺基菲（9,10-diaminophenanthrene）、4,4'-二胺基八氟聯苯、3,7-二胺基-2-甲氧基茀、4,4'-二胺基二苯甲酮、3,4-二胺基二苯甲酮、3,4-二胺基甲苯、2,6-二胺基蒽醌、2,6-二胺基甲苯、2,3-二胺基甲苯、1,8-二胺基萘、2,4-二胺基甲苯、2,5-二胺基甲苯、1,4-二胺基蒽醌、1,5-二胺基蒽醌、1,5-二胺基萘、1,2-二胺基蒽醌、2,4-異丙苯二胺、1,3-雙胺基甲基苯、1,3-雙胺基甲基環己烷、2-氯-1,4-二胺基苯、1,4-二胺基-2,5-二氯苯、1,4-二胺基-2,5-二甲基苯、4,4'-二胺基-2,2'-雙三氟甲基聯苯、雙(胺基-3-氯苯基)乙烷、雙(4-胺基-3,5-二甲基苯基)甲烷、雙(4-胺基-3,5-二乙基苯基)甲烷、9,9'-雙(4-胺基-3-乙基二胺基茀)、2,3-二胺基萘、2,3-二胺基苯酚、雙(4-胺基-5-甲基苯基)甲烷、雙(4-胺基-3-甲基苯基)甲烷、雙(4-胺基-3-乙基苯基)甲烷、4,4'-二胺基苯基碸、3,3'-二胺基苯基碸、雙(4-(4-胺基苯氧基)苯基)碸、雙(4-(3-胺基苯氧基)苯基)碸、4,4'-氧二苯胺、4,4'-二胺基二苯硫醚、3,4'-氧二苯胺、2,2-雙(4-(4-胺基苯氧基)苯基)丙烷、1,3-雙(4-胺基苯氧基)苯、4,4'-雙(4-胺基苯氧基)聯苯、4,4'-二胺基-3,3'-二羥基聯苯、4,4'-二胺基-3,3'-二甲基聯苯、4,4'-二胺基-3,3'-二甲氧基聯苯、Bisaniline M、Bisaniline P、9,9-雙(4-胺基苯基)茀、鄰聯甲苯胺碸（O-Tolidine Sulfone）、5,5'-亞甲基雙(鄰胺基苯甲酸)、1,3-雙(4-胺基苯氧基)-2,2-二甲基丙烷、1,3-雙(4-胺基苯氧基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、2,3,5,6-四甲基-1,4-苯二胺、3,3',5,5'-四甲基聯苯胺、4,4'-二胺基苯甲醯苯胺、2,2-雙(4-胺基苯基)六氟丙烷、聚氧伸烷基二胺類（例如Huntsman公司製造之Jeffamine D-230、D-400、D-2000、D-4000等）、1,3-環己烷雙(甲基胺)、間苯二甲胺、對苯二甲胺等。Examples of the aromatic diamine compound include 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminonaphthalene, Aminatoluene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-isopropylphenylenediamine, 1,3-diaminomethylbenzene, 1,3-diaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5- bis(4-amino-3,5-diethylphenyl)methane, 9,9'-bis(4-amino-3-ethyldiaminofluorene), 2,3-diaminonaphthalene, 2,3-diaminophenol, bis(4-amino-5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenylsulfonate, 3,3'-diaminophenylsulfonate, bis(4-(4-aminophenoxy)phenyl)sulfonate, bis(4-(3-aminophenoxy)phenyl)sulfonate 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, Bisaniline M, Bisaniline P, 9,9-Bis(4-aminophenyl)fluorene, o-Tolidine Sulfone, 5,5'-methylenebis(o-aminobenzoic acid), 1,3-Bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-Bis(4-aminophenoxy)propane, 1,4-Bis(4-aminophenoxy)butane, 1,5-Bis(4-aminophenoxy)pentane, 2,3,5,6-Tetramethyl-1,4-phenylenediamine, 3,3',5,5'-Tetramethylbenzidine, 4,4'-Diaminobenzanilide, 2,2-Bis(4-aminophenyl)hexafluoropropane, polyoxyalkylene diamines (e.g. Jeffamine manufactured by Huntsman Corporation) D-230, D-400, D-2000, D-4000, etc.), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, p-xylylenediamine, etc.

作為上述芳香族酸酐，例如可舉焦蜜石酸、1,2,5,6-萘四羧酸、2,3,6,7-萘四羧酸、1,2,4,5-萘四羧酸、1,4,5,8-萘四羧酸、3,3',4,4'-二苯甲酮四羧酸、3,3',4,4'-聯苯醚四羧酸、3,3',4,4'-聯苯四羧酸、2,3,5,6-吡啶四羧酸、3,4,9,10-苝四羧酸、4,4'-磺醯基二鄰苯二甲酸、1-三氟甲基-2,3,5,6-苯四羧酸、2,2',3,3'-聯苯四羧酸、2,2-雙(3,4-二羧基苯基)丙烷、2,2-雙(2,3-二羧基苯基)丙烷、1,1-雙(2,3-二羧基苯基)乙烷、1,1-雙(3,4-二羧基苯基)乙烷、雙(2,3-二羧基苯基)甲烷、雙(3,4-二羧基苯基)甲烷、雙(3,4-二羧基苯基)碸、雙(3,4-二羧基苯基)醚、苯-1,2,3,4-四羧酸、2,2',3,3'-二苯甲酮四羧酸、2,3,3',4'-二苯甲酮四羧酸、菲-1,8,9,10-四羧酸、吡-2,3,5,6-四羧酸、噻吩-2,3,4,5-四羧酸、2,3,3',4'-聯苯四羧酸、4,4'-雙(3,4-二羧基苯氧基)二苯硫醚、4,4'-(4,4'-亞異丙基二苯氧基)-雙(鄰苯二甲酸)等羧酸酐。Examples of the aromatic acid anhydride include pyromelitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyl ethertetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, and 2,2',3,3'-biphenyltetracarboxylic acid. 、2,2-bis(3,4-dicarboxyphenyl)propane、2,2-bis(2,3-dicarboxyphenyl)propane、1,1-bis(2,3-dicarboxyphenyl)ethane、1,1-bis(3,4-dicarboxyphenyl)ethane、bis(2,3-dicarboxyphenyl)methane、bis(3,4-dicarboxyphenyl)methane、bis(3,4-dicarboxyphenyl)sulfonium、bis(3,4-dicarboxyphenyl)ether、benzene-1,2,3,4-tetracarboxylic acid、2,2',3,3'-benzophenonetetracarboxylic acid、2,3,3',4'-benzophenonetetracarboxylic acid、phenanthrene-1,8,9,10-tetracarboxylic acid、pyridine carboxylic anhydrides such as 2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, and 4,4'-(4,4'-isopropylidene diphenoxy)-bis(phthalic acid).

上述硬化性樹脂100質量份中之上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之含量之較佳下限為10質量份，較佳上限為90質量份。藉由使上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之含量為該範圍內，上述接著膜、及已硬化之上述暫時固定材自被黏著體剝離時能夠更容易地剝離。就進而提高剝離性能之觀點而言，上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之含量的更佳下限為20質量份，更佳上限為80質量份。The preferred lower limit of the content of the resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain in 100 parts by mass of the curable resin is 10 parts by mass, and the preferred upper limit is 90 parts by mass. By making the content of the resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain within this range, the adhesive film and the hardened temporary fixing material can be more easily peeled off from the adherend. From the viewpoint of further improving the stripping performance, the content of the resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating units of the main chain has a more preferred lower limit of 20 parts by mass and a more preferred upper limit of 80 parts by mass.

上述在主鏈之重複單元具有醯亞胺骨架之樹脂較佳為含有具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂。藉由含有上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著膜、及上述暫時固定材藉由光之照射等，其整體均勻且迅速地聚合交聯，彈性模數上升，藉此，上述接著膜、及上述暫時固定材之接著力大幅降低。因此，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，對被黏著體之剝離性進一步提高，從而能夠防止剝離時產生糊劑殘留。 於上述主鏈之重複單元具有醯亞胺骨架之樹脂包含上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之情形時，較佳為除上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂以外，進而包含上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂。 The resin having an imide skeleton in the repeating unit of the main chain is preferably a resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain. By containing the functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain, the support can be peeled off more efficiently even when irradiated with low-energy laser light. In addition, the above-mentioned bonding film and the above-mentioned temporary fixing material are uniformly and rapidly polymerized and cross-linked by irradiation with light, and the elastic modulus increases, thereby greatly reducing the bonding force of the above-mentioned bonding film and the above-mentioned temporary fixing material. Therefore, the adhesion of the adhesive film and the hardened temporary fixing material to the adherend during high temperature processing can be further suppressed, and the peeling property of the adherend can be further improved, thereby preventing the generation of paste residue during peeling. When the resin having an imide skeleton in the repeating units of the main chain mentioned above includes the resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating units of the main chain mentioned above, it is preferred that in addition to the resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating units of the main chain mentioned above, it further includes the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating units of the main chain mentioned above.

作為上述具有碳-碳雙鍵之官能基，例如可舉可經取代之馬來醯亞胺基、甲基順丁烯二醯亞胺基（citraconimide group）、乙烯基醚基、烯丙基、(甲基)丙烯醯基等。其中，就獲得更高之耐熱性之方面而言，較佳為可經取代之馬來醯亞胺基。 再者，於本說明書中，「(甲基)丙烯醯基」意指丙烯醯基或甲基丙烯醯基。 As the functional group having a carbon-carbon double bond, for example, there can be substituted maleimide group, citraconimide group, vinyl ether group, allyl group, (meth)acryl group, etc. Among them, substituted maleimide group is preferred in terms of obtaining higher heat resistance. Furthermore, in this specification, "(meth)acryl group" means acryl group or methacryl group.

上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂的具有碳-碳雙鍵之官能基之官能基當量（重量平均分子量/具有碳-碳雙鍵之官能基之數）較佳為4000以下。藉由使上述具有碳-碳雙鍵之官能基之官能基當量為4000以下，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。認為其原因在於：藉由使樹脂之分子中以一定以上之密度具有含碳-碳雙鍵之官能基，交聯間距離變短，藉此，進一步抑制接著亢進。上述具有碳-碳雙鍵之官能基之官能基當量更佳為3000以下，進而較佳為2000以下。 又，上述具有碳-碳雙鍵之官能基之官能基當量之較佳下限並無特別，實質下限為600左右。 The functional group equivalent of the functional group having a carbon-carbon double bond of the resin having an imide skeleton in the repeating unit of the main chain (weight average molecular weight/number of functional groups having a carbon-carbon double bond) is preferably 4000 or less. By making the functional group equivalent of the functional group having a carbon-carbon double bond below 4000, the support can be more efficiently peeled off even when irradiated with low-energy laser light. In addition, the bonding layer and the temporary fixing material are more easily hardened by irradiation with light, so the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the peelability of the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured from the adherend is further improved, thereby being able to further prevent the generation of paste residues when peeling from the adherend. In addition, the heat resistance of the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured is more excellent. It is believed that the reason is that by making the functional group containing carbon-carbon double bonds in the molecules of the resin have a certain density or more, the crosslinking distance becomes shorter, thereby further suppressing the hyperadhesion. The functional group equivalent of the functional group having carbon-carbon double bonds is preferably less than 3000, and more preferably less than 2000. In addition, there is no particular lower limit for the functional group equivalent of the functional group having a carbon-carbon double bond, and the actual lower limit is about 600.

上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之重量平均分子量較佳為1000以上10萬以下。藉由使上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之重量平均分子量為1000以上，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 進而，上述硬化型接著劑容易成膜，並且上述接著膜、及上述暫時固定材發揮某一程度之柔軟性，因此，能夠對具有凹凸之被黏著體發揮較高之追隨性，且剝離時能夠更容易地剝離。 藉由使上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂的重量平均分子量為10萬以下，上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂與溶劑或其他成分之相容性優異。上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之重量平均分子量更佳為1500以上5萬以下，進而較佳為2000以上且未達2萬。 The weight average molecular weight of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain is preferably 1000 or more and 100,000 or less. By making the weight average molecular weight of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain above 1000, the support can be peeled off more efficiently even when irradiated with low-energy laser light. In addition, the above-mentioned bonding layer and the above-mentioned temporary fixing material are more easily hardened by irradiation with light, so that the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the above-mentioned adhesive film and the above-mentioned temporary fixing material that have been cured have further improved releasability from the adherend, thereby being able to further prevent the generation of adhesive residues when being peeled off from the adherend. Furthermore, the above-mentioned curing adhesive is easy to form a film, and the above-mentioned adhesive film and the above-mentioned temporary fixing material have a certain degree of softness, so that they can have a higher tracking ability for the adherend with uneven surfaces, and can be peeled off more easily when peeling off. By making the weight average molecular weight of the resin having a functional group containing a carbon-carbon double bond and an amide skeleton in the repeating unit of the main chain below 100,000, the resin having a functional group containing a carbon-carbon double bond and an amide skeleton in the repeating unit of the main chain has excellent compatibility with solvents or other components. The weight average molecular weight of the resin having a functional group containing a carbon-carbon double bond and an amide skeleton in the repeating unit of the main chain is preferably above 1500 and below 50,000, and further preferably above 2000 and below 20,000.

於上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂中，具有碳-碳雙鍵之官能基可存在於側鏈或末端之任一者，較佳為存在於兩末端，更佳為除兩末端以外亦進而存在於側鏈。 上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之兩末端之具有碳-碳雙鍵之官能基之反應性較高，能夠藉由光之照射等使上述接著層、及上述暫時固定材更充分地硬化。結果，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，能夠進一步防止剝離時產生糊劑殘留。又，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。 進而，藉由使具有碳-碳雙鍵之官能基存在於上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之側鏈，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著膜、及上述暫時固定材之耐熱性更優異。認為其原因在於：交聯間距離變短，藉此進一步抑制接著亢進。又，藉由使具有碳-碳雙鍵之官能基存在於上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之側鏈，容易將上述重量平均分子量設為1000以上，同時將上述官能基當量調整為4000以下。藉此，上述接著膜、及已硬化之上述暫時固定材具有充分之初始接著力，同時能夠進一步抑制產生接著亢進或剝離時產生糊劑殘留。進而，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。 In the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain, the functional group having a carbon-carbon double bond may be present in either the side chain or the terminal, preferably in both terminals, and more preferably in both terminals and in the side chain. The functional groups having carbon-carbon double bonds at both terminals of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain have a higher reactivity, and can make the above-mentioned bonding layer and the above-mentioned temporary fixing material more fully hardened by irradiation with light. As a result, the adhesion of the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured to the adherend during the high-temperature processing can be further suppressed, so the releasability of the adherend is further improved, and the generation of paste residues during the peeling can be further prevented. In addition, even when irradiated with low-energy laser light, the support can be peeled off more efficiently. Furthermore, by allowing a functional group having a carbon-carbon double bond to exist in the side chain of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain, the support can be peeled off more efficiently even when irradiated with low-energy laser light. Furthermore, the heat resistance of the above-mentioned adhesive film and the above-mentioned temporary fixing material is more excellent. The reason is believed to be that the cross-linking distance is shortened, thereby further suppressing the hyperadhesion. Furthermore, by allowing the functional group having a carbon-carbon double bond to exist in the side chain of the resin having a functional group containing a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain, it is easy to set the above-mentioned weight average molecular weight to more than 1000, and at the same time adjust the above-mentioned functional group equivalent to less than 4000. Thereby, the above-mentioned adhesive film and the hardened above-mentioned temporary fixing material have sufficient initial adhesion, and at the same time can further suppress the generation of hyperadhesion or the generation of paste residues during peeling. Furthermore, even when irradiating low-energy laser light, the support can be removed more efficiently.

如上所述，於上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂中，具有碳-碳雙鍵之官能基可存在於側鏈或末端之任一者。於側鏈或末端之任一者係具有碳-碳雙鍵之官能基以外之官能基（不具有碳-碳雙鍵之官能基）之情形時，作為該不具有碳-碳雙鍵之官能基，例如可舉脂肪族基、脂環式基、芳香族基、酸酐基、胺基等。具體而言，可舉成為上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之原料的酸酐、二胺化合物之未反應之單末端構成基等。於上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂於側鏈或末端具有2個以上之上述不具有碳-碳雙鍵之官能基之情形時，各不具有碳-碳雙鍵之官能基可相同，亦可不同。As described above, in the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain, the functional group having a carbon-carbon double bond may be present in either the side chain or the terminal. In the case where a functional group other than a functional group having a carbon-carbon double bond (a functional group not having a carbon-carbon double bond) is present in either the side chain or the terminal, examples of the functional group not having a carbon-carbon double bond include aliphatic groups, alicyclic groups, aromatic groups, acid anhydride groups, and amine groups. Specifically, examples include unreacted single terminal constituent groups of acid anhydrides and diamine compounds that are raw materials for the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain. When the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain has two or more functional groups not having a carbon-carbon double bond on the side chain or at the end, the functional groups not having a carbon-carbon double bond may be the same or different.

作為上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂，具體而言，例如可舉具有上述式（1）所表示之結構單元，於末端及側鏈之至少任一者具有含碳-碳雙鍵之官能基的樹脂等。Specific examples of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain include a resin having a structural unit represented by the above formula (1) and having a functional group containing a carbon-carbon double bond at at least one of the terminal and the side chain.

具有上述式（1）所表示之結構單元且於末端及側鏈之至少任一者具有含碳-碳雙鍵之官能基的樹脂亦可具有選自由下述式（4-1）所表示之結構單元及下述式（4-2）所表示之結構單元所組成之群中之至少1種結構單元。The resin having the structural unit represented by the above formula (1) and having a functional group containing a carbon-carbon double bond at at least one of the terminal and the side chain may also have at least one structural unit selected from the group consisting of the structural unit represented by the following formula (4-1) and the structural unit represented by the following formula (4-2).

式（4-1）中，P 3表示芳香族基，Q 3表示經取代或未經取代之具有芳香族結構之基，式（4-2）中，P 4表示芳香族基，R表示經取代或未經取代之支鏈狀之脂肪族基或芳香族基，X表示具有碳-碳雙鍵之官能基。 In formula (4-1), P 3 represents an aromatic group, Q 3 represents a substituted or unsubstituted group having an aromatic structure, and in formula (4-2), P 4 represents an aromatic group, R represents a substituted or unsubstituted branched aliphatic group or aromatic group, and X represents a functional group having a carbon-carbon double bond.

上述式（4-1）中之P 3及上述式（4-2）中之P 4較佳為碳數5～50之芳香族基。藉由使上述P 3及P 4為碳數5～50之芳香族基，上述接著層、及已硬化之上述暫時固定材之紫外區域之光的吸收性進一步提高，故即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故能夠進一步防止與被黏著體剝離時產生糊劑殘留。 P3 in the above formula (4-1) and P4 in the above formula (4-2) are preferably aromatic groups having 5 to 50 carbon atoms. By making P3 and P4 aromatic groups having 5 to 50 carbon atoms, the absorption of the light in the ultraviolet region of the above bonding layer and the above hardened temporary fixing material is further improved, so that even when irradiating low-energy laser light, the support can be more efficiently peeled off. In addition, the above bonding layer and the above temporary fixing material are more easily hardened by irradiation with light, so that the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the peelability of the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured to the adherend is further improved, thereby being able to further prevent the generation of paste residues when peeling off the adherend. In addition, the heat resistance of the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured is more excellent. That is, it is possible to further suppress the generation of gaps and bulges between the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured and the support during high-temperature processing. In addition, it is possible to further suppress the hyperadhesion of the above-mentioned adhesive film and the above-mentioned temporary fixing material to the adherend during high-temperature processing, so it is possible to further prevent the generation of paste residues when peeling off the adherend.

上述式（4-1）中，Q 3較佳為經取代或未經取代之碳數5～50之具有芳香族結構之基。藉由使上述Q 3為經取代或未經取代之碳數5～50之具有芳香族結構之基，上述接著層、及已硬化之上述暫時固定材之紫外區域之光之吸收性進一步提高，故即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 In the above formula (4-1), Q3 is preferably a substituted or unsubstituted group having 5 to 50 carbon atoms and having an aromatic structure. By making the above Q3 a substituted or unsubstituted group having 5 to 50 carbon atoms and having an aromatic structure, the absorption of the above bonding layer and the above hardened temporary fixing material in the ultraviolet region is further improved, so that even when irradiated with low-energy laser light, the support can be more efficiently peeled off. In addition, the above bonding layer and the above temporary fixing material are more easily hardened by irradiation with light, so that the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured have a further improved releasability to the adherend, thereby further preventing the generation of paste residues when peeling off the adherend. In addition, the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured have better heat resistance. That is, it is possible to further suppress the generation of gaps and bulges between the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured and the support during high-temperature processing. In addition, it is possible to further suppress the hyperadhesion of the above-mentioned adhesive film and the above-mentioned temporary fixing material to the adherend during high-temperature processing, so the releasability to the adherend is further improved, thereby further preventing the generation of paste residues when peeling off the adherend.

上述式（4-2）中，R較佳為經取代或未經取代之支鏈狀之碳數2～100之脂肪族基或芳香族基。藉由使上述R為經取代或未經取代之支鏈狀之碳數2～100之脂肪族基或芳香族基，上述接著膜、及上述暫時固定材之柔軟性更優異，能夠對具有凹凸之被黏著體發揮較高之追隨性，並且剝離時能夠更容易地剝離。In the above formula (4-2), R is preferably a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms. By making the above R a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms, the above adhesive film and the above temporary fixing material have better flexibility, can exhibit higher tracking properties to the adherend with uneven surfaces, and can be more easily peeled off.

上述式（4-2）中，較佳為R係具有芳香族酯基或芳香族醚基之芳香族基，並且該R中之該芳香族酯基或該芳香族醚基與X鍵結。 此處，上述「芳香族酯基」意指酯基直接鍵結於芳香環之基，上述「芳香族醚基」意指醚基直接鍵結於芳香環之基。藉由將如上所述般鍵結於酯基或醚基之部分設為芳香族基，上述接著層、及已硬化之上述暫時固定材之紫外區域之光之吸收性進一步提高，故即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 另一方面，藉由使X經由芳香族酯基或芳香族醚基鍵結於R，X中之碳-碳雙鍵不會與R共軛，因此，不會阻礙加熱或照射光時之聚合交聯。 In the above formula (4-2), it is preferred that R is an aromatic group having an aromatic ester group or an aromatic ether group, and the aromatic ester group or the aromatic ether group in R is bonded to X. Here, the above "aromatic ester group" means a group in which an ester group is directly bonded to an aromatic ring, and the above "aromatic ether group" means a group in which an ether group is directly bonded to an aromatic ring. By setting the portion bonded to the ester group or the ether group as an aromatic group, the absorption of the light in the ultraviolet region of the above bonding layer and the cured above temporary fixing material is further improved, so that even when irradiated with low-energy laser light, the support can be peeled off more efficiently. Furthermore, the above-mentioned bonding layer and the above-mentioned temporary fixing material are more easily hardened by irradiation with light, so that the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the peelability of the above-mentioned bonding film and the above-mentioned temporary fixing material that has been hardened to the adherend is further improved, thereby further preventing the generation of paste residues when peeling off the adherend. Furthermore, the above-mentioned bonding film and the above-mentioned temporary fixing material that has been hardened have better heat resistance. That is, the generation of gaps and bulges between the above-mentioned bonding film and the above-mentioned temporary fixing material that has been hardened and the support body during high-temperature processing can be further suppressed. In addition, the adhesion of the adhesive film and the hardened temporary fixing material to the adherend during high temperature processing can be further suppressed, so the peeling property of the adherend is further improved, thereby further preventing the generation of paste residues when peeling from the adherend. On the other hand, by allowing X to bond to R via an aromatic ester group or an aromatic ether group, the carbon-carbon double bond in X will not be conjugated with R, and therefore, it will not hinder polymerization crosslinking when heated or irradiated with light.

具有上述式（1）所表示之結構單元且於末端及側鏈之至少任一者具有含碳-碳雙鍵之官能基的樹脂中之上述式（1）所表示之結構單元之含有比率較佳為30莫耳%以上，更佳為50莫耳%以上，較佳為90莫耳%以下，更佳為80莫耳%以下。 於具有上述式（1）所表示之結構單元，於末端及側鏈之至少任一者具有含碳-碳雙鍵之官能基的樹脂具有上述式（4-1）所表示之結構單元之情形時，上述式（4-1）所表示之結構單元之含有比率較佳為5莫耳%以上，更佳為10莫耳%以上，進而較佳為20莫耳%以上，較佳為50莫耳%以下，更佳為30莫耳%以下。 於具有上述式（1）所表示之結構單元，於末端及側鏈之至少任一者具有含碳-碳雙鍵之官能基的樹脂具有上述式（4-2）所表示之結構單元之情形時，上述式（4-2）所表示之結構單元之含有比率較佳為10莫耳%以上，更佳為20莫耳%以上，較佳為50莫耳%以下，更佳為30莫耳%以下。 於上述式（1）所表示之結構單元、上述式（4-1）所表示之結構單元、及上述式（4-2）所表示之結構單元，藉由使各結構單元之含量為上述範圍內，上述接著層、及已硬化之上述暫時固定材之紫外區域之光之吸收性進一步提高，故即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。又，上述接著層、及上述暫時固定材藉由照射光更容易產生硬化，故能夠進一步抑制高溫加工處理中之對被黏著體之接著亢進。結果，上述接著膜、及已硬化之上述暫時固定材對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 又，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中與支持體之間產生空隙及隆起。又，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，從而能夠進一步防止與被黏著體剝離時產生糊劑殘留。 再者，上述式（1）所表示之結構單元、上述式（4-1）所表示之結構單元、及上述式（4-2）所表示之結構單元可具有各結構單元連續排列之由嵌段成分構成之嵌段結構，亦可具有各結構單元無規排列之無規結構。 The content ratio of the structural unit represented by the above formula (1) in the resin having the structural unit represented by the above formula (1) and having a functional group containing a carbon-carbon double bond at at least one of the terminal and the side chain is preferably 30 mol% or more, more preferably 50 mol% or more, preferably 90 mol% or less, and more preferably 80 mol% or less. In the case where the resin having the structural unit represented by the above formula (1) and having a functional group containing a carbon-carbon double bond at at least one of the terminal and the side chain has the structural unit represented by the above formula (4-1), the content ratio of the structural unit represented by the above formula (4-1) is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, preferably 50 mol% or less, and more preferably 30 mol% or less. In the case where the resin having the structural unit represented by the above formula (1) and having a functional group containing a carbon-carbon double bond at at least one of the terminal and the side chain has the structural unit represented by the above formula (4-2), the content ratio of the structural unit represented by the above formula (4-2) is preferably 10 mol% or more, more preferably 20 mol% or more, preferably 50 mol% or less, and more preferably 30 mol% or less. By making the content of each structural unit represented by the above formula (1), the above formula (4-1), and the above formula (4-2) within the above range, the absorption of the light in the ultraviolet region of the above bonding layer and the above hardened temporary fixing material is further improved, so that even when irradiated with low-energy laser light, the support body can be more efficiently peeled off. In addition, the above bonding layer and the above temporary fixing material are more easily hardened by irradiation with light, so that the hyperadhesion to the adherend during high-temperature processing can be further suppressed. As a result, the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured have a further improved releasability to the adherend, thereby further preventing the generation of paste residues when peeling off the adherend. In addition, the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured have better heat resistance. That is, it is possible to further suppress the generation of gaps and bulges between the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured and the support during high-temperature processing. In addition, it is possible to further suppress the hyperadhesion of the above-mentioned adhesive film and the above-mentioned temporary fixing material to the adherend during high-temperature processing, so the releasability to the adherend is further improved, thereby further preventing the generation of paste residues when peeling off the adherend. Furthermore, the structural unit represented by the above formula (1), the structural unit represented by the above formula (4-1), and the structural unit represented by the above formula (4-2) may have a block structure composed of block components in which each structural unit is arranged continuously, or may have a random structure in which each structural unit is arranged randomly.

作為製造上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂的方法，例如可舉以下方法等。 即，首先，使二胺化合物與芳香族酸酐反應而製備醯亞胺化合物。繼而，使該醯亞胺化合物之官能基與具有與該官能基反應之官能基及具有碳-碳雙鍵之官能基的化合物（以下，亦稱為「含官能基不飽和化合物」）反應，藉此，能夠獲得上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂。 又，亦可使二胺化合物與芳香族酸酐反應而製備醯亞胺化合物，進而，使例如馬來酸酐等與該醯亞胺化合物之末端反應，藉此，獲得上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂。 As a method for producing the above-mentioned resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain, for example, the following method can be cited. That is, first, a diamine compound is reacted with an aromatic acid anhydride to prepare an imide compound. Then, the functional group of the imide compound is reacted with a compound having a functional group that reacts with the functional group and a functional group having a carbon-carbon double bond (hereinafter, also referred to as a "functional group-containing unsaturated compound"), thereby obtaining the above-mentioned resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain. In addition, the diamine compound can be reacted with an aromatic anhydride to prepare an imide compound, and then, for example, maleic anhydride can be reacted with the end of the imide compound to obtain the above-mentioned resin having a functional group containing a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain.

作為製造上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂的方法所使用之二胺化合物及芳香族酸酐，可使用與製造上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂的方法所使用者相同者。The diamine compound and aromatic anhydride used in the method for producing the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating units of the main chain can be the same as those used in the method for producing the resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating units of the main chain.

作為上述含官能基不飽和化合物，根據上述醯亞胺化合物之末端或側鏈之官能基選擇使用。 例如於上述醯亞胺化合物之末端或側鏈之官能基為羥基之情形時，作為上述含官能基不飽和化合物，可舉具有羧基之馬來醯亞胺化合物、具有醚基之乙烯化合物、具有環氧丙基之烯丙基化合物、具有環氧丙基之烯丙醚化合物、具有環氧丙基之乙烯醚化合物、具有異氰酸基之烯丙基化合物、具有異氰酸基之(甲基)丙烯醯基化合物等。 又，例如於上述醯亞胺化合物之末端或側鏈之官能基為羧基之情形時，作為上述含官能基不飽和化合物，可舉具有羥基之烯丙基化合物、具有環氧丙基之烯丙基化合物、具有環氧丙基之烯丙醚化合物、具有環氧丙基之乙烯醚化合物等。 作為上述具有羧基之馬來醯亞胺化合物，例如可舉乙酸馬來醯亞胺、馬來醯亞胺丙酸、馬來醯亞胺丁酸、馬來醯亞胺己酸、反式-4-(N-馬來醯亞胺甲基)環己烷-1-羧酸、19-馬來醯亞胺-17-側氧基-4,7,10,13-四側氧基-16-氮雜十九酸（19-maleimido-17-oxo-4,7,10,13-tetraoxa-16-azanonadecanoic acid）等。 作為上述具有醚基之乙烯化合物，例如可舉丁基乙烯醚等。 作為上述具有環氧丙基之烯丙基化合物，例如可舉異氰尿酸二烯丙基單環氧丙酯等。 作為上述具有環氧丙基之烯丙醚化合物，例如可舉烯丙基環氧丙醚、甘油二烯丙基單環氧丙醚等。 作為上述具有環氧丙基之乙烯醚化合物，例如可舉環氧丙氧基乙基乙烯醚、環氧丙氧基丁基乙烯醚、環氧丙氧基己基乙烯醚、環氧丙基二乙二醇乙烯醚、環氧丙基環己烷二甲醇單乙烯醚等。 作為上述具有異氰酸基之烯丙基化合物，例如可舉異氰酸烯丙酯等。 作為上述具有異氰酸基之(甲基)丙烯醯基化合物，例如可舉異氰酸2-(甲基)丙烯醯氧基乙酯等。 作為上述具有羥基之烯丙基化合物，例如可舉三羥甲基丙烷二烯丙醚、新戊四醇三烯丙醚等。 As the above-mentioned functional group-containing unsaturated compound, it is selected and used according to the functional group of the terminal or side chain of the above-mentioned imide compound. For example, when the functional group of the terminal or side chain of the above-mentioned imide compound is a hydroxyl group, as the above-mentioned functional group-containing unsaturated compound, there can be mentioned maleimide compounds having a carboxyl group, vinyl compounds having an ether group, allyl compounds having a glycidyl group, allyl ether compounds having a glycidyl group, vinyl ether compounds having a glycidyl group, allyl compounds having an isocyanate group, (meth)acryl compounds having an isocyanate group, etc. Furthermore, for example, when the functional group at the terminal or side chain of the above-mentioned imide compound is a carboxyl group, the above-mentioned functional group-containing unsaturated compound may include an allyl compound having a hydroxyl group, an allyl compound having a glycidyl group, an allyl ether compound having a glycidyl group, a vinyl ether compound having a glycidyl group, etc. Examples of the maleimide compound having a carboxyl group include acetic maleimide, maleimide propionic acid, maleimide butyric acid, maleimide caproic acid, trans-4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, 19-maleimido-17-oxo-4,7,10,13-tetraoxa-16-azanonadecanoic acid, etc. Examples of the vinyl compound having an ether group include butyl vinyl ether, etc. Examples of the allyl compound having an epoxypropyl group include diallyl monoepoxypropyl isocyanurate, etc. As the above-mentioned allyl ether compound having a glycidyl group, for example, allyl glycidyl ether, glycerol diallyl monoglycidyl ether, etc. can be mentioned. As the above-mentioned vinyl ether compound having a glycidyl group, for example, glycidyl ethyl vinyl ether, glycidyl butyl vinyl ether, glycidyl hexyl vinyl ether, glycidyl diethylene glycol vinyl ether, glycidyl cyclohexanedimethanol monovinyl ether, etc. can be mentioned. As the above-mentioned allyl compound having an isocyanate group, for example, allyl isocyanate, etc. can be mentioned. As the above-mentioned (meth)acryloyl compound having an isocyanate group, for example, 2-(meth)acryloyloxyethyl isocyanate, etc. can be mentioned. Examples of the above-mentioned allyl compounds having a hydroxyl group include trihydroxymethylpropane diallyl ether, pentaerythritol triallyl ether, etc.

上述硬化性樹脂100質量份中之上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之含量之較佳下限為10質量份，較佳上限為100質量份。藉由使上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之含量為該範圍內，上述接著膜、及已硬化之上述暫時固定材於剝離時能夠更容易地剝離。就進而提高剝離性能之觀點而言，上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之含量之更佳下限為20質量份，進而較佳下限為30質量份，更佳上限為90質量份，進而較佳上限為80質量份，進而更佳上限為70質量份。The preferred lower limit of the content of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain in 100 parts by mass of the curable resin is 10 parts by mass, and the preferred upper limit is 100 parts by mass. By making the content of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain within this range, the bonding film and the hardened temporary fixing material can be more easily peeled off when peeling off. From the viewpoint of further improving the peeling performance, the content of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain has a better lower limit of 20 parts by mass, a further better lower limit of 30 parts by mass, a further better upper limit of 90 parts by mass, a further better upper limit of 80 parts by mass, and a further better upper limit of 70 parts by mass.

於上述在主鏈之重複單元具有醯亞胺骨架之樹脂包含上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂的情形時，較佳為上述硬化性樹脂進而包含分子內具有2個以上之具有碳-碳雙鍵之官能基，分子量為5000以下之多官能單體或多官能低聚物（以下，亦簡稱為「多官能單體或多官能低聚物」）。 又，於上述在主鏈之重複單元具有醯亞胺骨架之樹脂包含上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之情形時，上述硬化性樹脂亦可進而含有上述多官能單體或多官能低聚物。 藉由含有上述多官能單體或多官能低聚物，上述接著層、及上述暫時固定材藉由光之照射等更效率良好地進行三維網狀化，藉此，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，能夠進一步防止剝離時產生糊劑殘留。 When the resin having an imide skeleton in the repeating units of the main chain mentioned above includes the resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating units of the main chain mentioned above, it is preferred that the curable resin further includes a multifunctional monomer or multifunctional oligomer having two or more functional groups having a carbon-carbon double bond in the molecule and a molecular weight of 5000 or less (hereinafter, also referred to as "multifunctional monomer or multifunctional oligomer"). Furthermore, when the resin having an imide skeleton in the repeating unit of the main chain includes the functional group containing a carbon-carbon double bond and the resin having an imide skeleton in the repeating unit of the main chain, the curable resin may further contain the multifunctional monomer or multifunctional oligomer. By containing the multifunctional monomer or multifunctional oligomer, the bonding layer and the temporary fixing material are more efficiently three-dimensionally networked by light irradiation, etc., thereby further suppressing the adhesion of the bonding film and the cured temporary fixing material to the adherend, so that the releasability to the adherend is further improved, and the generation of paste residue during peeling can be further prevented.

再者，於上述在主鏈之重複單元具有醯亞胺骨架之樹脂本身不具有反應性之情形時，必須藉由使上述光硬化型接著劑進而含有具有反應性官能基之其他成分，作為整體具有反應性。較佳為使用上述多官能單體或多官能低聚物作為此種具有反應性官能基之其他成分。作為上述在主鏈之重複單元具有醯亞胺骨架之樹脂本身不具有反應性之情形，例如可舉上述在主鏈之重複單元具有醯亞胺骨架之樹脂僅包含上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂的情形等。Furthermore, when the resin having an imide skeleton in the repeating units of the main chain is not reactive itself, the photocurable adhesive must be made reactive as a whole by further containing other components having reactive functional groups. It is preferred to use the multifunctional monomer or multifunctional oligomer as such other components having reactive functional groups. As an example of the case where the resin having an imide skeleton in the repeating units of the main chain is not reactive itself, for example, the resin having an imide skeleton in the repeating units of the main chain only includes the resin having no functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating units of the main chain.

作為上述多官能單體或多官能低聚物中之具有碳-碳雙鍵之官能基，例如可舉可經取代之馬來醯亞胺基、甲基順丁烯二醯亞胺基、乙烯醚基、烯丙基、(甲基)丙烯醯基等。其中，就獲得更高之耐熱性而言，較佳為可經取代之馬來醯亞胺基。上述多官能單體或多官能低聚物尤佳為雙馬來醯亞胺化合物。Examples of the functional group having a carbon-carbon double bond in the multifunctional monomer or multifunctional oligomer include a substituted maleimide group, a methyl succinimidyl group, a vinyl ether group, an allyl group, a (meth)acryl group, etc. Among them, a substituted maleimide group is preferred in terms of obtaining higher heat resistance. The multifunctional monomer or multifunctional oligomer is particularly preferably a dimaleimide compound.

上述多官能單體或多官能低聚物較佳為具有源自二胺化合物之基。作為上述二胺化合物，可使用脂肪族二胺化合物或芳香族二胺化合物之任一者，較佳為脂肪族二胺化合物。即，上述多官能單體或多官能低聚物更佳為具有源自二胺化合物之脂肪族基。藉由使用脂肪族二胺化合物作為上述二胺化合物，上述接著膜、及上述暫時固定材之柔軟性更優異，能夠對具有凹凸之被黏著體發揮較高之追隨性，並且剝離時能夠更容易地剝離。The above-mentioned multifunctional monomer or multifunctional oligomer preferably has a group derived from a diamine compound. As the above-mentioned diamine compound, any one of an aliphatic diamine compound or an aromatic diamine compound can be used, and an aliphatic diamine compound is preferred. That is, the above-mentioned multifunctional monomer or multifunctional oligomer preferably has an aliphatic group derived from a diamine compound. By using an aliphatic diamine compound as the above-mentioned diamine compound, the above-mentioned adhesive film and the above-mentioned temporary fixing material have better flexibility, can exhibit higher tracking performance to an adherend with uneven surfaces, and can be more easily peeled off when peeling off.

上述脂肪族二胺化合物之中，就柔軟性、及上述多官能單體或多官能低聚物與溶劑或其他成分之相容性之觀點而言，較佳為如上述之二聚二胺。Among the aliphatic diamine compounds, the dimerized diamines described above are preferred from the viewpoint of flexibility and compatibility of the polyfunctional monomer or polyfunctional oligomer with the solvent or other components.

上述硬化性樹脂100質量份中之上述多官能單體或多官能低聚物之含量之較佳下限為5質量份，較佳上限為90質量份。藉由使上述多官能單體或多官能低聚物之含量為該範圍內，上述接著膜、及已硬化之上述暫時固定材於剝離時能夠更容易地剝離。就進而提高剝離性能之觀點而言，上述多官能單體或多官能低聚物之含量之更佳下限為10質量份，更佳上限為50質量份。The preferred lower limit of the content of the above-mentioned multifunctional monomer or multifunctional oligomer in 100 parts by mass of the above-mentioned curable resin is 5 parts by mass, and the preferred upper limit is 90 parts by mass. By making the content of the above-mentioned multifunctional monomer or multifunctional oligomer within this range, the above-mentioned adhesive film and the above-mentioned temporary fixing material that has been cured can be more easily peeled off when peeling. From the viewpoint of further improving the peeling performance, the preferred lower limit of the content of the above-mentioned multifunctional monomer or multifunctional oligomer is 10 parts by mass, and the preferred upper limit is 50 parts by mass.

於上述硬化型接著劑含有上述不具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂、上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂、及上述多官能單體或多官能低聚物之情形時，該等之合計100質量份中之上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂與上述多官能單體或多官能低聚物之合計含量之較佳下限為20質量份，較佳上限為80質量份。藉由使上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂與上述多官能單體或多官能低聚物之合計含量為該範圍內，上述接著膜、及已硬化之上述暫時固定材於剝離時能夠更容易地剝離。就進而提高剝離性能之觀點而言，上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂與上述多官能單體或多官能低聚物之合計含量之更佳下限為30質量份，進而較佳下限為40質量份，進而更佳下限為50質量份，更佳上限為70質量份。When the curable adhesive contains the resin having no functional group containing carbon-carbon double bonds and having an imide skeleton in the repeating units of the main chain, the resin having a functional group containing carbon-carbon double bonds and having an imide skeleton in the repeating units of the main chain, and the polyfunctional monomer or polyfunctional oligomer, the preferred lower limit of the total content of the resin having a functional group containing carbon-carbon double bonds and having an imide skeleton in the repeating units of the main chain and the polyfunctional monomer or polyfunctional oligomer in the total 100 parts by mass of the above-mentioned resins is 20 parts by mass, and the preferred upper limit is 80 parts by mass. By making the total content of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain and the multifunctional monomer or multifunctional oligomer within the range, the bonding film and the hardened temporary fixing material can be more easily peeled off during peeling. From the viewpoint of further improving the peeling performance, the total content of the resin having a functional group containing a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain and the multifunctional monomer or multifunctional oligomer has a better lower limit of 30 parts by mass, a further better lower limit of 40 parts by mass, a further better lower limit of 50 parts by mass, and a further better upper limit of 70 parts by mass.

上述硬化性樹脂較佳為含有具有馬來醯亞胺基之化合物。藉由含有上述具有馬來醯亞胺基之化合物，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。 上述具有馬來醯亞胺基之化合物較佳為雙馬來醯亞胺化合物、或具有馬來醯亞胺基且在主鏈之重複單元具有醯亞胺骨架之樹脂。即，上述硬化性樹脂較佳為含有上述雙馬來醯亞胺化合物作為上述多官能單體或多官能低聚物，或含有具有馬來醯亞胺基作為上述具有含碳-碳雙鍵之官能基且在主鏈之重複單元具有醯亞胺骨架之樹脂之上述具有碳-碳雙鍵之官能基的樹脂。 The curable resin preferably contains a compound having a maleimide group. By containing the compound having a maleimide group, the heat resistance of the bonding film and the hardened temporary fixing material is better. The compound having a maleimide group is preferably a dimaleimide compound, or a resin having a maleimide group and an imide skeleton in the repeating unit of the main chain. That is, the curable resin is preferably a resin having a carbon-carbon double bond functional group containing the dimaleimide compound as the polyfunctional monomer or polyfunctional oligomer, or a resin having a maleimide group as the functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain.

上述硬化型接著劑較佳為進而含有聚合起始劑。 藉由使上述硬化型接著劑含有聚合起始劑，上述接著層、及上述暫時固定材更容易硬化，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中之對被黏著體之接著亢進，故對被黏著體之剝離性進一步提高，與被黏著體剝離時能夠更容易地剝離。 上述聚合起始劑可為熱聚合起始劑，亦可為光聚合起始劑，但較佳為光聚合起始劑。 The curable adhesive preferably further contains a polymerization initiator. By making the curable adhesive contain a polymerization initiator, the adhesive layer and the temporary fixing material are easier to cure, and the adhesion of the adhesive film and the cured temporary fixing material to the adherend during high-temperature processing can be further suppressed, so the peelability of the adherend is further improved, and the adherend can be peeled off more easily. The polymerization initiator can be a thermal polymerization initiator or a photopolymerization initiator, but it is preferably a photopolymerization initiator.

作為上述光聚合起始劑，例如可舉藉由照射250～800 nm之波長之光而被活化者。 於本發明之接著膜中，就不易與上述在主鏈之重複單元具有醯亞胺骨架之樹脂或者上述多官能單體或多官能低聚物之吸收波長重疊，對上述接著層進行光照射時被充分地活化之方面而言，上述光聚合起始劑較佳為含有波長405 nm之吸光係數為10 ml/（g・cm）以上之化合物。上述光聚合起始劑更佳為含有波長405 nm之吸光係數為50 ml/（g・cm）以上之化合物，進而較佳為含有波長405 nm之吸光係數為100 ml/（g・cm）以上之化合物。上述波長405 nm之莫耳吸光係數為1以上之化合物於波長405 nm之莫耳吸光係數之較佳上限並無特別，實質上限為1.0×10 6ml/（g・cm）。 於本發明之暫時固定材中，就不易與上述在主鏈之重複單元具有醯亞胺骨架之樹脂或者上述多官能單體或多官能低聚物之吸收波長重疊，對暫時固定材進行光照射時被充分地活化之方面而言，上述光聚合起始劑較佳為含有405 nm之莫耳吸光係數為1以上之化合物。上述光聚合起始劑更佳為含有405 nm之莫耳吸光係數為200以上之化合物，進而較佳為含有405 nm之莫耳吸光係數為350以上之化合物。上述405 nm之莫耳吸光係數為1以上之化合物於405 nm下之莫耳吸光係數之較佳上限並無特別，實質上限為2000。 As the above-mentioned photopolymerization initiator, for example, there can be cited those that are activated by irradiation with light of a wavelength of 250 to 800 nm. In the adhesive film of the present invention, the above-mentioned photopolymerization initiator is preferably a compound having an absorption coefficient of 10 ml/(g・cm) or more at a wavelength of 405 nm, so as not to overlap with the absorption wavelength of the above-mentioned resin having an imide skeleton in the repeating unit of the main chain or the above-mentioned multifunctional monomer or multifunctional oligomer, and is fully activated when the above-mentioned adhesive layer is irradiated with light. The above-mentioned photopolymerization initiator is more preferably a compound having an absorption coefficient of 50 ml/(g・cm) or more at a wavelength of 405 nm, and is further preferably a compound having an absorption coefficient of 100 ml/(g・cm) or more at a wavelength of 405 nm. There is no particular upper limit for the molar absorption coefficient of the compound having a molar absorption coefficient of 1 or more at a wavelength of 405 nm, and the actual upper limit is 1.0×10 6 ml/(g・cm). In the temporary fixing material of the present invention, the photopolymerization initiator is preferably a compound having a molar absorption coefficient of 1 or more at a wavelength of 405 nm, so as not to overlap with the absorption wavelength of the resin having an imide skeleton in the repeating unit of the main chain or the multifunctional monomer or multifunctional oligomer, and to be fully activated when the temporary fixing material is irradiated with light. The photopolymerization initiator is more preferably a compound having a molar absorption coefficient of 200 or more at a wavelength of 405 nm, and further preferably a compound having a molar absorption coefficient of 350 or more at a wavelength of 405 nm. There is no particular upper limit on the molar absorbance at 405 nm of the compound having a molar absorbance at 405 nm of 1 or more, and the practical upper limit is 2000.

作為上述光聚合起始劑，例如可舉苯乙酮衍生物、安息香醚系化合物、縮酮衍生物、膦氧化物衍生物、肟酯化合物等。 作為上述苯乙酮衍生物，例如可舉甲氧基苯乙酮、2-苄基-2-(二甲基胺基)-4'-N-𠰌啉基苯丁酮、2-二甲基胺基-2-(4-甲基苄基)-1-(4-N-𠰌啉-4-基-苯基)-丁烷-1-酮等。 作為上述安息香醚系化合物，例如可舉安息香丙醚、安息香異丁醚等。 作為上述縮酮衍生物，例如可舉二苯乙二酮二甲基縮酮、苯乙酮二乙基縮酮等。 作為上述膦氧化物衍生物，例如可舉雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物、2,4,6-三甲基苯甲醯基-二苯基膦氧化物等。 作為上述肟酯化合物，可舉1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮、1-[4-(苯硫基)苯基]-2-(O-苯甲醯基肟)-1,2-辛二酮等。 又，作為上述光聚合起始劑，例如亦可舉雙(η5-環戊二烯基)二茂鈦衍生物化合物、二苯甲酮、米其勒酮（Michler's ketone）、氯9-氧硫𠮿（chlorothioxanthone）、十二烷基9-氧硫𠮿、二甲基9-氧硫𠮿、二乙基9-氧硫𠮿、α-羥基環己基苯基酮、2-羥甲基苯基丙烷等。 該等光聚合起始劑可單獨使用，亦可將2種以上組合使用。 Examples of the photopolymerization initiator include acetophenone derivatives, benzoin ether compounds, ketal derivatives, phosphine oxide derivatives, and oxime ester compounds. Examples of the acetophenone derivatives include methoxyacetophenone, 2-benzyl-2-(dimethylamino)-4'-N-oxo-1-butylphenyl ketone, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-N-oxo-1-4-yl-phenyl)-butane-1-one. Examples of the benzoin ether compounds include benzoin propyl ether and benzoin isobutyl ether. Examples of the ketal derivatives include dibenzodione dimethyl ketal and acetophenone diethyl ketal. Examples of the phosphine oxide derivatives include bis(2,4,6-trimethylbenzyl)phenylphosphine oxide and 2,4,6-trimethylbenzyl-diphenylphosphine oxide. Examples of the oxime ester compounds include 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone and 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)-1,2-octanedione. Examples of the photopolymerization initiator include bis(η5-cyclopentadienyl)titaniumocene derivative compounds, benzophenone, Michler's ketone, chloro-9-oxysulfonate, and the like. (chlorothioxanthone), dodecyl 9-oxythiothion , dimethyl 9-oxysulfide , diethyl 9-oxysulfide , α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenyl propane, etc. These photopolymerization initiators may be used alone or in combination of two or more.

相對於上述硬化性樹脂100質量份而言，上述聚合起始劑之含量之較佳下限為0.1質量份，較佳上限為10質量份。藉由使上述聚合起始劑之含量為該範圍內，藉由光之照射或加熱等，上述接著層或上述暫時固定材整體均勻且迅速地進行聚合交聯，彈性模數上升，藉此，所獲得之接著膜、及上述暫時固定材之接著力大幅降低，故能夠進一步抑制產生接著亢進或剝離時產生糊劑殘留。上述聚合起始劑之含量之更佳下限為0.5質量份，進而較佳下限為1質量份，更佳上限為7質量份，進而較佳上限為5質量份。The preferred lower limit of the content of the polymerization initiator is 0.1 parts by mass and the preferred upper limit is 10 parts by mass relative to 100 parts by mass of the curable resin. By making the content of the polymerization initiator within this range, the bonding layer or the temporary fixing material is uniformly and rapidly polymerized and crosslinked as a whole by irradiation with light or heating, etc., and the elastic modulus increases, thereby greatly reducing the bonding force of the obtained bonding film and the temporary fixing material, so that the generation of hyperadhesion or paste residue during peeling can be further suppressed. The preferred lower limit of the content of the polymerization initiator is 0.5 parts by mass, and further the preferred lower limit is 1 part by mass, and the preferred upper limit is 7 parts by mass, and further the preferred upper limit is 5 parts by mass.

於本發明之接著膜中，於上述硬化型接著劑含有上述光聚合起始劑之情形時，較佳為進而含有紫外線吸收劑。藉由使上述硬化型接著劑含有紫外線吸收劑，上述接著層之紫外區域之光之吸收性進一步提高，藉此，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。In the adhesive film of the present invention, when the curable adhesive contains the photopolymerization initiator, it is preferred to further contain an ultraviolet absorber. By making the curable adhesive contain an ultraviolet absorber, the light absorption of the ultraviolet region of the adhesive layer is further improved, thereby enabling the support to be more efficiently peeled off even when irradiated with low-energy laser light.

上述硬化型接著劑較佳為含有紫外線吸收劑或紫外線散射劑。藉由使上述硬化型接著劑含有紫外線吸收劑，已硬化之上述暫時固定材之紫外線吸收性更優異，對雷射加工性能進一步提高，從而能夠更效率良好地將支持體剝離。藉由使上述硬化型接著劑含有紫外線散射劑，已硬化之上述暫時固定材表面之對雷射加工性能進一步提高，從而能夠更效率良好地將支持體剝離。又，上述硬化型接著劑亦可含有紫外線吸收劑及紫外線散射劑之兩者。The curable adhesive preferably contains an ultraviolet absorber or an ultraviolet scatterer. By making the curable adhesive contain an ultraviolet absorber, the ultraviolet absorption of the cured temporary fixing material is better, and the laser processing performance is further improved, so that the support can be peeled off more efficiently. By making the curable adhesive contain an ultraviolet scatterer, the laser processing performance of the surface of the cured temporary fixing material is further improved, so that the support can be peeled off more efficiently. In addition, the curable adhesive may also contain both an ultraviolet absorber and an ultraviolet scatterer.

作為本發明之接著膜中之上述紫外線吸收劑，例如可舉三系紫外線吸收劑、苯并三唑系紫外線吸收劑、二苯甲酮系紫外線吸收劑、水楊酸酯系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑等。其中，就耐熱性之觀點而言，上述紫外線吸收劑較佳為包含三系紫外線吸收劑。As the above-mentioned ultraviolet absorber in the adhesive film of the present invention, for example, three kinds of ultraviolet absorbers can be cited: The UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, etc. Among them, from the viewpoint of heat resistance, the UV absorbers preferably include three It is a UV absorber.

作為本發明之暫時固定材中之上述紫外線吸收劑，例如可舉三系紫外線吸收劑、苯并三唑系紫外線吸收劑、二苯甲酮系紫外線吸收劑、水楊酸酯系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑等。作為上述紫外線散射劑，例如可舉氧化鈦、氧化鋅等。其中，就耐熱性之觀點而言，上述紫外線吸收劑或上述紫外線散射劑較佳為包含三系紫外線吸收劑或氧化鈦。As the above-mentioned ultraviolet absorber in the temporary fixing material of the present invention, for example, three kinds of ultraviolet absorbers can be cited: The ultraviolet light scattering agent may include, for example, titanium oxide, zinc oxide, etc. Among them, from the viewpoint of heat resistance, the ultraviolet light absorber or the ultraviolet light scattering agent preferably includes three It is a UV absorber or titanium oxide.

作為上述三系紫外線吸收劑，例如可舉Tinuvin400、Tinuvin405、Tinuvin460、Tinuvin477、Tinuvin479、Tinuvin1577ED、Tinuvin1600（均為BASF公司製造）、Adekastab LA46、Adekastab LA-F70（均為ADEKA公司製造）。其中，較佳為Tinuvin400、Tinuvin479、Tinuvin1600。As the above three It is an ultraviolet absorber, for example, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 1577ED, Tinuvin 1600 (all manufactured by BASF), Adekastab LA46, Adekastab LA-F70 (all manufactured by ADEKA). Among them, Tinuvin 400, Tinuvin 479, and Tinuvin 1600 are preferred.

相對於上述硬化性樹脂100質量份而言，上述紫外線吸收劑或紫外線散射劑之含量之較佳下限為1質量份，較佳上限為30質量份。若上述紫外線吸收劑或紫外線散射劑之含量為1質量份以上，則上述接著層、及已硬化之上述暫時固定材之紫外區域之光之吸收性進一步提高，藉此，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離。若上述紫外線吸收劑或紫外線散射劑之含量為30質量份以下，則上述接著膜、及已硬化之上述暫時固定材即便於加熱步驟後亦能夠容易地自被黏著體剝離。上述紫外線吸收劑或紫外線散射劑之更佳下限為5質量份，進而較佳下限為7質量份，更佳上限為20質量份，進而較佳上限為15質量份。The preferred lower limit of the content of the ultraviolet absorber or ultraviolet scatterer is 1 part by mass and the preferred upper limit is 30 parts by mass relative to 100 parts by mass of the curable resin. If the content of the ultraviolet absorber or ultraviolet scatterer is 1 part by mass or more, the light absorption of the ultraviolet region of the bonding layer and the cured temporary fixing material is further improved, thereby enabling the support to be peeled off more efficiently even when irradiated with low-energy laser light. If the content of the ultraviolet absorber or ultraviolet scatterer is 30 parts by mass or less, the bonding film and the cured temporary fixing material can be easily peeled off from the adherend even after the heating step. The more preferred lower limit of the ultraviolet absorber or ultraviolet scatterer is 5 parts by mass, and further preferably the lower limit is 7 parts by mass, and the more preferred upper limit is 20 parts by mass, and further preferably the upper limit is 15 parts by mass.

上述光硬化型接著劑較佳為進而含有離型劑。 作為上述離型劑，例如可舉聚矽氧系離型劑、氟系離型劑、丙烯酸系離型劑等。該等離型劑之耐熱性優異，因此，藉由使上述硬化型接著劑含有離型劑，即便經過300℃以上之高溫加工處理，亦防止上述接著層焦化，所獲得之接著膜於剝離時於被黏著體界面滲出，更容易剝離。 其中，就對環境友好且容易廢棄之觀點而言，較佳為聚矽氧系離型劑。又，就防止聚矽氧污染被黏著體之觀點而言，較佳為丙烯酸系離型劑。 The above-mentioned light-curing adhesive preferably further contains a release agent. As the above-mentioned release agent, for example, silicone-based release agents, fluorine-based release agents, acrylic-based release agents, etc. can be cited. Such release agents have excellent heat resistance. Therefore, by making the above-mentioned curing adhesive contain a release agent, even after a high-temperature processing treatment of more than 300°C, the above-mentioned adhesive layer is prevented from being charred, and the obtained adhesive film seeps out at the interface of the adherend during peeling, making it easier to peel off. Among them, from the perspective of being environmentally friendly and easy to dispose, silicone-based release agents are preferred. Furthermore, from the perspective of preventing silicone from contaminating the adherend, acrylic release agents are preferred.

上述離型劑亦可具有能夠與上述在主鏈之重複單元具有醯亞胺骨架之樹脂交聯之官能基。藉由使上述離型劑具有能夠與上述主鏈之重複單元中具有醯亞胺骨架之樹脂交聯之官能基，藉由光之照射或與交聯劑等之反應而上述離型劑與上述在主鏈之重複單元具有醯亞胺骨架之樹脂或者上述多官能單體或多官能低聚物進行化學反應而被組入。因此，能夠抑制上述離型劑附著並污染被黏著體。作為能夠與上述在主鏈之重複單元具有醯亞胺骨架之樹脂或者上述多官能單體或多官能低聚物交聯之官能基，例如可舉羧基、具有自由基聚合性之不飽和鍵之官能基（例如乙烯基、(甲基)丙烯醯基、可經取代之馬來醯亞胺基）、羥基、醯胺基、異氰酸基、環氧基等。The release agent may also have a functional group capable of crosslinking with the resin having an imide skeleton in the repeating unit of the main chain. By providing the release agent with a functional group capable of crosslinking with the resin having an imide skeleton in the repeating unit of the main chain, the release agent reacts chemically with the resin having an imide skeleton in the repeating unit of the main chain or the multifunctional monomer or multifunctional oligomer by irradiation with light or reaction with a crosslinking agent, and is incorporated. Therefore, the release agent can be prevented from being attached to and contaminating the adherend. Examples of the functional group capable of cross-linking with the resin having an imide skeleton in the repeating units of the main chain or the multifunctional monomer or multifunctional oligomer include carboxyl groups, functional groups having free radical polymerizable unsaturated bonds (e.g., vinyl groups, (meth)acryloyl groups, substituted maleimide groups), hydroxyl groups, amide groups, isocyanate groups, epoxy groups, and the like.

作為上述聚矽氧系離型劑，例如可舉聚矽氧油、聚矽氧二丙烯酸酯、聚矽氧系接枝共聚物等。具體而言，較佳為上述主鏈具有矽氧烷骨架，側鏈或末端具有含碳-碳雙鍵之官能基的聚矽氧化合物。 作為上述主鏈具有矽氧烷骨架，側鏈或末端具有含碳-碳雙鍵之官能基的聚矽氧化合物，較佳為選自由下述式（5-1）所表示之聚矽氧化合物、下述式（5-2）所表示之聚矽氧化合物、及下述式（5-3）所表示之聚矽氧化合物所組成之群中之至少1種。該等聚矽氧化合物由於耐熱性尤其優異、極性較高，故容易自上述接著膜、及上述暫時固定材中滲出。 As the above-mentioned polysilicone release agent, for example, polysilicone oil, polysilicone diacrylate, polysilicone graft copolymer, etc. can be cited. Specifically, it is preferred that the above-mentioned main chain has a siloxane skeleton, and the side chain or the end has a functional group containing a carbon-carbon double bond. As the above-mentioned polysilicone compound having a siloxane skeleton as the main chain, and the side chain or the end having a functional group containing a carbon-carbon double bond, it is preferred to be at least one selected from the group consisting of a polysilicone compound represented by the following formula (5-1), a polysilicone compound represented by the following formula (5-2), and a polysilicone compound represented by the following formula (5-3). Since these polysilicone compounds have particularly excellent heat resistance and high polarity, they are easy to seep out from the above-mentioned adhesive film and the above-mentioned temporary fixing material.

上述式（5-1）～（5-3）中之X、及上述式（5-1）、（5-3）中之Y分別獨立地表示0以上1200以下之整數，上述式（5-1）～（5-3）中，R表示具有碳-碳雙鍵之官能基。X in the above formulae (5-1) to (5-3) and Y in the above formulae (5-1) and (5-3) each independently represent an integer of 0 to 1200. In the above formulae (5-1) to (5-3), R represents a functional group having a carbon-carbon double bond.

上述式（5-1）～（5-3）中，作為R所表示之具有碳-碳雙鍵之官能基，例如可舉可經取代之馬來醯亞胺基、甲基順丁烯二醯亞胺基、乙烯醚基、烯丙基、(甲基)丙烯醯基等。其中，就上述接著膜、及上述暫時固定材之耐熱性更優異之方面而言，較佳為可經取代之馬來醯亞胺基。再者，於上述式（5-1）～（5-3）中，於存在多個R之情形時，各R可相同，亦可不同。In the above formulas (5-1) to (5-3), the functional group having a carbon-carbon double bond represented by R may be, for example, a substituted maleimide group, a methyl succinimidyl group, a vinyl ether group, an allyl group, a (meth)acryl group, etc. Among them, a substituted maleimide group is preferred in terms of better heat resistance of the above-mentioned adhesive film and the above-mentioned temporary fixing material. Furthermore, in the above-mentioned formulas (5-1) to (5-3), when there are multiple Rs, each R may be the same or different.

作為上述式（5-1）～（5-3）所表示之聚矽氧化合物中經市售者，例如可舉EBECRYL350、EBECRYL1360（均為DAICEL-ALLNEX公司製造）等。又，亦可舉BYK-UV3500（BYK-Chemie公司製造）、TEGO RAD2250（Evonik公司製造）（R均為丙烯醯基）等。Examples of commercially available polysiloxanes represented by the above formulae (5-1) to (5-3) include EBECRYL350 and EBECRYL1360 (both manufactured by DAICEL-ALLNEX). In addition, examples include BYK-UV3500 (manufactured by BYK-Chemie) and TEGO RAD2250 (manufactured by Evonik) (R in each case is an acryl group).

作為上述氟系離型劑，例如可舉具有氟原子之烴化合物等。Examples of the fluorine-based release agent include hydrocarbon compounds having fluorine atoms.

作為上述丙烯酸系離型劑，例如可舉BYK-394、BYK-350、BYK-381（均為BYK-Chemie公司製造）、Disparlon1970（楠本化成公司製造）等。Examples of the acrylic release agent include BYK-394, BYK-350, BYK-381 (all manufactured by BYK-Chemie), Disparlon 1970 (manufactured by Kusumoto Chemicals Co., Ltd.), and the like.

上述離型劑之含量相對於上述硬化性樹脂100質量份而言，較佳下限為0.1質量份，較佳上限為20質量份。藉由使上述離型劑之含量為該範圍內，上述接著膜、及硬化後之上述暫時固定材不會污染被黏著體且剝離性能更優異。就抑制污染並且進而提高剝離性能之觀點而言，上述離型劑之含量之更佳下限為0.3質量份，更佳上限為10質量份。The content of the release agent is preferably 0.1 parts by mass and 20 parts by mass relative to 100 parts by mass of the curable resin. When the content of the release agent is within this range, the adhesive film and the temporary fixing material after curing will not contaminate the adherend and the peeling performance is better. From the perspective of suppressing contamination and further improving the peeling performance, the content of the release agent is more preferably 0.3 parts by mass and 10 parts by mass.

上述硬化型接著劑亦可進而含有氣體產生劑。藉由使上述硬化型接著劑含有氣體產生劑，即便經過300℃以上之高溫加工處理後，藉由照射光等而產生之氣體被釋放至與被黏著體之界面，因此，能夠更容易地將上述接著膜、及上述暫時固定材剝離，且能夠於無糊劑殘留之情況下將被黏著體剝離。又，即便於進行300℃以上之高溫加工處理後將較薄之被黏著體剝離之情形，亦能夠防止被黏著體破損。The curable adhesive may further contain a gas generator. By making the curable adhesive contain a gas generator, even after high-temperature processing at 300°C or above, the gas generated by irradiation with light or the like is released to the interface with the adherend, so that the adhesive film and the temporary fixing material can be peeled off more easily, and the adherend can be peeled off without leaving any paste residue. In addition, even in the case of peeling off a thinner adherend after high-temperature processing at 300°C or above, damage to the adherend can be prevented.

上述氣體產生劑較佳為於TG-DTA（熱重量-示差熱分析）測定中，於氮氣環境下經以10℃/min之升溫速度自30℃加熱至300℃時之於300℃之重量減少率為5%以下。若上述重量減少率為5%以下，則即便於進行300℃以上之高溫加工處理之情形時，亦不易產生上述氣體產生劑之分解，上述接著膜、及已硬化之上述暫時固定材之耐熱性更優異。即，能夠進一步抑制高溫加工處理中之剝落，又，能夠進一步防止產生接著亢進或剝離時產生糊劑殘留。 再者，上述TG-DTA（熱重量-示差熱分析）測定例如可使用TG-DTA裝置（Hitachi High-Tech Science公司製造，「STA7200RV」）等進行。 The gas generator preferably has a weight loss rate of 5% or less at 300°C when heated from 30°C to 300°C at a heating rate of 10°C/min in a nitrogen environment in a TG-DTA (thermogravimetric-differential thermal analysis) measurement. If the weight loss rate is 5% or less, the gas generator is not easily decomposed even when subjected to high-temperature processing at 300°C or above, and the heat resistance of the bonding film and the hardened temporary fixing material is better. That is, peeling during high-temperature processing can be further suppressed, and the generation of paste residues during bonding or peeling can be further prevented. Furthermore, the above-mentioned TG-DTA (thermogravimetric-differential thermal analysis) measurement can be performed using, for example, a TG-DTA device (manufactured by Hitachi High-Tech Science, "STA7200RV"), etc.

作為上述氣體產生劑，例如可舉藉由加熱產生氣體之氣體產生劑、藉由照射光產生氣體之氣體產生劑等。其中，較佳為藉由照射光產生氣體之氣體產生劑，更佳為藉由照射紫外線產生氣體之氣體產生劑。 作為上述氣體產生劑，例如可舉四唑化合物或其鹽、三唑化合物或其鹽、偶氮化合物、疊氮化合物、𠮿酮乙酸、碳酸鹽等。該等氣體產生劑可單獨使用，亦可將2種以上組合使用。其中，就耐熱性尤其優異之方面而言，較佳為四唑化合物或其鹽。 As the above-mentioned gas generator, for example, there can be mentioned a gas generator that generates gas by heating, a gas generator that generates gas by irradiating light, etc. Among them, a gas generator that generates gas by irradiating light is preferred, and a gas generator that generates gas by irradiating ultraviolet rays is more preferred. As the above-mentioned gas generator, for example, there can be mentioned tetrazole compounds or their salts, triazole compounds or their salts, azo compounds, azide compounds, oxone acetic acid, carbonates, etc. These gas generators can be used alone or in combination of two or more. Among them, tetrazole compounds or their salts are preferred in terms of particularly excellent heat resistance.

上述氣體產生劑之含量相對於上述硬化性樹脂100質量份，較佳下限為5質量份，較佳上限為50質量份。藉由使上述氣體產生劑之含量為該範圍內，上述接著膜、及已硬化之上述暫時固定材之剝離性能尤其優異。上述氣體產生劑之含量之更佳下限為8質量份，更佳上限為30質量份。The content of the gas generator is preferably 5 parts by mass and 50 parts by mass relative to 100 parts by mass of the curable resin. When the content of the gas generator is within this range, the peeling performance of the adhesive film and the hardened temporary fixing material is particularly excellent. The more preferable lower limit of the content of the gas generator is 8 parts by mass and the more preferable upper limit is 30 parts by mass.

上述光硬化型接著劑亦可進而含有無機填充劑。藉由含有上述無機填充劑，能夠抑制上述接著層、及上述暫時固定材於高溫下彈性模數降低，即便於上述接著膜、及已硬化之上述暫時固定材進行300℃以上之高溫加工處理之情形時，亦能夠進一步抑制高溫加工處理中之剝落。The light-curing adhesive may further contain an inorganic filler. By containing the inorganic filler, the elastic modulus of the adhesive layer and the temporary fixing material can be suppressed from decreasing at high temperatures, and even when the adhesive film and the hardened temporary fixing material are subjected to high-temperature processing at 300°C or above, peeling during the high-temperature processing can be further suppressed.

作為上述無機填充劑，例如可舉由選自由矽、鋁、鈣、硼、鎂及氧化鋯之氧化物、以及該等之複合物所組成之群中之至少1種構成的無機填充劑。其中，就市售品便宜且容易獲取之方面而言，較佳為二氧化矽或滑石。As the above-mentioned inorganic filler, for example, there can be mentioned an inorganic filler composed of at least one selected from the group consisting of oxides of silicon, aluminum, calcium, boron, magnesium and zirconium oxide, and complexes thereof. Among them, silicon dioxide or talc is preferred in terms of being inexpensive and easily available commercially.

上述無機填充劑亦可經表面改質。作為對上述無機填充劑進行表面改質之改質官能基，例如可舉烷基矽烷基、甲基丙烯醯基及二甲基矽氧烷基等。其中，就具有適度之疏水性之方面而言，較佳為二甲基矽氧烷基。The inorganic filler may also be surface-modified. Examples of the modified functional group for surface-modified inorganic filler include alkylsilyl, methacrylic acid, and dimethylsiloxyalkyl. Among them, dimethylsiloxyalkyl is preferred in terms of having a moderate hydrophobicity.

上述無機填充劑之平均粒徑之較佳下限為5 nm，較佳上限為30 μm。藉由使上述無機填充劑之平均粒徑為該範圍內，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中剝落，又，剝離時能夠藉由剝離處理剝離。上述無機填充劑之平均粒徑之更佳下限為10 nm，進而較佳下限為15 nm，更佳上限為20 μm，進而較佳上限為15 μm。 再者，上述平均粒徑例如可藉由如下方式求出：利用電子顯微鏡或光學顯微鏡觀察任意50個無機填充劑，算出各無機填充劑之粒徑之平均值，或進行雷射光繞射式粒度分佈測定。 The preferred lower limit of the average particle size of the inorganic filler is 5 nm, and the preferred upper limit is 30 μm. By making the average particle size of the inorganic filler within this range, the above-mentioned bonding film and the above-mentioned temporary fixing material that has been cured can be further inhibited from peeling off during high-temperature processing, and can be peeled off by peeling treatment. The preferred lower limit of the average particle size of the inorganic filler is 10 nm, and further the preferred lower limit is 15 nm, and the preferred upper limit is 20 μm, and further the preferred upper limit is 15 μm. Furthermore, the above average particle size can be obtained, for example, by observing 50 random inorganic fillers using an electron microscope or an optical microscope, calculating the average particle size of each inorganic filler, or performing laser light diffraction particle size distribution measurement.

上述無機填充劑之含量相對於上述硬化性樹脂100質量份而言，較佳下限為1質量份，較佳上限為20質量份。藉由使上述無機填充劑之含量為該範圍內，能夠進一步抑制上述接著膜、及已硬化之上述暫時固定材於高溫加工處理中剝落，又，剝離時能夠藉由剝離處理剝離。上述無機填充劑之含量之更佳下限為3質量份，進而較佳下限為5質量份，更佳上限為15質量份，進而較佳上限為10質量份。The content of the inorganic filler is preferably 1 part by mass and 20 parts by mass relative to 100 parts by mass of the curable resin. By making the content of the inorganic filler within this range, the adhesive film and the hardened temporary fixing material can be further inhibited from peeling off during the high temperature processing, and can be peeled off by a peeling treatment. The content of the inorganic filler is more preferably 3 parts by mass, and further preferably 5 parts by mass, and the upper limit is more preferably 15 parts by mass, and further preferably 10 parts by mass.

上述硬化型接著劑例如亦可含有光敏劑、熱穩定劑、抗氧化劑、抗靜電劑、塑化劑、樹脂、界面活性劑、蠟等公知之添加劑。The curable adhesive may contain known additives such as photosensitizer, heat stabilizer, antioxidant, antistatic agent, plasticizer, resin, surfactant, wax, etc.

本發明之接著膜可具有基材，亦可不具有基材。於不具有上述基材之情形時，無須選定兼具光穿透性及耐熱性之基材，能夠將本發明之接著膜製成更便宜且簡易之構成。於具有上述基材之情形時，本發明之接著膜之操作性進一步提高。又，就操作性之觀點而言，本發明之接著膜較佳為帶狀。 於具有上述基材之情形時，本發明之接著膜亦可於基材之一面或兩面具有上述光硬化型接著劑。作為該基材，例如可舉：丙烯酸、烯烴、聚碳酸酯、氯乙烯、ABS、聚對苯二甲酸乙二酯（PET）、聚萘二甲酸乙二酯（PEN）、尼龍、胺酯（urethane）、聚醯亞胺、聚醚醚酮（PEEK）、聚醯胺（PA）等樹脂片，可較佳地使用透光性較高之樹脂片。又，亦可使用具有網目狀結構之片材、開設有孔之片材、玻璃等。 就提高柔軟性之觀點而言，上述基材之厚度之較佳下限為5 μm，更佳下限為10 μm，較佳上限為150 μm，更佳上限為100 μm。 The adhesive film of the present invention may or may not have a substrate. In the case of not having the above-mentioned substrate, there is no need to select a substrate that has both light transmittance and heat resistance, and the adhesive film of the present invention can be made into a cheaper and simpler structure. In the case of having the above-mentioned substrate, the operability of the adhesive film of the present invention is further improved. In addition, from the perspective of operability, the adhesive film of the present invention is preferably in a strip shape. In the case of having the above-mentioned substrate, the adhesive film of the present invention may also have the above-mentioned light-curing adhesive on one or both sides of the substrate. As the substrate, for example, there can be cited resin sheets such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, polyetheretherketone (PEEK), polyamide (PA), etc., and resin sheets with higher light transmittance can be preferably used. In addition, sheets with mesh structures, sheets with holes, glass, etc. can also be used. From the perspective of improving flexibility, the preferred lower limit of the thickness of the above-mentioned substrate is 5 μm, the more preferred lower limit is 10 μm, the preferred upper limit is 150 μm, and the more preferred upper limit is 100 μm.

本發明之暫時固定材可為液狀、糊狀，亦可為具有含硬化型接著劑之接著層的帶狀等之暫時固定材，較佳為帶狀之暫時固定材。於該情形時，上述帶可於基材之一面或兩面具有上述接著層，亦可不具有基材。於不具有上述基材之情形時，無須選定兼具光穿透性及耐熱性之基材，可將上述帶製成更便宜且簡易之構成。於具有上述基材之情形時，本發明之暫時固定材之操作性進一步提高。 於具有上述基材之情形時，作為該基材，例如可舉：丙烯酸、烯烴、聚碳酸酯、氯乙烯、ABS、聚對苯二甲酸乙二酯（PET）、聚萘二甲酸乙二酯（PEN）、尼龍、胺酯、聚醯亞胺、聚醚醚酮（PEEK）、聚醯胺（PA）等樹脂片，可較佳地使用透光性較高之樹脂片。又，亦可使用具有網目狀結構之片材、開設有孔之片材、玻璃等。 就提高柔軟性之觀點而言，上述基材之厚度之較佳下限為5 μm，更佳下限為10 μm，較佳上限為150 μm，更佳上限為100 μm。 The temporary fixing material of the present invention may be in liquid or paste form, or in the form of a belt having an adhesive layer containing a curing adhesive, and preferably in the form of a belt. In this case, the belt may have the adhesive layer on one or both sides of the substrate, or may not have a substrate. In the case of not having the substrate, there is no need to select a substrate that has both light transmittance and heat resistance, and the belt may be made into a cheaper and simpler structure. In the case of having the substrate, the operability of the temporary fixing material of the present invention is further improved. In the case of the above-mentioned substrate, the substrate may be, for example, a resin sheet such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, amine, polyimide, polyetheretherketone (PEEK), polyamide (PA), etc., and a resin sheet with high light transmittance may be preferably used. In addition, a sheet having a mesh structure, a sheet with holes, glass, etc. may also be used. From the viewpoint of improving flexibility, the thickness of the above-mentioned substrate has a preferred lower limit of 5 μm, a more preferred lower limit of 10 μm, a preferred upper limit of 150 μm, and a more preferred upper limit of 100 μm.

製造本發明之接著膜之方法並無特別限定，可藉由先前公知之方法製造。具體而言，例如可藉由如下方式獲得：首先，使用珠磨機、超音波分散、均質機、高輸出分散機、輥磨機等將上述在主鏈之重複單元具有醯亞胺骨架之樹脂、及視需要摻合之添加劑進行混合，製備上述硬化型接著劑。繼而，利用刮刀將所製備之硬化型接著劑塗佈於單面實施了離型處理之厚度50 μm之離型聚對苯二甲酸乙二酯（PET）膜之離型處理面上，以130℃加熱10分鐘而使塗佈溶液乾燥從而形成接著層後，將厚度50 μm之離型PET膜以離型處理面與接著層對向之方式重疊。 又，於本發明之接著膜具有基材之情形時，可藉由如下方式獲得：利用刮刀將所製備之硬化型接著劑塗佈於單面實施了離型處理之厚度50 μm之離型聚對苯二甲酸乙二酯（PET）膜之離型處理面上，並以130℃加熱10分鐘而使塗佈溶液乾燥，藉此製作形成有接著層之積層膜，並將積層膜之接著層重合於基材層之面。 The method for producing the adhesive film of the present invention is not particularly limited and can be produced by a previously known method. Specifically, for example, it can be obtained by the following method: First, the resin having an imide skeleton in the repeating unit of the main chain and an additive blended as needed are mixed using a bead mill, ultrasonic disperser, homogenizer, high-output disperser, roll mill, etc. to prepare the above-mentioned curing adhesive. Next, the prepared curing adhesive was applied to the release-treated surface of a 50 μm thick release polyethylene terephthalate (PET) film that had been subjected to release treatment on one side using a doctor blade. The coating solution was dried by heating at 130°C for 10 minutes to form an adhesive layer. Then, a 50 μm thick release PET film was overlapped with the release-treated surface facing the adhesive layer. Furthermore, when the adhesive film of the present invention has a substrate, it can be obtained by applying the prepared curing adhesive on the release-treated surface of a release-treated polyethylene terephthalate (PET) film with a thickness of 50 μm and subjected to release treatment on one side using a doctor blade, and drying the applied solution by heating at 130°C for 10 minutes to prepare a laminated film with an adhesive layer, and overlapping the adhesive layer of the laminated film on the surface of the substrate layer.

作為製造上述暫時固定材之方法，例如於上述暫時固定材為液狀或糊狀之情形時，可舉使用珠磨機、超音波分散、均質機、高輸出分散機、輥磨機等將上述在主鏈之重複單元具有醯亞胺骨架之樹脂、及視需要摻合之添加劑進行混合之方法等。 又，於上述暫時固定材為具有含硬化型接著劑之接著層之帶狀等之暫時固定材之情形時，可藉由與上述接著膜相同之方法製造。 As a method for manufacturing the above-mentioned temporary fixing material, for example, when the above-mentioned temporary fixing material is in a liquid or paste state, a method of mixing the above-mentioned resin having an imide skeleton in the repeating unit of the main chain and the additive blended as needed can be cited. In addition, when the above-mentioned temporary fixing material is a temporary fixing material in the form of a belt having an adhesive layer containing a curing adhesive, it can be manufactured by the same method as the above-mentioned adhesive film.

本發明之接著膜之總厚度（於具有基材之情形時，係將接著層之厚度與基材之厚度合在一起之厚度）之較佳下限為5 μm，較佳上限為550 μm。藉由使本發明之接著膜之總厚度為5 μm以上，能夠於初期具有充分之感壓或感熱接著力。藉由使本發明之接著膜之總厚度為550 μm以下，能夠發揮較高之柔軟性，從而能夠對具有凹凸之被黏著體發揮較高之追隨性，並且剝離時能夠更容易地剝離。本發明之接著膜之總厚度的更佳下限為10 μm，進而較佳下限為20 μm，更佳上限為400 μm，進而較佳上限為300 μm。The preferred lower limit of the total thickness of the adhesive film of the present invention (when there is a substrate, the thickness of the adhesive layer and the thickness of the substrate are combined) is 5 μm, and the preferred upper limit is 550 μm. By making the total thickness of the adhesive film of the present invention more than 5 μm, it can have sufficient pressure-sensitive or heat-sensitive adhesion in the initial stage. By making the total thickness of the adhesive film of the present invention less than 550 μm, it can exert higher flexibility, thereby being able to exert higher tracking performance for the adherend with uneven surfaces, and can be peeled off more easily when peeling off. The more preferred lower limit of the total thickness of the adhesive film of the present invention is 10 μm, and further preferably the lower limit is 20 μm, and the more preferred upper limit is 400 μm, and further preferably the upper limit is 300 μm.

本發明之接著膜以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後，於氮氣環境下，經以升溫速度10℃/min加熱之情形時之5%重量減少溫度（以下，亦有時僅表示為「照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度」）之較佳下限為300℃。若本發明之接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度為300℃以上，則所獲得之接著膜之耐熱性更優異，能夠進一步抑制高溫加工處理中之剝落。本發明之接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度之更佳下限為350℃，進而較佳下限為375℃。 又，本發明之接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度之較佳上限並無特別，實質上限為600℃。 再者，本發明之接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時的5%重量減少溫度，例如可藉由使用TG-DTA裝置（Hitachi High-Tech Science公司製造，「STA7200RV」）等之TG-DTA（熱重量-示差熱分析）進行測定。 The adhesive film of the present invention is irradiated with light of a wavelength of 405 nm in such a way that the cumulative light amount becomes 20000 mJ/ cm2 , and then heated at a heating rate of 10°C/min in a nitrogen environment. The preferred lower limit of the 5% weight loss temperature (hereinafter, sometimes simply expressed as "the 5% weight loss temperature when heated at a heating rate of 10°C/min in a nitrogen environment after irradiation with light") is 300°C. If the 5% weight loss temperature of the adhesive film of the present invention when heated at a heating rate of 10°C/min in a nitrogen environment after irradiation with light is 300°C or more, the heat resistance of the adhesive film obtained is more excellent, and peeling during high-temperature processing can be further suppressed. The preferred lower limit of the 5% weight loss temperature of the adhesive film of the present invention when heated at a temperature increase rate of 10°C/min in a nitrogen environment after irradiation with light is 350°C, and the further preferred lower limit is 375°C. In addition, the preferred upper limit of the 5% weight loss temperature of the adhesive film of the present invention when heated at a temperature increase rate of 10°C/min in a nitrogen environment after irradiation with light is not particularly limited, and the actual upper limit is 600°C. Furthermore, the 5% weight loss temperature of the adhesive film of the present invention when heated at a temperature increase rate of 10°C/min in a nitrogen environment after irradiation with light can be measured, for example, by using a TG-DTA (thermogravimetric-differential thermal analysis) such as a TG-DTA device (manufactured by Hitachi High-Tech Science, "STA7200RV").

本發明之暫時固定材硬化後於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率的較佳上限為7%。若上述重量減少率為7%以下，則硬化後之上述暫時固定材之耐熱性更優異，能夠進一步抑制高溫加工處理中之剝落。上述重量減少率之更佳上限為5%，進而較佳上限為3%。 又，上述重量減少率之較佳下限並無特別，實質下限為0.01%。 再者，上述於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率例如可藉由使用TG-DTA裝置（Hitachi High-Tech Science公司製造，「STA7200RV」）等的TG-DTA（熱重量-示差熱分析）進行測定。 The preferred upper limit of the weight loss rate of the temporary fixing material of the present invention after hardening is 7% when heated at 290°C for 30 minutes in a nitrogen environment. If the above weight loss rate is less than 7%, the heat resistance of the above temporary fixing material after hardening is better, and it can further inhibit peeling during high-temperature processing. The better upper limit of the above weight loss rate is 5%, and the better upper limit is 3%. In addition, the better lower limit of the above weight loss rate is not special, and the actual lower limit is 0.01%. Furthermore, the weight loss rate when heated at 290°C for 30 minutes in a nitrogen environment can be measured by TG-DTA (thermogravimetric-differential thermal analysis) using a TG-DTA device (manufactured by Hitachi High-Tech Science, "STA7200RV").

本發明之暫時固定材硬化後之紫外線吸收率的較佳下限為80%。若上述紫外線吸收率為80%以上，則硬化後之上述暫時固定材之紫外線吸收性更優異，對雷射加工性能進一步提高，能夠更效率良好地將支持體剝離。又，硬化後之上述暫時固定材之剝離性能進一步提高，且能夠進一步抑制硬化後之上述暫時固定材之糊劑殘留。上述紫外線吸收率之較佳下限為90%，進而較佳下限為95%。 又，上述紫外線吸收率之較佳上限並無特別，實質上限為100%。 再者，上述紫外線吸收率可使用分光光度計進行測定。此時之光程長度設為硬化後之上述暫時固定材之厚度。作為上述分光光度計，例如可舉U-3900（Hitachi High-Tech Science公司製造）等。 The preferred lower limit of the ultraviolet absorption rate of the temporary fixing material of the present invention after curing is 80%. If the above ultraviolet absorption rate is 80% or more, the ultraviolet absorption of the above temporary fixing material after curing is better, the laser processing performance is further improved, and the support body can be peeled off more efficiently. In addition, the peeling performance of the above temporary fixing material after curing is further improved, and the paste residue of the above temporary fixing material after curing can be further suppressed. The preferred lower limit of the above ultraviolet absorption rate is 90%, and the preferred lower limit is 95%. In addition, the preferred upper limit of the above ultraviolet absorption rate is not special, and the actual upper limit is 100%. Furthermore, the above ultraviolet absorption rate can be measured using a spectrophotometer. The optical path length at this time is set to the thickness of the temporary fixing material after hardening. As the above-mentioned spectrophotometer, for example, U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.) can be cited.

本發明之暫時固定材硬化後之凝膠分率的較佳下限為50質量%，較佳上限為99質量%。藉由使上述暫時固定材之硬化後之凝膠分率為上述範圍內，與被黏著體剝離時能夠更容易地剝離。上述硬化物之凝膠分率之更佳下限為60質量%，更佳上限為95質量%。 再者，上述暫時固定材之硬化後之凝膠分率例如係藉由以下方法進行測定。 即，採集質量W 0（g）之硬化後之暫時固定材，將所採集之硬化後之暫時固定材於23℃於甲苯中浸漬24小時。浸漬後，使用金屬網（網眼＃200目，質量：W 1（g））對吸收了甲苯而已膨潤之硬化後之暫時固定材進行過濾，使分離後之硬化後之暫時固定材於110℃之條件下乾燥1小時。繼而，測定乾燥後之硬化後之暫時固定材之質量W 2（g），並使用下述式算出凝膠分率等，藉此，能夠測定上述硬化後之暫時固定材之凝膠分率。 凝膠分率（質量%）＝100×（W 2－W 1）/W 0（W 0：初始硬化後之暫時固定材之質量、W 1：金屬網之初始質量、W 2：乾燥後之包含金屬網之硬化後之暫時固定材的質量） The preferred lower limit of the gel fraction of the temporary fixing material of the present invention after hardening is 50% by mass, and the preferred upper limit is 99% by mass. By making the gel fraction of the temporary fixing material after hardening within the above range, it can be more easily peeled off from the adherend. The preferred lower limit of the gel fraction of the hardened material is 60% by mass, and the preferred upper limit is 95% by mass. Furthermore, the gel fraction of the temporary fixing material after hardening is measured, for example, by the following method. That is, a mass of W0 (g) of hardened temporary fixing material is collected, and the collected hardened temporary fixing material is immersed in toluene at 23°C for 24 hours. After immersion, the hardened temporary fixing material that has absorbed toluene and swelled is filtered using a metal mesh (mesh size #200, mass: W 1 (g)), and the separated hardened temporary fixing material is dried at 110°C for 1 hour. Then, the mass W 2 (g) of the hardened temporary fixing material after drying is measured, and the gel fraction is calculated using the following formula, thereby making it possible to measure the gel fraction of the hardened temporary fixing material. Gel fraction (mass %) = 100 × (W 2 - W 1 ) / W 0 (W 0 : mass of temporary fixing material after initial hardening, W 1 : initial mass of metal mesh, W 2 : mass of temporary fixing material after hardening including metal mesh after drying)

於本發明之暫時固定材並非為液狀或糊狀之情形（例如帶狀之暫時固定材之情形等）時，硬化後之厚度之較佳下限為5 μm，較佳上限為550 μm。藉由使上述暫時固定材之硬化後之厚度為5 μm以上，能夠使上述暫時固定材於初期具有充分之感壓或感熱接著力。藉由使上述暫時固定材之硬化後之厚度為550 μm以下，上述暫時固定材即便於硬化後亦能夠發揮較高之柔軟性，能夠對具有凹凸之被黏著體發揮較高之追隨性，並且剝離時能夠更容易地剝離。上述暫時固定材之硬化後之厚度之更佳下限為10 μm，進而較佳下限為20 μm，進而更佳下限為30 μm。上述暫時固定材之硬化後之厚度之更佳上限為400 μm，進而較佳上限為300 μm，進而更佳上限為200 μm，尤佳上限為150 μm。When the temporary fixing material of the present invention is not in liquid or paste form (e.g., in the case of a tape-shaped temporary fixing material, etc.), the preferred lower limit of the thickness after curing is 5 μm, and the preferred upper limit is 550 μm. By making the thickness of the temporary fixing material after curing to be 5 μm or more, the temporary fixing material can have sufficient pressure-sensitive or heat-sensitive adhesion in the initial stage. By making the thickness of the temporary fixing material after curing to be 550 μm or less, the temporary fixing material can exhibit higher flexibility even after curing, can exhibit higher tracking performance for an adherend with uneven surfaces, and can be more easily peeled off when peeled off. The preferred lower limit of the thickness of the temporary fixing material after hardening is 10 μm, further preferred lower limit is 20 μm, further preferred lower limit is 30 μm. The preferred upper limit of the thickness of the temporary fixing material after hardening is 400 μm, further preferred upper limit is 300 μm, further preferred upper limit is 200 μm, and particularly preferred upper limit is 150 μm.

本發明之接著膜即便於照射低能量之雷射光之情形時，亦能夠容易地將支持體剝離，又，即便於進行高溫加工處理之情形時，亦能夠容易地將接著膜自被黏著體剝離。因此，本發明之接著膜可較佳地用於具有藉由照射雷射光而進行之支持體剝離步驟或高溫加工處理步驟的電子零件之製造。尤其是於半導體裝置等電子零件之製造中，可較佳地用於電子零件之暫時固定。The adhesive film of the present invention can easily peel off the support even when irradiated with low-energy laser light, and can also easily peel off the adherend even when subjected to high-temperature processing. Therefore, the adhesive film of the present invention can be preferably used in the manufacture of electronic parts having a support peeling step or a high-temperature processing step performed by irradiating laser light. In particular, in the manufacture of electronic parts such as semiconductor devices, it can be preferably used for temporary fixation of electronic parts.

本發明之暫時固定材即便於硬化後照射低能量之雷射光之情形時，藉由具有適度之對雷射加工性能，亦能夠容易地將支持體剝離。因此，本發明之暫時固定材可較佳地用於具有藉由照射雷射光而進行之支持體剝離步驟的電子零件之製造。尤其是於半導體裝置之製造中可較佳地使用。The temporary fixing material of the present invention can easily peel off the support body even when irradiated with low-energy laser light after hardening due to its moderate laser processing performance. Therefore, the temporary fixing material of the present invention can be preferably used in the manufacture of electronic parts having a support body peeling step performed by irradiating laser light. It can be preferably used in the manufacture of semiconductor devices in particular.

使本發明之接著膜或本發明之暫時固定材硬化而成之硬化物亦為本發明之一。 本發明之硬化物即便於照射低能量之雷射光的情形時，藉由具有適度之加工性能，亦能夠容易地將支持體剝離。因此，上述硬化物可較佳地用於具有藉由照射雷射光而進行之支持體剝離步驟的電子零件之製造。尤其是於半導體裝置之製造中可較佳地使用。 The hardened product formed by hardening the bonding film of the present invention or the temporary fixing material of the present invention is also one of the present invention. The hardened product of the present invention can easily peel off the support even when irradiated with low-energy laser light because it has appropriate processing performance. Therefore, the above-mentioned hardened product can be preferably used in the manufacture of electronic parts having a support peeling step performed by irradiating laser light. In particular, it can be preferably used in the manufacture of semiconductor devices.

本發明之硬化物可為使液狀、糊狀等之暫時固定材硬化者，亦可為使接著膜或帶狀等之暫時固定材硬化者，其中，較佳為使接著膜或帶狀之暫時固定材硬化者。 於上述接著膜或上述暫時固定材具有光硬化性之情形時，上述硬化物例如能夠藉由以累計光量成為20000 mJ/cm 2之方式對上述暫時固定材照射波長365 nm之紫外線等，從而使上述暫時固定材硬化而獲得。 於上述接著膜或上述暫時固定材具有熱硬化性之情形時，上述硬化物例如能夠藉由將上述暫時固定材於氮氣環境下，經以290℃加熱30分鐘等，從而使上述暫時固定材硬化而獲得。 The hardened material of the present invention may be a temporary fixing material in a liquid or paste state, or a temporary fixing material in a bonding film or tape state. Preferably, a temporary fixing material in a bonding film or tape state is hardened. When the bonding film or the temporary fixing material is light-curable, the hardened material can be obtained by, for example, irradiating the temporary fixing material with ultraviolet light having a wavelength of 365 nm so that the accumulated light amount becomes 20,000 mJ/ cm2 , thereby hardening the temporary fixing material. When the bonding film or the temporary fixing material is heat-curable, the hardened material can be obtained by, for example, heating the temporary fixing material at 290°C for 30 minutes in a nitrogen environment, thereby hardening the temporary fixing material.

使上述接著膜硬化之上述硬化物經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之較佳下限為0.10 μm。藉由使上述硬化物之經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將上述硬化物自支持體剝離。上述硬化物之經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的更佳下限為0.15 μm，進而較佳下限為0.20 μm。 再者，使上述接著膜硬化之上述硬化物經脈衝照射上述波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之下限較佳為於硬化物的至少一面滿足上述範圍，更佳為於硬化物之兩面滿足上述範圍。 使上述暫時固定材硬化之上述硬化物經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的下限為0.10 μm。藉由使上述硬化物之經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上，即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將上述硬化物自支持體剝離。上述硬化物之經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的較佳下限為0.15 μm，更佳下限為0.20 μm。 再者，於上述硬化物並非為液狀或糊狀之暫時固定材之硬化物的情形時，經脈衝照射上述波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之下限只要於硬化物的至少一面滿足上述範圍即可，較佳為於硬化物之兩面滿足上述範圍。 The preferred lower limit of the laser processing depth when the above-mentioned cured product of the above-mentioned adhesive film is pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 is 0.10 μm. By setting the laser processing depth of the above-mentioned cured product to be 0.10 μm or more when the above-mentioned cured product is pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 , the above-mentioned cured product can be more efficiently peeled off from the support even when irradiating low-energy laser light. The lower limit of the laser processing depth of the above-mentioned cured product when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/cm 2 is irradiated by pulse is more preferably 0.15 μm, and further preferably 0.20 μm. Furthermore, the lower limit of the laser processing depth of the above-mentioned cured product when the above-mentioned adhesive film is cured by the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/cm 2 is preferably satisfied in the above range on at least one side of the cured product, and more preferably satisfied in the above range on both sides of the cured product. The lower limit of the laser processing depth when the temporary fixing material is pulsed with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/cm 2 is 0.10 μm. By setting the laser processing depth of the hardened material to 0.10 μm or more when the hardened material is pulsed with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/cm 2 , the hardened material can be more efficiently peeled off from the support even when low-energy laser light is irradiated. The preferred lower limit of the laser processing depth of the above-mentioned cured product when the laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 is pulsed is 0.15 μm, and the more preferred lower limit is 0.20 μm. Furthermore, in the case where the above-mentioned cured product is not a cured product of a temporary fixing material in a liquid or paste state, the lower limit of the laser processing depth when the laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 is pulsed is sufficient as long as at least one side of the cured product satisfies the above range, and preferably satisfies the above range on both sides of the cured product.

上述硬化物之經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的較佳上限為1.0 μm。若經脈衝照射上述波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為1.0 μm以下，則硬化後之上述暫時固定材之對雷射加工性能進一步提高，能夠更效率良好地將支持體剝離。經脈衝照射上述波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度的更佳上限為0.80 μm，進而較佳上限為0.60 μm。 再者，於上述硬化物並非為液狀或糊狀之暫時固定材之硬化物的情形時，經脈衝照射上述波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度之上限較佳為於硬化物的至少一面滿足上述範圍，更佳為於硬化物之兩面滿足上述範圍。 The preferred upper limit of the laser processing depth of the above-mentioned cured product when irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 by pulse is 1.0 μm. If the laser processing depth when irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 by pulse is 1.0 μm or less, the laser processing performance of the above-mentioned temporary fixing material after curing is further improved, and the support body can be peeled off more efficiently. The upper limit of the laser processing depth when the laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 is pulsed is preferably 0.80 μm, and the further upper limit is preferably 0.60 μm. Furthermore, in the case where the cured product is not a temporary fixing material in a liquid or paste state, the upper limit of the laser processing depth when the laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/cm 2 is pulsed is preferably such that at least one side of the cured product satisfies the above range, and more preferably such that both sides of the cured product satisfy the above range.

上述硬化物經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度的較佳上限為1.0 μm。若上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度為1.0 μm以下，則上述硬化物之對雷射加工性能進一步提高，能夠更效率良好地將支持體剝離。上述硬化物之經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度的更佳上限為0.80 μm，進而較佳上限為0.60 μm。 又，上述硬化物之經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度的較佳下限為0.10 μm。若上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上，則上述硬化之對雷射加工性能進一步提高，能夠更效率良好地將支持體剝離。上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度的更佳下限為0.15 μm，進而較佳下限為0.20 μm。 再者，於上述硬化物並非為液狀或糊狀之暫時固定材之硬化物之情形時，上述經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度較佳為於硬化物的至少一面滿足上述範圍，更佳為於硬化物之兩面滿足上述範圍。 The preferred upper limit of the laser processing depth of the above-mentioned hardened material when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ/cm 2 is pulsed is 1.0 μm. If the laser processing depth of the above-mentioned hardened material when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ/cm 2 is less than 1.0 μm, the laser processing performance of the above-mentioned hardened material is further improved, and the support body can be peeled off more efficiently. The upper limit of the laser processing depth of the above-mentioned cured product when the laser light with a pulse irradiation wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 400 mJ/ cm2 is preferably 0.80 μm, and the further upper limit is preferably 0.60 μm. In addition, the lower limit of the laser processing depth of the above-mentioned cured product when the laser light with a pulse irradiation wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 400 mJ/ cm2 is preferably 0.10 μm. If the laser processing depth when the above-mentioned laser light with a pulse irradiation wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ/ cm2 is 0.10 μm or more, the above-mentioned hardening further improves the laser processing performance, and the support body can be peeled off more efficiently. The lower limit of the laser processing depth when the above-mentioned laser light with a pulse irradiation wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ/ cm2 is 0.15 μm, and the further lower limit is 0.20 μm. Furthermore, when the hardened material is not a temporary fixing material in a liquid or paste state, the laser processing depth when the pulse irradiation is performed with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ/ cm2 is preferably within the above range on at least one side of the hardened material, and more preferably on both sides of the hardened material.

本發明之接著膜較佳為用於依序具有支持體、本發明之接著膜及半導體裝置之積層體。若將本發明之接著膜用於具有上述構成之積層體，則能夠更佳地用於製造電子零件。 依序具有支持體、本發明之接著膜及半導體裝置之積層體（以下，亦有時表示為「積層體（a）」）亦為本發明之一。 The bonding film of the present invention is preferably used for a laminate having a support, the bonding film of the present invention, and a semiconductor device in sequence. If the bonding film of the present invention is used for a laminate having the above-mentioned structure, it can be more preferably used for manufacturing electronic components. A laminate having a support, the bonding film of the present invention, and a semiconductor device in sequence (hereinafter, sometimes referred to as "laminate (a)") is also one of the present invention.

本發明之暫時固定材之硬化物較佳為用於依序具有支持體、該硬化物及半導體裝置的積層體。若將本發明之暫時固定材之硬化物用於具有上述構成之積層體，則即便於照射低能量之雷射光之情形時，亦能夠更效率良好地將支持體剝離，故能夠較佳地用於製造電子零件。 依序具有支持體、本發明之暫時固定材之硬化物及半導體裝置，上述支持體之波長300 nm以上400 nm以下之光的穿透率為50%以上的積層體（以下，有時亦表示為「積層體（b）」）亦為本發明之一。 The hardened temporary fixing material of the present invention is preferably used for a laminate having a support, the hardened material, and a semiconductor device in sequence. If the hardened temporary fixing material of the present invention is used for a laminate having the above-mentioned structure, the support can be more efficiently peeled off even when irradiated with low-energy laser light, so it can be preferably used for manufacturing electronic components. A laminate having a support, a hardened temporary fixing material of the present invention, and a semiconductor device in sequence, wherein the transmittance of the support for light with a wavelength of 300 nm to 400 nm is 50% or more (hereinafter, sometimes referred to as "laminated body (b)") is also one of the present invention.

以下，關於上述積層體（a）與上述積層體（b）中共通之事項，並無特別指定，或者簡記為「上述積層體」。Hereinafter, matters common to the above-mentioned laminate (a) and the above-mentioned laminate (b) are not particularly specified or are simply referred to as "the above-mentioned laminate".

作為上述支持體之原材料，較佳為光之穿透率較高之原材料，例如可舉玻璃、石英、藍寶石等。The material of the support is preferably a material with high light transmittance, such as glass, quartz, sapphire, etc.

於上述積層體（a）中，上述支持體之波長200 nm以上355 nm以下之光的穿透率之較佳下限為20%。若上述支持體之波長200 nm以上355 nm以下之光之穿透率為20%以上，則能夠效率良好地將上述支持體自上述接著膜剝離。上述支持體之波長200 nm以上355 nm以下之光之穿透率的更佳下限為30%，進而較佳下限為50%。 又，上述支持體之波長200 nm以上355 nm以下之光之穿透率的較佳上限並無特別，實質上限為95%。 In the above-mentioned laminate (a), the preferred lower limit of the transmittance of the above-mentioned support for light with a wavelength of 200 nm to 355 nm is 20%. If the transmittance of the above-mentioned support for light with a wavelength of 200 nm to 355 nm is 20% or more, the above-mentioned support can be efficiently peeled off from the above-mentioned adhesive film. The preferred lower limit of the transmittance of the above-mentioned support for light with a wavelength of 200 nm to 355 nm is 30%, and the further preferred lower limit is 50%. In addition, the preferred upper limit of the transmittance of the above-mentioned support for light with a wavelength of 200 nm to 355 nm is not particularly limited, and the actual upper limit is 95%.

於上述積層體（b）中，上述支持體之波長300 nm以上400 nm以下之光之穿透率的較佳下限為50%。若上述支持體之波長300 nm以上400 nm以下之光之穿透率為50%以上，則上述硬化物之對雷射加工性能進一步提高，藉此，能夠更效率良好地將上述支持體剝離。上述支持體之波長300 nm以上400 nm以下之光之穿透率的更佳下限為60%，進而較佳下限為70%。 又，上述支持體之波長300 nm以上400 nm以下之光之穿透率的較佳上限並無特別，實質上限為95%。 In the above-mentioned laminate (b), the preferred lower limit of the transmittance of the above-mentioned support body for light with a wavelength of 300 nm to 400 nm is 50%. If the transmittance of the above-mentioned support body for light with a wavelength of 300 nm to 400 nm is 50% or more, the laser processing performance of the above-mentioned cured product is further improved, thereby enabling the above-mentioned support body to be peeled off more efficiently. The preferred lower limit of the transmittance of the above-mentioned support body for light with a wavelength of 300 nm to 400 nm is 60%, and the further preferred lower limit is 70%. In addition, the preferred upper limit of the transmittance of the above-mentioned support body for light with a wavelength of 300 nm to 400 nm is not special, and the actual upper limit is 95%.

上述支持體之霧度之上限並無特別限定，就將雷射光自上述支持體側照射至上述接著膜或上述暫時固定材之硬化物之觀點而言，較佳為上述支持體之霧度較小。上述支持體之霧度之較佳上限為10%，更佳上限為5%。 又，上述支持體之霧度之較佳下限並無特別，實質下限為0.001%。 再者，上述支持體之霧度例如可使用霧度計（日本電色工業公司製造，「NDH4000」）等進行測定。 The upper limit of the haze of the support is not particularly limited. From the perspective of irradiating the laser light from the side of the support to the adhesive film or the cured product of the temporary fixing material, it is preferred that the haze of the support is smaller. The preferred upper limit of the haze of the support is 10%, and the more preferred upper limit is 5%. In addition, the preferred lower limit of the haze of the support is not particularly limited, and the actual lower limit is 0.001%. Furthermore, the haze of the support can be measured, for example, using a haze meter (manufactured by Nippon Denshoku Industries, "NDH4000"), etc.

上述積層體（a）只要依序具有如上述之支持體、本發明之接著膜、半導體裝置即可，亦可於無損本發明之效果之範圍內進而具有其他層。 又，上述積層體（b）只要依序具有如上述之支持體、暫時固定材之硬化物、半導體裝置即可，亦可於無損本發明之效果之範圍內進而具有其他層。 The above-mentioned laminate (a) only needs to have the above-mentioned support, the bonding film of the present invention, and the semiconductor device in order, and may also have other layers within the scope that does not damage the effect of the present invention. In addition, the above-mentioned laminate (b) only needs to have the above-mentioned support, the hardened material of the temporary fixing material, and the semiconductor device in order, and may also have other layers within the scope that does not damage the effect of the present invention.

具有使用上述積層體（a），自上述支持體側對上述積層體（a）照射光之光照射步驟、對上述積層體實施加熱處理或伴隨發熱之處理的高溫加工處理步驟、自上述支持體側對上述積層體（a）照射波長200 nm以上355 nm以下之雷射光而將上述支持體自上述接著膜剝離之支持體剝離步驟（以下，亦有時表示為「支持體剝離步驟（a）」）、及將上述接著膜自上述半導體裝置剝離之接著膜剝離步驟的電子零件之製造方法亦為本發明之一。 本發明之電子零件之製造方法即便於照射低能量之雷射光之情形時，亦能夠效率良好地將上述支持體自上述接著膜剝離，即便於進行高溫加工處理之情形時，亦能夠效率良好地將上述接著膜自上述半導體裝置剝離。結果，能夠在不會伴有接著膜之碳化、支持體之損傷、接著膜或支持體之污染、支持體之剝離性能惡化、及接著膜之剝離時產生糊劑殘留等而導致電子零件之加工品質降低之情況下製造電子零件。 One of the present inventions is a method for manufacturing an electronic component comprising a light irradiation step of irradiating the laminate (a) with light from the support side, a high temperature processing step of subjecting the laminate to a heat treatment or a treatment accompanied by heating, a support peeling step of peeling the support from the bonding film by irradiating the laminate (a) with laser light having a wavelength of not less than 200 nm and not more than 355 nm from the support side (hereinafter sometimes referred to as "support peeling step (a)"), and a bonding film peeling step of peeling the bonding film from the semiconductor device. The method for manufacturing electronic components of the present invention can efficiently peel the support from the bonding film even when irradiating low-energy laser light, and can efficiently peel the bonding film from the semiconductor device even when performing high-temperature processing. As a result, electronic components can be manufactured without carbonization of the bonding film, damage to the support, contamination of the bonding film or the support, deterioration of the stripping performance of the support, and generation of paste residues during stripping of the bonding film, which would reduce the processing quality of the electronic components.

作為上述光照射步驟中所照射之光之光源，可舉超高壓水銀燈、LED等。其中，就容易使上述光硬化型接著劑硬化之觀點而言，較佳為超高壓水銀燈。As a light source of the light irradiated in the light irradiation step, there can be mentioned an ultra-high pressure mercury lamp, LED, etc. Among them, from the viewpoint of easily curing the light-curing adhesive, an ultra-high pressure mercury lamp is preferred.

上述光照射步驟中所照射之光之波長的較佳下限為356 nm，較佳上限為500 nm。藉由使上述光照射步驟中所照射之光之波長為上述範圍內，於上述光照射步驟中，上述接著膜更效率良好地進行光硬化，從而於上述接著膜剝離步驟中能夠容易地將接著膜剝離。又，於上述支持體剝離步驟中，能夠使用下述範圍之波長之雷射光更效率良好地將上述支持體自上述接著膜剝離。上述光照射步驟中所照射之光之波長的更佳下限為360 nm，進而較佳下限為375 nm，更佳上限為450 nm，進而較佳上限為420 nm。The wavelength of the light irradiated in the light irradiation step preferably has a lower limit of 356 nm and an upper limit of 500 nm. By making the wavelength of the light irradiated in the light irradiation step within the above range, the bonding film is more efficiently photocured in the light irradiation step, so that the bonding film can be easily peeled off in the bonding film peeling step. In addition, in the support peeling step, the support can be more efficiently peeled off from the bonding film using laser light of a wavelength in the following range. The wavelength of the light irradiated in the light irradiation step preferably has a lower limit of 360 nm, further preferably has a lower limit of 375 nm, and a higher limit of 450 nm, further preferably has a higher limit of 420 nm.

上述光照射步驟中所照射之光之累計光量的較佳下限為1000 mJ/cm 2，較佳上限為30000 mJ/cm 2。藉由以上述光照射步驟中所照射之光之累計光量成為1000 mJ/cm 2以上之方式照射，能夠使上述接著膜更充分地硬化。藉由以上述光照射步驟中所照射之光之累計光量成為30000 mJ/cm 2以下之方式照射，能夠抑制低分子化合物之光分解，於上述高溫加工處理步驟中能夠應用於更高之溫度。上述光照射步驟中所照射之光之累計光量的更佳下限為3000 mJ/cm 2，進而較佳下限為5000 mJ/cm 2，更佳上限為25000 mJ/cm 2，進而較佳上限為20000 mJ/cm 2。 The preferred lower limit of the cumulative light quantity of the light irradiated in the above-mentioned light irradiation step is 1000 mJ/cm 2 , and the preferred upper limit is 30000 mJ/cm 2 . By irradiating in such a way that the cumulative light quantity of the light irradiated in the above-mentioned light irradiation step becomes 1000 mJ/cm 2 or more, the above-mentioned adhesive film can be more fully cured. By irradiating in such a way that the cumulative light quantity of the light irradiated in the above-mentioned light irradiation step becomes 30000 mJ/cm 2 or less, the photodecomposition of low molecular weight compounds can be suppressed, and a higher temperature can be applied in the above-mentioned high temperature processing step. The cumulative light amount of the light irradiated in the light irradiation step is more preferably 3000 mJ/cm 2 , more preferably 5000 mJ/cm 2 , and more preferably 25000 mJ/cm 2 , more preferably 20000 mJ/cm 2 .

作為上述高溫加工處理步驟，例如可舉回焊、濺鍍、熱壓接接合（TCB）等處理。As the high temperature processing step, for example, reflow, sputtering, thermal compression bonding (TCB) and the like can be used.

上述支持體剝離步驟（a）中所照射之雷射光之波長的較佳下限為200 nm，較佳上限為355 nm。藉由使上述支持體剝離步驟（a）中所照射之雷射光之波長為上述範圍內，能夠進一步抑制上述支持體之損傷等，並且能夠更效率良好地將上述支持體自上述接著膜剝離。The wavelength of the laser light irradiated in the support stripping step (a) preferably has a lower limit of 200 nm and an upper limit of 355 nm. By making the wavelength of the laser light irradiated in the support stripping step (a) within the above range, damage to the support can be further suppressed, and the support can be more efficiently stripped from the bonding film.

上述支持體剝離步驟（a）中所照射之雷射光之照射能量密度的較佳上限為500 mJ/cm 2。若上述支持體剝離步驟（a）中所照射之雷射光之照射能量密度為500 mJ/cm 2以下，則能夠進一步抑制上述支持體之損傷等，並且能夠更效率良好地將上述支持體自上述接著膜剝離。上述支持體剝離步驟（a）中所照射之雷射光之照射能量密度之更佳上限為400 mJ/cm 2，進而較佳上限為300 mJ/cm 2。 又，上述支持體剝離步驟（a）中所照射之雷射光之照射能量密度並無較佳下限，實質下限為100 mJ/cm 2。 The upper limit of the irradiation energy density of the laser light irradiated in the support stripping step (a) is preferably 500 mJ/cm 2 . If the irradiation energy density of the laser light irradiated in the support stripping step (a) is 500 mJ/cm 2 or less, damage to the support can be further suppressed, and the support can be more efficiently stripped from the adhesive film. The upper limit of the irradiation energy density of the laser light irradiated in the support stripping step (a) is more preferably 400 mJ/cm 2 , and further preferably 300 mJ/cm 2 . In addition, there is no preferred lower limit for the irradiation energy density of the laser light irradiated in the support stripping step (a), but the practical lower limit is 100 mJ/cm 2 .

上述支持體剝離步驟（a）中所照射之雷射光可為CW（Continuous Wave）雷射，亦可為脈衝雷射。The laser light irradiated in the support stripping step (a) may be a CW (Continuous Wave) laser or a pulsed laser.

於上述支持體剝離步驟（a）中所照射之雷射光為脈衝雷射之情形時，脈衝寬度之較佳上限為100 nsec。若上述支持體剝離步驟（a）中所照射之雷射光之脈衝寬度為100 nsec以下，則能夠進一步抑制上述支持體之損傷等，並且能夠更效率良好地將上述支持體自上述接著膜剝離。上述支持體剝離步驟（a）中所照射之雷射光之脈衝寬度之更佳上限為50 nsec，進而較佳上限為20 nsec。 上述支持體剝離步驟（a）中所照射之雷射光之脈衝寬度之較佳下限並無特別，實質下限為5 fsec。 When the laser light irradiated in the support stripping step (a) is a pulse laser, the upper limit of the pulse width is preferably 100 nsec. If the pulse width of the laser light irradiated in the support stripping step (a) is less than 100 nsec, damage to the support can be further suppressed, and the support can be more efficiently stripped from the bonding film. The upper limit of the pulse width of the laser light irradiated in the support stripping step (a) is more preferably 50 nsec, and the upper limit is further preferably 20 nsec. There is no particular lower limit for the pulse width of the laser light irradiated in the support stripping step (a), and the practical lower limit is 5 fsec.

具有自支持體側對依序含有支持體、暫時固定材之硬化物及半導體裝置之積層體脈衝照射波長308 nm以上355 nm以下、脈衝寬度100 nsec以下、照射能量密度500 mJ/cm 2以下之雷射光，藉此，將上述支持體自上述積層體剝離之支持體剝離步驟（以下，亦有時表示為「支持體剝離步驟（b）」）的電子零件之製造方法亦為本發明之一。 本發明之電子零件之製造方法含有支持體剝離步驟，其係自上述支持體側對依序具有支持體、暫時固定材之硬化物及半導體裝置之積層體脈衝照射波長308 nm以上355 nm以下、脈衝寬度100 nsec以下、照射能量密度500 mJ/cm 2以下之雷射光，而將上述支持體剝離。藉由使上述製造方法含有上述支持體剝離步驟（b），即便於照射低能量之雷射之情形時，亦能夠效率良好地將上述支持體剝離，從而能夠在不會伴有暫時固定材之碳化、支持體損傷、暫時固定材或支持體之污染、及支持體之剝離性能惡化等而導致電子零件之加工品質降低的情況下製造電子零件。 One of the present inventions is a method for manufacturing an electronic component having a support stripping step (hereinafter sometimes referred to as "support stripping step (b)") in which a laminate containing a support, a cured product of a temporary fixing material, and a semiconductor device is pulsed with laser light having a wavelength of not less than 308 nm and not more than 355 nm, a pulse width of not more than 100 nsec, and an irradiation energy density of not more than 500 mJ/ cm2 from the support side to strip the support from the laminate. The manufacturing method of the electronic component of the present invention includes a support peeling step, which is to peel the support from the side of the support by pulse irradiating a layered body having a support, a hardened temporary fixing material, and a semiconductor device in sequence with laser light having a wavelength of 308 nm to 355 nm, a pulse width of 100 nsec or less, and an irradiation energy density of 500 mJ/cm2 or less . By making the above-mentioned manufacturing method include the above-mentioned support stripping step (b), the above-mentioned support can be efficiently stripped even when irradiated with low-energy laser, thereby being able to manufacture electronic components without carbonization of the temporary fixing material, damage to the support, contamination of the temporary fixing material or the support, and deterioration of the stripping performance of the support, which would lead to a decrease in the processing quality of the electronic components.

於本發明之電子零件之製造方法中，可較佳地使用與上述依序含有支持體、暫時固定材之硬化物及半導體裝置之積層體相同者。In the method for manufacturing the electronic component of the present invention, it is preferable to use the same laminated body as described above which sequentially contains a support, a hardened material of a temporary fixing material, and a semiconductor device.

上述支持體剝離步驟（b）中所照射之雷射光之波長之下限為308 nm，上限為355 nm。藉由使上述支持體剝離步驟（b）中所照射之雷射光之波長為上述範圍內，上述硬化物之對雷射加工性能提高，從而能夠效率良好地將上述支持體剝離。The wavelength of the laser light irradiated in the support stripping step (b) has a lower limit of 308 nm and an upper limit of 355 nm. By setting the wavelength of the laser light irradiated in the support stripping step (b) to be within the above range, the laser processing performance of the cured product is improved, thereby enabling the support to be stripped efficiently.

上述支持體剝離步驟（b）中所照射之雷射光之脈衝寬度之上限為100 nsec。若上述支持體剝離步驟（b）中所照射之雷射光之脈衝寬度為100 nsec以下，則上述硬化物之對雷射加工性能提高，能夠抑制支持體之損傷等，並且能夠效率良好地將上述支持體剝離。上述支持體剝離步驟（b）中所照射之雷射光之脈衝寬度之較佳上限為50 nsec，更佳上限為20 nsec。 上述支持體剝離步驟（b）中所照射之雷射光之脈衝寬度的較佳下限並無特別，實質下限為50 fsec。 The upper limit of the pulse width of the laser light irradiated in the support stripping step (b) is 100 nsec. If the pulse width of the laser light irradiated in the support stripping step (b) is less than 100 nsec, the laser processing performance of the hardened material is improved, the damage to the support can be suppressed, and the support can be stripped efficiently. The upper limit of the pulse width of the laser light irradiated in the support stripping step (b) is preferably 50 nsec, and the more preferably 20 nsec. There is no particular lower limit for the pulse width of the laser light irradiated in the support stripping step (b), and the actual lower limit is 50 fsec.

上述支持體剝離步驟（b）中所照射之雷射光之照射能量密度之上限為500 mJ/cm 2。若上述支持體剝離步驟（b）中所照射之雷射光之照射能量密度為500 mJ/cm 2以下，則上述硬化物之對雷射加工性能提高，從而能夠效率良好地將上述支持體剝離。上述支持體剝離步驟（b）中所照射之雷射光之照射能量密度之較佳上限為400 mJ/cm 2，更佳上限為300 mJ/cm 2。 又，上述支持體剝離步驟（b）中所照射之雷射光之照射能量密度並無較佳下限，實質下限為100 mJ/cm 2。 The upper limit of the irradiation energy density of the laser light irradiated in the support stripping step (b) is 500 mJ/cm 2 . If the irradiation energy density of the laser light irradiated in the support stripping step (b) is 500 mJ/cm 2 or less, the laser processing performance of the hardened material is improved, so that the support can be stripped efficiently. The upper limit of the irradiation energy density of the laser light irradiated in the support stripping step (b) is preferably 400 mJ/cm 2 , and the more preferred upper limit is 300 mJ/cm 2 . In addition, the irradiation energy density of the laser light irradiated in the support stripping step (b) has no preferred lower limit, and the actual lower limit is 100 mJ/cm 2 .

本發明之電子零件之製造方法於上述支持體剝離步驟（b）前具有使暫時固定材硬化之步驟。上述硬化步驟較佳為具有例如照射光使上述暫時固定材硬化之光硬化步驟、及/或對上述暫時固定材進行加熱而使上述暫時固定材硬化之熱硬化步驟。The method for manufacturing electronic components of the present invention includes a step of hardening the temporary fixing material before the support stripping step (b). The hardening step is preferably a light hardening step of hardening the temporary fixing material by irradiating light and/or a heat hardening step of hardening the temporary fixing material by heating the temporary fixing material.

上述支持體剝離步驟（a）及上述支持體剝離步驟（b）中所照射之雷射光之較佳照射形狀下之強度的分佈根據目的而有所變化，較佳為高斯波形或經平坦化處理。 於上述支持體剝離步驟中所照射之雷射光之照射形狀下之強度之分佈為高斯波形的情形時，能夠藉由照射1個脈衝之雷射光處理成加工均等之圓形。 於上述支持體剝離步驟中所照射之雷射光之照射形狀下之強度之分佈經平坦化處理之情形時，無須重複照射雷射光，能夠更均勻地照射雷射光。再者，作為上述平坦化處理之方法，例如可舉使用分光器或遮罩之方法等。 The intensity distribution of the laser light irradiated in the support stripping step (a) and the support stripping step (b) varies according to the purpose, and is preferably a Gaussian waveform or flattened. In the case where the intensity distribution of the laser light irradiated in the support stripping step is a Gaussian waveform, it can be processed into a uniformly processed circle by irradiating one pulse of laser light. In the case where the intensity distribution of the laser light irradiated in the support stripping step is flattened, it is not necessary to irradiate the laser light repeatedly, and the laser light can be irradiated more uniformly. Furthermore, as the above-mentioned flattening processing method, for example, a method using a spectrometer or a mask can be cited.

上述支持體剝離步驟（a）及上述支持體剝離步驟（b）中所照射之雷射光之照射形狀較佳為四邊形。藉由使上述雷射光之照射形狀為四邊形，能夠在不產生空白之情況下更均勻地照射雷射光。The irradiation shape of the laser light irradiated in the support peeling step (a) and the support peeling step (b) is preferably a quadrilateral. By making the irradiation shape of the laser light a quadrilateral, the laser light can be irradiated more uniformly without generating blanks.

於上述支持體剝離步驟（a）及上述支持體剝離步驟（b）中，較佳為使雷射光照射裝置、或搭載有上述積層體之平台於縱橫方向移動，藉此，對上述積層體之上述支持體之整個表面照射雷射光。此時，對上述積層體施加偏移（offset），並以與偏移重合之方式照射雷射光。In the support peeling step (a) and the support peeling step (b), it is preferred that the laser irradiation device or the platform carrying the laminate is moved in the longitudinal and transverse directions, thereby irradiating the entire surface of the support of the laminate with laser light. At this time, an offset is applied to the laminate, and the laser light is irradiated in a manner that overlaps with the offset.

於在上述支持體剝離步驟（a）及上述支持體剝離步驟（b）中照射雷射光之情形時，有時會產生白煙。若產生上述白煙，則雷射光被遮住而雷射光照射裝置之加工性能降低。因此，較佳為於上述支持體剝離步驟（a）及上述支持體剝離步驟（b）中，於照射雷射光時進行換氣。 [發明之效果] When laser light is irradiated in the support stripping step (a) and the support stripping step (b), white smoke may be generated. If the white smoke is generated, the laser light is blocked and the processing performance of the laser light irradiation device is reduced. Therefore, it is preferable to ventilate when irradiating laser light in the support stripping step (a) and the support stripping step (b). [Effect of the invention]

根據本發明，能夠提供一種接著膜，其即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離，進而，即便於進行高溫加工處理之情形時，對被黏著體之剝離性亦優異。又，根據本發明，能夠提供一種該接著膜之硬化物。進而，根據本發明，能夠提供一種依序具有支持體、該接著膜、及半導體之積層體。進而，根據本發明，能夠提供一種電子零件之製造方法，其具有：使用該積層體，即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離之步驟；及即便於進行高溫加工處理之情形時，亦能夠容易地將被黏著體剝離之步驟。 又，根據本發明，能夠提供一種暫時固定材，其即便於硬化後照射低能量之雷射光之情形時，對雷射加工性能亦優異，從而能夠效率良好地將支持體剝離。又，根據本發明，能夠提供一種該暫時固定材之硬化物。進而，根據本發明，能夠提供一種具有該硬化物之積層體。進而，根據本發明，能夠提供一種電子零件之製造方法，其具有如下步驟：即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離。 According to the present invention, a bonding film can be provided, which can efficiently peel off a support even when irradiated with low-energy laser light, and has excellent peeling properties from an adherend even when subjected to high-temperature processing. In addition, according to the present invention, a cured product of the bonding film can be provided. Furthermore, according to the present invention, a laminate having a support, the bonding film, and a semiconductor in sequence can be provided. Furthermore, according to the present invention, a method for manufacturing electronic components can be provided, which has: using the laminate, even when irradiated with low-energy laser light, the step of efficiently peeling off the support body can be carried out; and even when high-temperature processing is carried out, the step of easily peeling off the adhered body can be carried out. Furthermore, according to the present invention, a temporary fixing material can be provided, which has excellent laser processing performance even when irradiated with low-energy laser light after curing, so that the support body can be peeled off efficiently. Furthermore, according to the present invention, a cured product of the temporary fixing material can be provided. Furthermore, according to the present invention, a laminate having the cured product can be provided. Furthermore, according to the present invention, a method for manufacturing electronic components can be provided, which has the following steps: even when irradiated with low-energy laser light, the support body can be efficiently peeled off.

以下，舉實施例對本發明之態樣更詳細地進行說明，但本發明並不僅限定於該等實施例。The present invention is described in more detail below with reference to embodiments, but the present invention is not limited to these embodiments.

（合成例1） 於放入了Teflon（註冊商標）攪拌器之容量500 ml之圓底燒瓶中投入250 ml之甲苯。依序添加二聚二胺（Croda公司製造，「Priamine 1075」）31.9 g（0.06莫耳）、2,2-雙(3-胺基-4-羥基苯基)-六氟丙烷5.5 g（0.015莫耳）、及4,4'-(4,4'-亞異丙基二苯氧基)二鄰苯二甲酸酐39.8 g（0.0765莫耳）。將迪安-斯塔克（Dean-Stark）管與電容器安裝於燒瓶，使所獲得之混合物回流6小時，並冷卻至室溫。獲得褐色固體狀之具有下述式（6-1）所表示之結構單元及下述式（6-2）所表示之結構單元的聚醯亞胺A。 針對所獲得之聚醯亞胺A，藉由使用作為溶出液之THF、作為管柱之HR-MB-M（Waters公司製造）的凝膠滲透層析（GPC）法進行測定，結果重量平均分子量為78000。 (Synthesis Example 1) 250 ml of toluene was placed in a 500 ml round-bottom flask with a Teflon (registered trademark) stirrer. 31.9 g (0.06 mol) of dimerized diamine (manufactured by Croda, "Priamine 1075"), 5.5 g (0.015 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, and 39.8 g (0.0765 mol) of 4,4'-(4,4'-isopropyldiphenoxy)diphthalic anhydride were added in sequence. A Dean-Stark tube and a capacitor were installed in the flask, and the obtained mixture was refluxed for 6 hours and cooled to room temperature. A brown solid polyimide A having a structural unit represented by the following formula (6-1) and a structural unit represented by the following formula (6-2) was obtained. The obtained polyimide A was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (manufactured by Waters) as a column. The result showed that the weight average molecular weight was 78,000.

（合成例2） 於放入了Teflon（註冊商標）攪拌器之容量500 ml之圓底燒瓶中投入250 ml之甲苯。添加二聚二胺（Croda公司製造，「Priamine 1075」）56 g（0.1莫耳）及馬來酸酐19.6 g（0.2莫耳），繼而，添加甲磺酸酐5 g。使所獲得之溶液回流12小時後，冷卻至室溫，將甲苯300 ml添加至燒瓶中，並藉由靜置進行層分離，將作為雜質之下層去除。使所獲得之溶液通過填充有矽膠之玻璃料漏斗進行過濾後，將溶劑於真空去除，獲得茶色液狀之下述式（7）所表示之雙馬來醯亞胺化合物D。 (Synthesis Example 2) 250 ml of toluene was placed in a 500 ml round-bottom flask equipped with a Teflon (registered trademark) stirrer. 56 g (0.1 mol) of dimerized diamine ("Priamine 1075" manufactured by Croda) and 19.6 g (0.2 mol) of maleic anhydride were added, and then 5 g of methanesulfonic anhydride was added. The obtained solution was refluxed for 12 hours, cooled to room temperature, 300 ml of toluene was added to the flask, and the layers were separated by standing to remove the lower layer as impurities. The obtained solution was filtered through a glass funnel filled with silica gel, and the solvent was removed in vacuum to obtain a brown liquid bismaleimide compound D represented by the following formula (7).

（合成例3） 於放入了Teflon（註冊商標）攪拌器之容量500 ml之圓底燒瓶中投入250 ml之甲苯。依序添加二聚二胺（Croda公司製造，「Priamine 1075」）39.9 g（0.075莫耳）、及4,4'-(4,4'-亞異丙基二苯氧基)二鄰苯二甲酸酐39.8 g（0.0765莫耳）。將迪安-斯塔克管與電容器安裝於燒瓶，使所獲得之混合物回流6小時，並冷卻至室溫。獲得褐色固體狀之具有下述式（8）所表示之結構單元之聚醯亞胺B。 針對所獲得之聚醯亞胺B，藉由使用作為溶出液之THF、作為管柱之HR-MB-M（Waters公司製造）的凝膠滲透層析（GPC）法進行測定，結果重量平均分子量為90000。 (Synthesis Example 3) 250 ml of toluene was placed in a 500 ml round-bottom flask with a Teflon (registered trademark) stirrer. 39.9 g (0.075 mol) of dimerized diamine (manufactured by Croda, "Priamine 1075") and 39.8 g (0.0765 mol) of 4,4'-(4,4'-isopropyldiphenoxy)diphthalic anhydride were added in sequence. A Dean-Stark tube and a capacitor were installed in the flask, and the obtained mixture was refluxed for 6 hours and cooled to room temperature. A brown solid polyimide B having a structural unit represented by the following formula (8) was obtained. The obtained polyimide B was measured by gel permeation chromatography (GPC) using THF as the eluent and HR-MB-M (manufactured by Waters) as the column, and the weight average molecular weight was 90,000.

再者，表1～8中之雙馬來醯亞胺C使用下述式（9）所表示之雙馬來醯亞胺化合物（Designer Molecules公司製造，「BMI-3000GEL」）。Note that the bismaleimide C in Tables 1 to 8 used a bismaleimide compound represented by the following formula (9) (manufactured by Designer Molecules, “BMI-3000GEL”).

式（9）中，n為重複數目。In formula (9), n is the number of repetitions.

（丙烯酸系共聚物E之合成） 準備具備溫度計、攪拌機、冷凝管之反應器，於該反應器內添加丙烯酸2-乙基己酯94質量份、甲基丙烯酸羥乙酯6質量份、月桂硫醇0.01質量份、及乙酸乙酯80質量份後，對反應器進行加熱而開始回流。繼而，於上述反應器內添加作為聚合起始劑之1,1-雙(第三己基過氧基)-3,3,5-三甲基環己烷0.01質量份，於回流下開始聚合。繼而，於聚合開始1小時後及2小時後，均分別添加1,1-雙(第三己基過氧基)-3,3,5-三甲基環己烷0.01質量份，進而，於聚合開始4小時後添加過氧化特戊酸第三己酯0.05質量份以繼續進行聚合反應。繼而，於聚合開始8小時後，獲得固形物成分55質量%、重量平均分子量50萬之包含含官能基丙烯酸系聚合物之乙酸乙酯溶液。 相對於所獲得之包含含官能基丙烯酸系聚合物之乙酸乙酯溶液之樹脂固形物成分100質量份，添加甲基丙烯酸2-異氰酸基乙酯3.5質量份進行反應，獲得丙烯酸共聚物D。丙烯酸共聚物之重量平均分子量為55萬。 再者，針對所獲得之丙烯酸系共聚物之重量平均分子量，藉由使用作為溶出液之THF、作為管柱之HR-MB-M 6.0×150 mm（Waters公司製造）的凝膠滲透層析（GPC，裝置名：Acquity APC系統（Waters公司製造））法進行測定。 (Synthesis of acrylic copolymer E) Prepare a reactor equipped with a thermometer, a stirrer, and a condenser. Add 94 parts by mass of 2-ethylhexyl acrylate, 6 parts by mass of hydroxyethyl methacrylate, 0.01 parts by mass of lauryl mercaptan, and 80 parts by mass of ethyl acetate to the reactor, and then heat the reactor to start reflux. Then, add 0.01 parts by mass of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator to the reactor, and start polymerization under reflux. Then, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane 0.01 parts by weight was added 1 hour and 2 hours after the start of the polymerization, and then 0.05 parts by weight of tert-hexyl peroxypivalate was added 4 hours after the start of the polymerization to continue the polymerization reaction. Then, 8 hours after the start of the polymerization, an ethyl acetate solution containing a functional acrylic polymer with a solid content of 55% and a weight average molecular weight of 500,000 was obtained. Relative to 100 parts by weight of the resin solid content of the obtained ethyl acetate solution containing a functional acrylic polymer, 3.5 parts by weight of 2-isocyanatoethyl methacrylate was added for reaction to obtain acrylic copolymer D. The weight average molecular weight of the acrylic copolymer is 550,000. Furthermore, the weight average molecular weight of the obtained acrylic copolymer was measured by gel permeation chromatography (GPC, device name: Acquity APC system (manufactured by Waters)) using THF as the eluent and HR-MB-M 6.0×150 mm (manufactured by Waters) as the column.

（實施例1-1～1-23、比較例1-1～1-7） （接著膜之製作） 於甲苯150 ml中添加表1～2、4所記載之各材料並進行混合，獲得光硬化型接著劑之甲苯溶液。 利用刮刀將所獲得之光硬化型接著劑之甲苯溶液以乾燥皮膜之厚度成為80 μm之方式塗佈於單面實施了離型處理之厚度50 μm之離型聚對苯二甲酸乙二酯（PET）膜之離型處理面上，以130℃加熱10分鐘，使塗佈溶液乾燥，獲得積層膜。進而，將單面實施了離型處理之厚度50 μm之離型PET膜以離型處理面與乾燥皮膜對向之方式重疊於積層膜，藉此，獲得附離型PET膜之接著膜。 (Examples 1-1 to 1-23, Comparative Examples 1-1 to 1-7) (Preparation of adhesive film) The materials listed in Tables 1 to 2 and 4 were added to 150 ml of toluene and mixed to obtain a toluene solution of a light-curing adhesive. The obtained toluene solution of a light-curing adhesive was applied to a release-treated surface of a release-treated polyethylene terephthalate (PET) film with a thickness of 50 μm on one side thereof using a scraper so that the thickness of the dry film became 80 μm. The applied solution was dried by heating at 130°C for 10 minutes to obtain a laminated film. Furthermore, a 50 μm thick release PET film with release treatment applied on one side was overlapped on the laminated film in such a way that the release treatment surface and the dry film faced each other, thereby obtaining a bonding film of the release PET film.

（接著層之凝膠分率） 將所獲得之接著膜之其中一PET膜剝離，採集質量W 0（g）之接著層，將所採集之光硬化型接著劑於23℃於甲苯中浸漬24小時。浸漬後，使用金屬網（網眼＃200目，質量：W 1（g）），對吸收甲苯并已膨潤之接著層進行過濾，將分離後之光硬化型接著劑於110℃之條件下乾燥1小時。繼而，測定乾燥後之接著層之質量W 2（g），並使用下述式算出凝膠分率等，藉此，測定接著層照射光前之凝膠分率。將結果示於表1～2、4中。 凝膠分率（質量%）＝100×（W 2－W 1）/W 0（W 0：初始接著層之質量、W 1：金屬網之初始質量、W 2：乾燥後之含有金屬網之接著層的質量） 又，藉由超高壓水銀燈以累計光量成為20000 mJ/cm 2之方式對所獲得之接著膜照射波長405 nm之光後，將接著膜之其中一PET膜剝離，藉由與上述接著層之照射光前之凝膠分率相同之方法測定接著層照射光後之凝膠分率。將結果示於表1～2、4中。 (Gel fraction of adhesive layer) One of the PET films of the adhesive film obtained was peeled off, and the adhesive layer with a mass of W 0 (g) was collected. The collected light-curing adhesive was immersed in toluene at 23°C for 24 hours. After immersion, the adhesive layer that absorbed toluene and swelled was filtered using a metal mesh (mesh #200 mesh, mass: W 1 (g)), and the separated light-curing adhesive was dried at 110°C for 1 hour. Then, the mass W 2 (g) of the adhesive layer after drying was measured, and the gel fraction was calculated using the following formula, thereby measuring the gel fraction of the adhesive layer before irradiation with light. The results are shown in Tables 1 to 2 and 4. Gel fraction (mass %) = 100 × (W 2 - W 1 ) / W 0 (W 0 : mass of initial bonding layer, W 1 : initial mass of metal mesh, W 2 : mass of bonding layer containing metal mesh after drying) In addition, the bonding film obtained was irradiated with light of wavelength 405 nm by an ultra-high pressure mercury lamp in such a way that the accumulated light amount became 20000 mJ/cm 2 , and then one of the PET films of the bonding film was peeled off, and the gel fraction of the bonding layer after irradiation was measured by the same method as the gel fraction of the bonding layer before irradiation. The results are shown in Tables 1 to 2 and 4.

（接著層對波長308 nm之光之消光係數） (A)穿透率X之測定 將所獲得之接著膜（接著層）剪裁成20 mm×30 mm之俯視長方形狀後，將兩面之PET膜剝離，將所獲得之測定樣品貼附於分光光度計V-670之積分球ISN-723（均為日本分光公司製造）之開口部，將測定光之入射角設為0°，測定波長220 nm至1500 nm之光之穿透率X。 (Extinction coefficient of bonding layer for light with a wavelength of 308 nm) (A) Measurement of transmittance X After cutting the bonding film (bonding layer) into a 20 mm × 30 mm rectangular shape when viewed from above, peel off the PET films on both sides, attach the obtained measurement sample to the opening of the integrating sphere ISN-723 (both manufactured by Nippon SCOP Corporation) of the spectrophotometer V-670, set the incident angle of the measurement light to 0°, and measure the transmittance X of light with a wavelength of 220 nm to 1500 nm.

（B）反射率Y之測定 將絕對反射率測定單元ARSN-733安裝於分光光度計V-670（均為日本分光公司製造）。將接著膜（接著層）之單面之PET膜剝離，並貼附用以截斷背面之反射之黑色乙烯膠帶（積水化學工業公司製造，「Eslon Tape No.360」，黑色，寬度19 mm）。將接著膜之與貼附有黑色乙烯膠帶之面相反側之面的PET膜剝離。使用板簧（絕對反射率測定單元ARSN-733之附屬品）將接著膜以測定光自與貼附有黑色乙烯膠帶之面相反側之面入射之方式設置於試樣台，將測定光之入射角設為5°及將反射角設為5°，測定波長220 nm至1500 nm之光之反射率Y。 (B) Measurement of reflectivity Y The absolute reflectivity measurement unit ARSN-733 was installed on the spectrophotometer V-670 (both manufactured by JASCO Corporation). The PET film on one side of the adhesive film (adhesive layer) was peeled off, and a black vinyl tape (manufactured by Sekisui Chemical Industry Co., Ltd., "Eslon Tape No. 360", black, width 19 mm) was attached to cut off the reflection on the back side. The PET film on the side of the adhesive film opposite to the side with the black vinyl tape was peeled off. Using a leaf spring (accessory of the absolute reflectance measurement unit ARSN-733), the adhesive film is placed on the test stand in a manner such that the measuring light is incident from the side opposite to the side with the black vinyl tape attached. The incident angle of the measuring light is set to 5° and the reflection angle is set to 5°. The reflectance Y of light with a wavelength of 220 nm to 1500 nm is measured.

（C）接著層之厚度之測定 將接著膜（接著層）之兩面之PET膜剝離，測定接著層之厚度。厚度之測定使用厚度計（MITUTOYO公司製造，「Digimatic Indicator ID-H」）。 (C) Measurement of the thickness of the bonding layer The PET films on both sides of the bonding film (bonding layer) are peeled off and the thickness of the bonding layer is measured. The thickness is measured using a thickness gauge ("Digimatic Indicator ID-H" manufactured by MITUTOYO).

（D）消光係數之導出 使用所測得之穿透率X、反射率Y、及接著層之厚度，並藉由光譜橢偏儀解析軟體（J.A.Woollam公司製造，「WVASE32」）對折射率n及消光係數k進行解析。利用Cauchy之多項式對可見區域（波長380 nm以上780 nm以下）之折射率進行近似，藉此，使用穿透率X求出吸收端至波長780 nm之折射率n1之值。固定所求出之折射率n1並用作波長220 nm至1500 nm之光的折射率，使用穿透率X計算出消光係數k1，進而，使用所算出之折射率n1、消光係數k1計算出反射率y1。接著層表面之光之反射並非完全為鏡面反射，所測得之反射率Y成為低於理想反射率之值，故以可見區域之反射率Y與反射率y1變成一致之方式進行調節，設為反射率y2。繼而，固定消光係數k1並使用反射率y2計算出波長220 nm至1500 nm之折射率n2。重複該程序直至反射率之測定值與計算值變成一致為止，求出波長220 nm至1500 nm之折射率n及消光係數k。 於本實施例、比較例中，除比較例1-4以外，波長308 nm之穿透率均為1%以下，故假定使用穿透率大於1%之長波長區域之消光係數（波長395 nm至425 nm之消光係數）近似成指數函數，藉由最小平方法求出近似曲線之式（y＝A（常數）×e ＾（B（常數）×x）、y：消光係數、x：波長（nm））。根據所獲得之近似曲線之式求出波長308 nm的消光係數k。於穿透率成為1%以下之波長短於波長308 nm之情形時，根據上述解析結果求出波長308 nm之消光係數k。 比較例1-4之波長308 nm之穿透率超過1%，故根據上述解析結果求出波長308 nm之消光係數k。 藉由進行以上解析，求出接著層照射光前對波長308 nm之光的消光係數。將結果示於表1～2、4中。 (D) Derivation of extinction coefficient The measured transmittance X, reflectance Y, and thickness of the bonding layer were used to analyze the refractive index n and the extinction coefficient k using the spectroscopic ellipsometer analysis software (manufactured by JA Woollam, "WVASE32"). The refractive index in the visible region (wavelengths above 380 nm and below 780 nm) was approximated using Cauchy's polynomials, and the refractive index n1 from the absorption end to the wavelength of 780 nm was calculated using the transmittance X. The calculated refractive index n1 was fixed and used as the refractive index for light with a wavelength of 220 nm to 1500 nm, and the extinction coefficient k1 was calculated using the transmittance X. Furthermore, the reflectance y1 was calculated using the calculated refractive index n1 and extinction coefficient k1. Then, the reflection of the light on the surface of the layer is not completely mirror reflection, and the measured reflectivity Y becomes a value lower than the ideal reflectivity, so the reflectivity Y of the visible area is adjusted in a way that it becomes consistent with the reflectivity y1, and is set as reflectivity y2. Then, the extinction coefficient k1 is fixed and the refractive index n2 of the wavelength from 220 nm to 1500 nm is calculated using the reflectivity y2. Repeat this procedure until the measured value of the reflectivity becomes consistent with the calculated value, and the refractive index n and extinction coefficient k of the wavelength from 220 nm to 1500 nm are obtained. In the present embodiment and comparative examples, except for comparative examples 1-4, the transmittance at a wavelength of 308 nm is less than 1%, so it is assumed that the extinction coefficient in the long wavelength region with a transmittance greater than 1% (extinction coefficient at wavelengths of 395 nm to 425 nm) is approximated to an exponential function, and the formula of the approximate curve is obtained by the least square method (y = A (constant) × e ^ (B (constant) × x), y: extinction coefficient, x: wavelength (nm)). The extinction coefficient k at a wavelength of 308 nm is obtained based on the obtained formula of the approximate curve. When the wavelength at which the transmittance becomes less than 1% is shorter than the wavelength of 308 nm, the extinction coefficient k at a wavelength of 308 nm is obtained based on the above analytical results. The transmittance of the wavelength 308 nm of Comparative Example 1-4 exceeds 1%, so the extinction coefficient k of the wavelength 308 nm is obtained based on the above analysis results. By performing the above analysis, the extinction coefficient of the wavelength 308 nm light before the next layer is irradiated with light is obtained. The results are shown in Tables 1-2 and 4.

又，藉由超高壓水銀燈以累計光量成為20000 mJ/cm 2之方式對所獲得之接著膜（接著層）照射波長405 nm之光後，進行與上述「（A）穿透率X之測定」、「（B）反射率Y之測定」、「（C）黏著膜之厚度之測定」、及「（D）消光係數之導出」相同之方法，測定接著層照射光後對波長308 nm之光的消光係數。將結果示於表1～2、4中。 Furthermore, the obtained adhesive film (adhesive layer) was irradiated with light of wavelength 405 nm by an ultra-high pressure mercury lamp in such a way that the accumulated light amount became 20000 mJ/ cm2 , and then the extinction coefficient of the adhesive layer to light of wavelength 308 nm after irradiation was measured by the same method as the above-mentioned "(A) Measurement of transmittance X", "(B) Measurement of reflectivity Y", "(C) Measurement of thickness of adhesive film", and "(D) Derivation of extinction coefficient". The results are shown in Tables 1-2 and 4.

（接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度） 將所獲得之接著膜剪裁成100 mm×200 mm之俯視長方形狀後，藉由超高壓水銀燈以累計光量成為20000 mJ/cm 2之方式對所剪裁之接著膜照射波長405 nm之光。稱取經光照射之黏著膜並置於鋁鍋中，將接著膜之兩面之PET膜剝離，將該鋁鍋設置於示差熱熱重量同時測定裝置（Hitachi High-Tech Science公司製造，「STA7200」）後，於氮氣環境下以升溫速度10℃/min進行熱重量分析。將接著膜之重量成為初始重量之95%之溫度設為接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度，將結果示於表1～2、4中。 (5% weight loss temperature when the adhesive film is irradiated with light and then heated at a temperature increase rate of 10°C/min in a nitrogen environment) The obtained adhesive film was cut into a 100 mm × 200 mm rectangular shape when viewed from above, and then irradiated with light of a wavelength of 405 nm by an ultra-high pressure mercury lamp in such a way that the accumulated light amount becomes 20,000 mJ/cm 2. The light-irradiated adhesive film was weighed and placed in an aluminum pot, and the PET films on both sides of the adhesive film were peeled off. The aluminum pot was set in a differential thermal thermogravimetric simultaneous measurement device (manufactured by Hitachi High-Tech Science, "STA7200"), and thermogravimetric analysis was performed at a temperature increase rate of 10°C/min in a nitrogen environment. The temperature at which the adhesive film weight became 95% of the initial weight was set as the 5% weight loss temperature when the adhesive film was heated at a heating rate of 10°C/min in a nitrogen environment after irradiation with light. The results are shown in Tables 1-2 and 4.

＜評價＞ 對實施例1-1～1-23、比較例1-1～1-7中所獲得之接著膜進行以下評價。將結果示於表1～2、4中。 <Evaluation> The following evaluation was performed on the adhesive films obtained in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7. The results are shown in Tables 1 to 2 and 4.

（積層體之製作） 將所獲得之接著膜之其中一離型PET膜剝離，並於真空、40℃之條件下貼附於直徑200 mm、厚度700 μm之矽晶圓，將接著膜切成矽晶圓之形狀。繼而，將所貼附之接著膜之另一離型PET膜剝離，並將直徑200 mm、厚度600 μm之玻璃（SCHOTT公司製造，「Tempax」）於真空、90℃之條件下，使用加壓貼合裝置（Takatori公司製造，「GWSM-300M」）貼附於與貼附於矽晶圓之面相反之面，藉此獲得積層體。 又，進行使用超高壓水銀燈自所獲得之積層體之玻璃側以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光之處理、及於氮氣環境下使用290℃之加熱板（MSA FACTORY公司製造，「PH224/225」）加熱30分鐘之處理。 (Production of a laminate) One of the release PET films of the obtained bonding film was peeled off and attached to a silicon wafer with a diameter of 200 mm and a thickness of 700 μm under vacuum and 40°C conditions, and the bonding film was cut into the shape of the silicon wafer. Next, the other release PET film of the attached bonding film was peeled off, and a glass with a diameter of 200 mm and a thickness of 600 μm (manufactured by SCHOTT, "Tempax") was attached to the surface opposite to the surface attached to the silicon wafer under vacuum and 90°C conditions using a pressure bonding device (manufactured by Takatori, "GWSM-300M") to obtain a laminate. Furthermore, the obtained laminate was irradiated with light having a wavelength of 405 nm from the glass side using an ultra-high pressure mercury lamp so that the accumulated light intensity became 20000 mJ/ cm2 , and heated for 30 minutes using a 290°C heating plate (manufactured by MSA FACTORY, "PH224/225") in a nitrogen atmosphere.

（支持體之剝離性） 針對上述進行了光照射處理及加熱處理且自然氣冷後之積層體，自玻璃側對整個玻璃表面照射波長308 nm、照射能量密度250 mJ/cm 2、脈衝寬度20 nsec之脈衝雷射。其後，將矽晶圓側固定於吸附台，將吸盤掛鉤附於玻璃側，將數位測力計（IMADA公司製造，「ZTS-50N」）懸掛於掛鉤。以如上方式利用數位測力計測定將玻璃自接著膜剝離之剝離力。 將所獲得之剝離力為20 N/inch以下之情形設為「◎」，將大於20 N/inch且30 N/inch以下之情形設為「○」，將大於30 N/inch之情形設為「×」來對支持體之剝離性進行評價。 (Releasability of the support) The above-mentioned laminated body, which had been subjected to light irradiation treatment and heat treatment and naturally cooled, was irradiated with a pulsed laser of 308 nm wavelength, 250 mJ/cm 2 irradiation energy density, and 20 nsec pulse width from the glass side to the entire glass surface. Thereafter, the silicon wafer side was fixed to the adsorption table, the suction cup was attached to the glass side, and a digital dynamometer (manufactured by IMADA, "ZTS-50N") was hung on the hook. The peeling force for peeling the glass from the adhesive film was measured using the digital dynamometer in the above manner. The peeling property of the support was evaluated by setting "◎" when the peeling force was 20 N/inch or less, "○" when it was greater than 20 N/inch and less than 30 N/inch, and "×" when it was greater than 30 N/inch.

（接著膜之剝離性） 針對上述「（支持體之剝離性）」中所使用之將支持體剝離後之積層體，將積層體上之接著膜切成寬25 mm，使用拉伸試驗機（島津製作所公司製造，「AG-IS」），於剝離速度300 mm/min、剝離角度180°之條件下將接著膜自半導體裝置剝離，藉此測定接著膜之180°剝離力。 將所獲得之180°剝離力為1.0 N/inch以下之情形設為「○」，將大於1.0 N/inch且3.0 N/inch以下之情形設為「Δ」，將大於3.0 N/inch之情形設為「×」來對接著膜之剝離性進行評價。 (Releasability of adhesive film) For the laminated body after the support was peeled off as described in the above "(Releasability of support)", the adhesive film on the laminated body was cut into 25 mm wide pieces, and the adhesive film was peeled off from the semiconductor device using a tensile tester (manufactured by Shimadzu Corporation, "AG-IS") at a peeling speed of 300 mm/min and a peeling angle of 180° to measure the 180° peeling force of the adhesive film. The peeling property of the adhesive film was evaluated by setting the obtained 180° peeling force of 1.0 N/inch or less as "○", the case of greater than 1.0 N/inch and less than 3.0 N/inch as "Δ", and the case of greater than 3.0 N/inch as "×".

（實施例1-24～1～26） （接著膜之製作） 藉由與實施例1-1～1-23、比較例1-1～1-7相同之方法製作2片積層膜後，以乾燥被膜對向之方式於表3所示之基材之2個表面各重疊1片積層膜，藉此獲得具有基材、及基材之兩面之具有相同組成及厚度之接著層的接著膜。 (Examples 1-24 to 1-26) (Preparation of bonding film) After preparing two laminated films by the same method as in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7, one laminated film is stacked on each of the two surfaces of the substrate shown in Table 3 in such a manner that the dried films face each other, thereby obtaining a bonding film having a substrate and bonding layers of the same composition and thickness on both sides of the substrate.

再者，表3所示之基材之種類示出以下者。 ·含PA（聚醯胺）之基材（Unitika公司製造，「UNIAMIDE（註冊商標）」） ·含透明PI（聚醯亞胺）之基材（A&D公司製造，「TORMED（註冊商標）」） ·含PEEK（聚醚醚酮）之基材（倉敷紡織公司製造，「EXPEEK」） Furthermore, the types of substrates shown in Table 3 are shown below. ·Substrate containing PA (polyamide) (manufactured by Unitika, "UNIAMIDE (registered trademark)") ·Substrate containing transparent PI (polyimide) (manufactured by A&D, "TORMED (registered trademark)") ·Substrate containing PEEK (polyetheretherketone) (manufactured by Kurashiki Textile Co., Ltd., "EXPEEK")

（接著層之凝膠分率） 藉由與實施例1-1～1-23、比較例1-1～1-7相同之方法，獲得接著層照射光前之凝膠分率、及接著層照射光後之凝膠分率。將結果示於表3中。 (Gel fraction of the connecting layer) The gel fraction before the connecting layer was irradiated with light and the gel fraction after the connecting layer was irradiated with light were obtained by the same method as in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7. The results are shown in Table 3.

（接著層對波長308 nm之光之消光係數） 於所獲得之接著性膜中，於基材與接著層之間插入截切刀，藉此將基材與接著層分離。針對經分離之接著層，藉由與實施例1-1～1-23、比較例1-1～1-3、1-5～1-7相同之方法測定穿透率X、反射率Y、及厚度，導出消光係數。將結果示於表3中。 (Extinction coefficient of bonding layer for light with a wavelength of 308 nm) In the obtained bonding film, a cutting knife was inserted between the substrate and the bonding layer to separate the substrate and the bonding layer. For the separated bonding layer, the transmittance X, reflectance Y, and thickness were measured by the same method as in Examples 1-1 to 1-23, Comparative Examples 1-1 to 1-3, 1-5 to 1-7, and the extinction coefficient was derived. The results are shown in Table 3.

（接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度） 藉由與實施例1-1～1-23、比較例1-1～1-7相同之方法，測定接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度。將結果示於表3中。 (5% weight loss temperature when the film is heated at a heating rate of 10°C/min in a nitrogen environment after being irradiated with light) The 5% weight loss temperature when the film is heated at a heating rate of 10°C/min in a nitrogen environment after being irradiated with light was measured by the same method as in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7. The results are shown in Table 3.

藉由與實施例1-1～1-23、比較例1-1～1-7相同之方法進行評價。將結果示於表3中。Evaluation was performed by the same method as in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7. The results are shown in Table 3.

[表1] 實施例1-1 實施例1-2 實施例1-3 實施例1-4 實施例1-5 實施例1-6 實施例1-7 實施例1-8 實施例1-9 實施例1-10 實施例1-11 實施例1-12 接著層之組成（質量份） 硬化性樹脂 聚醯亞胺A 60 - - - - - - - - - - - 聚醯亞胺B - 60 70 70 70 70 70 70 70 70 60 100 雙馬來醯亞胺化合物C 30 30 - - 30 - - - - - 30 - 雙馬來醯亞胺化合物D 10 10 30 30 - 30 30 30 30 30 10 - 光聚合起始劑 雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物 （IGM Resins公司製造，「Omnirad 819」） 2 2 - 1.5 2 1.5 1.5 1.5 - 1.5 2 - 1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮 （BASF公司製造，「Irgacure OXE02」） - - - - - - - - 1 - - - 離型劑 聚矽氧系離型劑 （BYK-Chemie公司製造，「BYK-UV 3500」） 1 1 1 1 1 1 1 - 1 - 1 1 丙烯酸系離型劑 （BYK-Chemie公司製造，「BYK-394」） - - - - - - - 1 - - - - 紫外線吸收劑 2-[4,6-雙(1,1'-聯苯-4-基)-1,3,5-三-2-基]-5-[(2-乙基己基)氧基]苯酚 （BASF公司製造，「Tinuvin 1600」） - - - 10 10 - - - 10 10 30 - 羥基苯基三系紫外線吸收劑 （BASF公司製造，「Tinuvin 479」） - - - - - 5 10 10 - - - - 2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三-2-基]-5-[3-(十二烷基氧基)-2-羥基丙氧基]苯酚 （BASF公司製造，「Tinuvin 400」） - - - - - - - - - - - - 紫外線散射劑 氧化鈦 （石原產業公司製造，「TTO-55（S）」） - - - - - - - - - - - - 無機填充劑 二氧化矽填料（Tokuyama公司製造，MT-10） - - - - - - - - - - - - 接著層之厚度（μm） 80 80 80 80 80 80 80 80 80 80 80 50 接著層之凝膠分率（質量%） 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之前 0 0 0 0 0 0 0 0 0 0 0 0 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之後 89 97 95 82 78 87 83 82 80 81 68 66 接著層對波長308 nm之光之消光係數 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之前 1.8×10 -2 1.3×10 -2 2.4×10 -4 3.2×10 -1 4.7×10 -1 3.0×10 -2 1.0×10 -1 1.1×10 -1 1.3 1.5 3.5 1.9 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之後 1.5×10 -3 1.3×10 -3 1.1×10 -3 3.3×10 -1 4.5×10 -1 5.1×10 -2 2.6×10 -1 2.2×10 -1 1.3 1.6 3.8 1.8 接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度（℃） 421 431 433 425 429 425 414 415 435 430 419 449 評價 支持體之 剝離性 剝離力（N/inch） 30 30 30 10 10 25 20 20 20 20 10 20 判定 ○ ○ ○ ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ 接著膜之 剝離性 180°剝離力（N/inch） 0.8 0.3 0.03 0.7 0.3 0.5 0.7 0.8 0.3 1.2 2.4 1.8 判定 ○ ○ ○ ○ ○ ○ ○ ○ ○ Δ Δ Δ [Table 1] Embodiment 1-1 Embodiment 1-2 Embodiment 1-3 Embodiment 1-4 Embodiment 1-5 Embodiment 1-6 Embodiment 1-7 Embodiment 1-8 Embodiment 1-9 Embodiment 1-10 Embodiment 1-11 Embodiment 1-12 Composition of the next layer (by mass) Hardening resin Polyimide A 60 - - - - - - - - - - - Polyimide B - 60 70 70 70 70 70 70 70 70 60 100 Bismaleimide Compound C 30 30 - - 30 - - - - - 30 - Bismaleimide D 10 10 30 30 - 30 30 30 30 30 10 - Photopolymerization initiator Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (manufactured by IGM Resins, "Omnirad 819") 2 2 - 1.5 2 1.5 1.5 1.5 - 1.5 2 - 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone (manufactured by BASF, "Irgacure OXE02") - - - - - - - - 1 - - - Release agent Silicone release agent (BYK-Chemie, "BYK-UV 3500") 1 1 1 1 1 1 1 - 1 - 1 1 Acrylic release agent (BYK-Chemie, "BYK-394") - - - - - - - 1 - - - - UV absorber 2-[4,6-Bis(1,1'-biphenyl-4-yl)-1,3,5-tri -2-yl]-5-[(2-ethylhexyl)oxy]phenol (produced by BASF, "Tinuvin 1600") - - - 10 10 - - - 10 10 30 - Hydroxyphenyltrimethoxy Ultraviolet light absorber (produced by BASF, "Tinuvin 479") - - - - - 5 10 10 - - - - 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri -2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol (produced by BASF, "Tinuvin 400") - - - - - - - - - - - - UV scattering agent Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., "TTO-55 (S)") - - - - - - - - - - - - Inorganic fillers Silica filler (MT-10 manufactured by Tokuyama Co., Ltd.) - - - - - - - - - - - - Thickness of the next layer (μm) 80 80 80 80 80 80 80 80 80 80 80 50 Gel fraction of the next layer (mass %) Before irradiation with ultra-high pressure mercury lamp (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 0 0 0 0 0 0 0 0 0 0 0 0 After irradiation with ultra-high pressure mercury lamp light (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 89 97 95 82 78 87 83 82 80 81 68 66 Next, the extinction coefficient of the layer for light with a wavelength of 308 nm Before irradiation with ultra-high pressure mercury lamp (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 1.8×10 -2 1.3×10 -2 2.4× 10-4 3.2× 10-1 4.7× 10-1 3.0×10 -2 1.0× 10-1 1.1× 10-1 1.3 1.5 3.5 1.9 After irradiation with ultra-high pressure mercury lamp light (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 1.5× 10-3 1.3×10 -3 1.1×10 -3 3.3× 10-1 4.5× 10-1 5.1×10 -2 2.6× 10-1 2.2× 10-1 1.3 1.6 3.8 1.8 After the film was irradiated with light, it was heated at a rate of 10°C/min in a nitrogen environment. The 5% weight loss temperature (°C) 421 431 433 425 429 425 414 415 435 430 419 449 Reviews Removability of support Peeling force (N/inch) 30 30 30 10 10 25 20 20 20 20 10 20 determination ○ ○ ○ ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ The peelability of the adhesive film 180° peeling force (N/inch) 0.8 0.3 0.03 0.7 0.3 0.5 0.7 0.8 0.3 1.2 2.4 1.8 determination ○ ○ ○ ○ ○ ○ ○ ○ ○ Δ Δ Δ

[表2] 實施例1-13 實施例1-14 實施例1-15 實施例1-16 實施例1-17 實施例1-18 實施例1-19 實施例1-20 實施例1-21 實施例1-22 實施例1-23 接著層之組成（質量份） 硬化性樹脂 聚醯亞胺A - - - - - - - - - - - 聚醯亞胺B 70 - 70 70 70 70 50 50 50 50 40 雙馬來醯亞胺化合物C 30 100 - 30 - - - - - - - 雙馬來醯亞胺化合物D - - 30 - 30 30 50 50 50 50 60 光聚合起始劑 雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物 （IGM Resins公司製造，「Omnirad 819」） - - 2 - 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮 （BASF公司製造，「Irgacure OXE02」） - - - - - - - - - - - 離型劑 聚矽氧系離型劑 （BYK-Chemie公司製造，「BYK-UV 3500」） 1 - 1 1 - - - - - - - 丙烯酸系離型劑 （BYK-Chemie公司製造，「BYK-394」） - - - - - - - - - - - 紫外線吸收劑 2-[4,6-雙(1,1'-聯苯-4-基)-1,3,5-三-2-基]-5-[(2-乙基己基)氧基]苯酚 （BASF公司製造，「Tinuvin 1600」） - - 10 5 10 10 10 20 20 30 30 羥基苯基三系紫外線吸收劑 （BASF公司製造，「Tinuvin 479」） - - - - - - - - - - - 2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三-2-基]-5-[3-(十二烷基氧基)-2-羥基丙氧基]苯酚 （BASF公司製造，「Tinuvin 400」） - - - - - - - - - - - 紫外線散射劑 氧化鈦 （石原產業公司製造，「TTO-55（S）」） - - - - - - - - - - - 無機填充劑 二氧化矽填料（Tokuyama公司製造，MT-10） - - - - - - - - 5 - - 接著層之厚度（μm） 80 50 80 80 50 20 20 20 20 20 20 接著層之凝膠分率（質量%） 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）前 0 0 0 0 0 0 0 0 0 0 0 藉由超高壓水銀燈之光（波長405 nm、累計光量20000 mJ/cm 2）照射後 71 85 85 65 79 80 83 77 76 72 75 接著層對波長308 nm之光之消光係數 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之前 4.2×10 -3 1.7 4.7×10 -1 2.4×10 -2 4.5×10 -1 4.8×10 -1 4.0×10 -1 2.6 1.1 4.1 3.2 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之後 5.1×10 -3 1.7 4.9×10 -1 3.3×10 -2 4.3×10 -1 4.9×10 -1 4.5×10 -1 2.3 1.3 4.4 3.5 接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度（℃） 430 432 422 428 430 430 426 413 418 410 408 評價 支持體之 剝離性 剝離力（N/inch） 30 20 10 30 15 10 10 10 10 10 10 判定 ○ ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 接著膜之 剝離性 180°剝離力（N/inch） 1 0.8 0.6 1.5 1.3 1.2 1 1.4 1.5 1.8 1.6 判定 ○ ○ ○ Δ Δ Δ ○ Δ Δ Δ Δ [Table 2] Embodiment 1-13 Embodiment 1-14 Embodiment 1-15 Embodiment 1-16 Embodiment 1-17 Embodiment 1-18 Embodiment 1-19 Embodiment 1-20 Embodiment 1-21 Embodiment 1-22 Embodiment 1-23 Composition of the next layer (by mass) Hardening resin Polyimide A - - - - - - - - - - - Polyimide B 70 - 70 70 70 70 50 50 50 50 40 Bismaleimide Compound C 30 100 - 30 - - - - - - - Bismaleimide D - - 30 - 30 30 50 50 50 50 60 Photopolymerization initiator Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (manufactured by IGM Resins, "Omnirad 819") - - 2 - 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone (manufactured by BASF, "Irgacure OXE02") - - - - - - - - - - - Release agent Silicone release agent (BYK-Chemie, "BYK-UV 3500") 1 - 1 1 - - - - - - - Acrylic release agent (BYK-Chemie, "BYK-394") - - - - - - - - - - - UV absorber 2-[4,6-Bis(1,1'-biphenyl-4-yl)-1,3,5-tri -2-yl]-5-[(2-ethylhexyl)oxy]phenol (produced by BASF, "Tinuvin 1600") - - 10 5 10 10 10 20 20 30 30 Hydroxyphenyltrimethoxy Ultraviolet light absorber (produced by BASF, "Tinuvin 479") - - - - - - - - - - - 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri -2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol (produced by BASF, "Tinuvin 400") - - - - - - - - - - - UV scattering agent Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., "TTO-55 (S)") - - - - - - - - - - - Inorganic fillers Silica filler (MT-10 manufactured by Tokuyama Co., Ltd.) - - - - - - - - 5 - - Thickness of the next layer (μm) 80 50 80 80 50 20 20 20 20 20 20 Gel fraction of the next layer (mass %) Irradiation with ultra-high pressure mercury lamp (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 0 0 0 0 0 0 0 0 0 0 0 After irradiation with ultra-high pressure mercury lamp light (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 71 85 85 65 79 80 83 77 76 72 75 Next, the extinction coefficient of the layer for light with a wavelength of 308 nm Before irradiation with ultra-high pressure mercury lamp (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 4.2×10 -3 1.7 4.7× 10-1 2.4×10 -2 4.5× 10-1 4.8× 10-1 4.0× 10-1 2.6 1.1 4.1 3.2 After irradiation with ultra-high pressure mercury lamp light (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 5.1×10 -3 1.7 4.9×10 -1 3.3×10 -2 4.3× 10-1 4.9×10 -1 4.5× 10-1 2.3 1.3 4.4 3.5 After the film was irradiated with light, it was heated at a rate of 10°C/min in a nitrogen environment. The 5% weight loss temperature (°C) 430 432 422 428 430 430 426 413 418 410 408 Reviews Removability of support Peeling force (N/inch) 30 20 10 30 15 10 10 10 10 10 10 determination ○ ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ The peelability of the adhesive film 180° peeling force (N/inch) 1 0.8 0.6 1.5 1.3 1.2 1 1.4 1.5 1.8 1.6 determination ○ ○ ○ Δ Δ Δ ○ Δ Δ Δ Δ

[表3] 實施例1-24 實施例1-25 實施例1-26 接著層之組成（質量份） 硬化性樹脂 聚醯亞胺A - - - 聚醯亞胺B 60 60 60 雙馬來醯亞胺化合物C 30 30 30 雙馬來醯亞胺化合物D 10 10 10 光聚合起始劑 雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物 （IGM Resins公司製造，「Omnirad 819」） 2 2 2 1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮 （BASF公司製造，「Irgacure OXE02」） - - - 離型劑 聚矽氧系離型劑 （BYK-Chemie公司製造，「BYK-UV 3500」） 1 1 1 丙烯酸系離型劑 （BYK-Chemie公司製造，「BYK-394」） - - - 紫外線吸收劑 2-[4,6-雙(1,1'-聯苯-4-基)-1,3,5-三-2-基]-5-[(2-乙基己基)氧基]苯酚 （BASF公司製造，「Tinuvin 1600」） - - - 羥基苯基三系紫外線吸收劑 （BASF公司製造，「Tinuvin 479」） - - - 2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三-2-基]-5-[3-(十二烷基氧基)-2-羥基丙氧基]苯酚 （BASF公司製造，「Tinuvin 400」） - - - 紫外線散射劑 氧化鈦 （石原產業公司製造，「TTO-55（S）」） - - - 基材 種類 含PA之基材 含透明PI之基材 含PEEK之基材 厚度（μm） 25 25 25 接著層之厚度（μm） 80 80 80 接著層之凝膠分率（質量%） 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之前 0 0 0 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之後 97 97 97 接著層對波長308 nm之光之消光係數 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之前 1.3×10 -2 1.3×10 -2 1.3×10 -2 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之後 1.3×10 -3 1.3×10 -3 1.3×10 -3 接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度（℃） 421 426 425 評價 支持體之 剝離性 剝離力（N/inch） 30 30 30 判定 ○ ○ ○ 接著膜之 剝離性 180°剝離力（N/inch） 0.4 0.4 0.4 判定 ○ ○ ○ [Table 3] Embodiment 1-24 Embodiment 1-25 Embodiment 1-26 Composition of the next layer (by mass) Hardening resin Polyimide A - - - Polyimide B 60 60 60 Bismaleimide Compound C 30 30 30 Bismaleimide D 10 10 10 Photopolymerization initiator Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (manufactured by IGM Resins, "Omnirad 819") 2 2 2 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone (manufactured by BASF, "Irgacure OXE02") - - - Release agent Silicone release agent (BYK-Chemie, "BYK-UV 3500") 1 1 1 Acrylic release agent (BYK-Chemie, "BYK-394") - - - UV absorber 2-[4,6-Bis(1,1'-biphenyl-4-yl)-1,3,5-tri -2-yl]-5-[(2-ethylhexyl)oxy]phenol (produced by BASF, "Tinuvin 1600") - - - Hydroxyphenyltrimethoxy Ultraviolet light absorber (produced by BASF, "Tinuvin 479") - - - 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri -2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol (produced by BASF, "Tinuvin 400") - - - UV scattering agent Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., "TTO-55 (S)") - - - Substrate Type PA-containing substrate Substrate containing transparent PI PEEK-containing substrate Thickness (μm) 25 25 25 Thickness of the next layer (μm) 80 80 80 Gel fraction of the next layer (mass %) Before irradiation with ultra-high pressure mercury lamp (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 0 0 0 After irradiation with ultra-high pressure mercury lamp light (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 97 97 97 Next, the extinction coefficient of the layer for light with a wavelength of 308 nm Before irradiation with ultra-high pressure mercury lamp (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 1.3×10 -2 1.3×10 -2 1.3×10 -2 After irradiation with ultra-high pressure mercury lamp light (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 1.3×10 -3 1.3×10 -3 1.3×10 -3 After the film was irradiated with light, it was heated at a rate of 10°C/min in a nitrogen environment. The 5% weight loss temperature (°C) 421 426 425 Reviews Removability of support Peeling force (N/inch) 30 30 30 determination ○ ○ ○ The peelability of the adhesive film 180° peeling force (N/inch) 0.4 0.4 0.4 determination ○ ○ ○

[表4] 比較例1-1 比較例1-2 比較例1-3 比較例1-4 比較例1-5 比較例1-6 比較例1-7 接著層之組成（質量份） 硬化性樹脂 聚醯亞胺A - - - - - - - 聚醯亞胺B 30 70 70 - 70 70 70 雙馬來醯亞胺化合物C 0 - - - 30 30 - 雙馬來醯亞胺化合物D 70 30 30 - - - 30 丙烯酸系共聚物E - - - 100 - - - 光聚合起始劑 雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物 （IGM Resins公司製造，「Omnirad 819」） - - - 2 - - - 1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮 （BASF公司製造，「Irgacure OXE02」） - - - - 1 1 1 離型劑 聚矽氧系離型劑 （BYK-Chemie公司製造，「BYK-UV 3500」） 1 1 1 1 - - - 丙烯酸系離型劑 （BYK-Chemie公司製造，「BYK-394」） - - - 0 0 - - 紫外線吸收劑 2-[4,6-雙(1,1'-聯苯-4-基)-1,3,5-三-2-基]-5-[(2-乙基己基)氧基]苯酚 （BASF公司製造，「Tinuvin 1600」） - 10 - 0 10 - - 羥基苯基三系紫外線吸收劑 （BASF公司製造，「Tinuvin 479」） - - - 0 - 10 - 2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三-2-基]-5-[3-(十二烷基氧基)-2-羥基丙氧基]苯酚 （BASF公司製造，「Tinuvin 400」） - - 10 0 - - 10 紫外線散射劑 氧化鈦 （石原產業公司製造，「TTO-55（S）」） - - - - - - - 接著層之厚度（μm） 80 80 80 80 80 80 80 接著層之凝膠分率（質量%） 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之前 0 0 0 0 0 0 0 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之後 98 47 56 95 50 53 49 接著層對波長308 nm之光之消光係數 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之前 9.1×10 -5 2.3×10 -1 7.7×10 -2 5.7×10 -5 4.6×10 -1 1.3×10 -1 6.1×10 -2 藉由超高壓水銀燈照射光（波長405 nm、累計光量20000 mJ/cm 2）之後 8.5×10 -5 1.9×10 -1 8.9×10 -2 3.2×10 -5 4.7×10 -1 9.1×10 -2 5.9×10 -2 接著膜照射光後於氮氣環境下經以升溫速度10℃/min加熱之情形時之5%重量減少溫度（℃） 419 432 414 331 434 422 428 評價 支持體之 剝離性 剝離力（N/inch） 超過30 30 30 超過30 30 30 30 判定 × ○ ○ × ○ ○ ○ 接著膜之 剝離性 180°剝離力（N/inch） 0.5 3.9 3.7 無法評價 3.5 3.8 4.1 判定 ○ × × × × × × [Table 4] Comparison Example 1-1 Comparison Example 1-2 Comparison Example 1-3 Comparison Example 1-4 Comparison Examples 1-5 Comparison Example 1-6 Comparison Examples 1-7 Composition of the next layer (by mass) Hardening resin Polyimide A - - - - - - - Polyimide B 30 70 70 - 70 70 70 Bismaleimide Compound C 0 - - - 30 30 - Bismaleimide D 70 30 30 - - - 30 Acrylic copolymer E - - - 100 - - - Photopolymerization initiator Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (manufactured by IGM Resins, "Omnirad 819") - - - 2 - - - 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone (manufactured by BASF, "Irgacure OXE02") - - - - 1 1 1 Release agent Silicone release agent (BYK-Chemie, "BYK-UV 3500") 1 1 1 1 - - - Acrylic release agent (BYK-Chemie, "BYK-394") - - - 0 0 - - UV absorber 2-[4,6-Bis(1,1'-biphenyl-4-yl)-1,3,5-tri -2-yl]-5-[(2-ethylhexyl)oxy]phenol (produced by BASF, "Tinuvin 1600") - 10 - 0 10 - - Hydroxyphenyltrimethoxy Ultraviolet light absorber (produced by BASF, "Tinuvin 479") - - - 0 - 10 - 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri -2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol (produced by BASF, "Tinuvin 400") - - 10 0 - - 10 UV scattering agent Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., "TTO-55 (S)") - - - - - - - Thickness of the next layer (μm) 80 80 80 80 80 80 80 Gel fraction of the next layer (mass %) Before irradiation with ultra-high pressure mercury lamp (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 0 0 0 0 0 0 0 After irradiation with ultra-high pressure mercury lamp (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 98 47 56 95 50 53 49 Next, the extinction coefficient of the layer for light with a wavelength of 308 nm Before irradiation with ultra-high pressure mercury lamp (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 9.1×10 -5 2.3×10 -1 7.7×10 -2 5.7×10 -5 4.6× 10-1 1.3× 10-1 6.1×10 -2 After irradiation with ultra-high pressure mercury lamp light (wavelength 405 nm, cumulative light intensity 20000 mJ/ cm2 ) 8.5× 10-5 1.9×10 -1 8.9×10 -2 3.2×10 -5 4.7× 10-1 9.1×10 -2 5.9×10 -2 After the film was irradiated with light, it was heated at a rate of 10°C/min in a nitrogen environment. The 5% weight loss temperature (°C) 419 432 414 331 434 422 428 Reviews Removability of support Peeling force (N/inch) Over 30 30 30 Over 30 30 30 30 determination × ○ ○ × ○ ○ ○ The peelability of the adhesive film 180° peeling force (N/inch) 0.5 3.9 3.7 Unable to rate 3.5 3.8 4.1 determination ○ × × × × × ×

（實施例2-1～2-2、2-7～2-8、2-10～2-16、比較例2-1～2-2） （暫時固定材之製作） 於甲苯150 mL中添加表5～6、8中所記載之各材料並進行混合，製備硬化型接著劑之甲苯溶液。 利用刮刀將所獲得之硬化型接著劑之甲苯溶液以乾燥皮膜之厚度成為80 μm之方式塗佈於單面實施了離型處理之厚度50 μm之離型聚對苯二甲酸乙二酯（PET）膜之離型處理面上，並以130℃加熱10分鐘而使塗佈溶液乾燥，獲得積層膜。進而，將單面實施了離型處理之厚度50 μm之離型PET膜以離型處理面與乾燥皮膜對向之方式重疊於積層膜，藉此，獲得附離型PET膜之暫時固定材。 (Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, Comparative Examples 2-1 to 2-2) (Preparation of temporary fixing material) The materials listed in Tables 5 to 6 and 8 were added to 150 mL of toluene and mixed to prepare a toluene solution of a curable adhesive. The obtained toluene solution of a curable adhesive was applied to a release-treated surface of a release-treated polyethylene terephthalate (PET) film with a thickness of 50 μm on one side thereof using a spatula so that the thickness of the dry film became 80 μm, and the applied solution was dried by heating at 130°C for 10 minutes to obtain a laminated film. Furthermore, a 50 μm thick release PET film with release treatment applied on one side was overlapped on the laminated film in such a way that the release treatment surface and the dry film faced each other, thereby obtaining a temporary fixing material for the release PET film.

（使暫時固定材硬化後之雷射加工深度） 自所獲得之暫時固定材將其中一離型PET膜剝離，並於真空、40℃之條件下貼附於直徑200 mm、厚度700 μm之矽晶圓，將暫時固定材切成矽晶圓之形狀。自貼附於矽晶圓之暫時固定材之另一離型PET膜之側，藉由超高壓水銀燈以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之紫外線。進而，照射紫外線後，將另一離型PET膜剝離，於氮氣環境下，使用290℃之加熱板（MSA FACTORY公司製造，「PH224/225」）進行30分鐘加熱處理，藉此使暫時固定材硬化。對已硬化之暫時固定材脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光。脈衝照射雷射光後，使用雷射顯微鏡（Olympus公司製造，「OLS4100-SAT」，波長405 nm）對硬化物之雷射光照射側之表面進行階差測定，藉此測定雷射加工深度。 又，照射照射能量密度為400 mJ/cm 2之雷射光時之雷射加工深度亦利用相同方法進行測定。將所獲得之各雷射加工深度示於表5～6、8中。 (Laser processing depth after the temporary fixing material is hardened) One of the release PET films is peeled off from the obtained temporary fixing material, and attached to a silicon wafer with a diameter of 200 mm and a thickness of 700 μm under vacuum and 40°C, and the temporary fixing material is cut into the shape of the silicon wafer. From the side of the other release PET film of the temporary fixing material attached to the silicon wafer, ultraviolet light with a wavelength of 365 nm is irradiated by an ultra-high pressure mercury lamp in such a way that the accumulated light amount becomes 20,000 mJ/ cm2 . After UV irradiation, the other release PET film was peeled off and heated for 30 minutes in a nitrogen environment using a 290°C heating plate (manufactured by MSA FACTORY, "PH224/225") to harden the temporary fixing material. The hardened temporary fixing material was pulsed with laser light of 308 nm wavelength, 10 nsec pulse width, and 300 mJ/ cm2 irradiation energy density. After pulsed laser irradiation, the laser microscope (manufactured by Olympus, "OLS4100-SAT", wavelength 405 nm) was used to measure the step difference of the surface of the laser irradiation side of the hardened material to measure the laser processing depth. The laser processing depth when irradiated with laser light having an irradiation energy density of 400 mJ/cm 2 was also measured by the same method. The obtained laser processing depths are shown in Tables 5 to 6 and 8.

（使暫時固定材硬化後於氮氣環境下且經以290℃加熱30分鐘之情形時之重量減少率） 藉由超高壓水銀燈以累計光量成為20000 mJ/cm 2之方式對所獲得之暫時固定材照射波長365 nm之紫外線後，於氮氣環境下，使用290℃之加熱板（MSA FACTORY公司製造，「PH224/225」）進行30分鐘加熱處理，藉此使暫時固定材硬化。將已硬化之暫時固定材之其中一離型PET膜剝離，稱取質量W 5（mg）之已硬化之暫時固定材並置於鋁鍋中，將該鋁鍋設置於示差熱熱重量同時測定裝置（Hitachi High-Tech Science公司製造，「STA7200」）後，於氮氣環境下，以290℃加熱30分鐘，然後測定已硬化之暫時固定材之重量W 6（mg），根據以下計算式計算出重量減少率。將結果示於表5～6、8中。 重量減少率（%）＝100×（W 5－W 6）/W 5 (Weight loss rate when the temporary fixing material is heated at 290°C for 30 minutes in a nitrogen environment after being cured) The temporary fixing material obtained was irradiated with ultraviolet light of a wavelength of 365 nm by an ultra-high pressure mercury lamp in such a way that the cumulative light amount becomes 20000 mJ/ cm2 , and then heated for 30 minutes using a heating plate (manufactured by MSA FACTORY, "PH224/225") at 290°C in a nitrogen environment to cure the temporary fixing material. One of the release PET films of the hardened temporary fixing material was peeled off, and the mass W 5 (mg) of the hardened temporary fixing material was weighed and placed in an aluminum pot. The aluminum pot was set in a differential thermal thermogravimetric simultaneous measuring device (manufactured by Hitachi High-Tech Science, "STA7200"), and then heated at 290°C for 30 minutes in a nitrogen environment. Then, the weight W 6 (mg) of the hardened temporary fixing material was measured, and the weight loss rate was calculated according to the following calculation formula. The results are shown in Tables 5 to 6 and 8. Weight loss rate (%) = 100 × (W 5 -W 6 )/W 5

＜評價＞ 對實施例2-1～2-2、2-7～2-8、2-10～2-16、比較例2-1～2-2中所獲得之暫時固定材進行以下評價。將結果示於表5～6、8中。 <Evaluation> The temporary fixing materials obtained in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2 were evaluated as follows. The results are shown in Tables 5 to 6 and 8.

（積層體之製作） 將所獲得之暫時固定材之其中一離型PET膜剝離，使用真空層壓機（Takatori公司製造，「ATM-812M」）於真空、40℃之條件下貼附於直徑200 mm、厚度700 μm之矽晶圓，並將暫時固定材切成矽晶圓之形狀。繼而，將所貼附之暫時固定材之另一離型PET膜剝離，將直徑200 mm、厚度600 μm之玻璃（SCHOTT公司製造，「Tempax」）於真空、90℃之條件下，使用加壓貼合裝置（Takatori公司製造，「GWSM-300M」）貼附於與貼附於矽晶圓之面相反之面。自貼附有矽晶圓及玻璃之暫時固定材之玻璃側，使用超高壓水銀燈以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之紫外線後，於氮氣環境下，使用290℃之加熱板（MSA FACTORY公司製造，「PH224/225」）加熱30分鐘，藉此獲得積層體。 (Production of laminated body) One of the release PET films of the obtained temporary fixing material was peeled off, and it was attached to a silicon wafer with a diameter of 200 mm and a thickness of 700 μm using a vacuum lamination press (manufactured by Takatori, "ATM-812M") under vacuum and 40°C conditions, and the temporary fixing material was cut into the shape of the silicon wafer. Then, the other release PET film of the attached temporary fixing material was peeled off, and glass (manufactured by SCHOTT, "Tempax") with a diameter of 200 mm and a thickness of 600 μm was attached to the surface opposite to the surface attached to the silicon wafer using a pressure bonding device (manufactured by Takatori, "GWSM-300M") under vacuum and 90°C conditions. From the glass side of the temporary fixing material to which the silicon wafer and the glass were attached, ultraviolet light with a wavelength of 365 nm was irradiated using an ultra-high pressure mercury lamp in such a way that the accumulated light amount became 20,000 mJ/ cm2 , and then heated for 30 minutes using a heating plate (manufactured by MSA FACTORY, "PH224/225") at 290°C in a nitrogen environment to obtain a laminate.

（雷射剝離（laser lift off）評價） 針對所獲得之積層體，自玻璃側對整個玻璃表面脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光。其後，將積層體之矽晶圓側固定於吸附台，將吸盤掛鉤附於積層體之玻璃側，將數位測力計（IMADA公司製造，「ZTS-50N」）懸掛於掛鉤。以如上方式利用數位測力計測定將玻璃自硬化物剝離之剝離力，進行雷射剝離評價。 將所獲得之剝離力為20 N/inch以下之情形設為「◎」，將大於20 N/inch且30 N/inch以下之情形設為「○」，將大於30 N/inch之情形設為「×」來對硬化物之支持體剝離性能進行評價。 (Laser lift-off evaluation) The obtained laminate was pulsed with laser light of wavelength 308 nm, pulse width 10 nsec, and energy density 300 mJ/cm 2 from the glass side to the entire glass surface. Afterwards, the silicon wafer side of the laminate was fixed to the adsorption table, the suction cup was attached to the glass side of the laminate, and a digital dynamometer (manufactured by IMADA, "ZTS-50N") was hung on the hook. The peeling force for peeling off the glass self-hardening object was measured using the digital dynamometer in the above manner to perform laser lift-off evaluation. The peeling force obtained was set as "◎" when it was 20 N/inch or less, "○" when it was greater than 20 N/inch and less than 30 N/inch, and "×" when it was greater than 30 N/inch to evaluate the support peeling performance of the cured product.

（實施例2-3～2-5） 於上述「（使暫時固定材硬化後之雷射加工深度）」、「（使暫時固定材硬化後於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率）」、及「（積層體之製作）」中，未進行照射波長365 nm之紫外線之步驟，除此以外，以與實施例2-1～2-2、2-7～2-8、2-10～2-16、比較例2-1～2-2相同之方式製作暫時固定材、及積層體，並進行評價。將結果示於表5中。 (Examples 2-3 to 2-5) In the above "(Laser processing depth after hardening the temporary fixing material)", "(Weight reduction rate when heating at 290°C for 30 minutes in a nitrogen environment after hardening the temporary fixing material)", and "(Preparation of laminated body)", the step of irradiating ultraviolet light with a wavelength of 365 nm was not performed. Except for this, temporary fixing materials and laminated bodies were prepared and evaluated in the same manner as Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2. The results are shown in Table 5.

（實施例2-6） 於上述「（使暫時固定材硬化後之雷射加工深度）」、「（使暫時固定材硬化後於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率）」、及「（積層體之製作）」中，未進行於紫外線照射後進行加熱處理之步驟，除此以外，以與實施例2-1～2-2、2-7～2-8、2-10～2-16、比較例2-1～2-2相同之方式製作暫時固定材、及積層體，並進行評價。將結果示於表6中。 (Example 2-6) In the above "(Laser processing depth after hardening the temporary fixing material)", "(Weight reduction rate when heating at 290°C for 30 minutes in a nitrogen environment after hardening the temporary fixing material)", and "(Preparation of laminated body)", the step of heat treatment after ultraviolet irradiation was not performed. Except for this, the temporary fixing material and laminated body were prepared and evaluated in the same manner as Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2. The results are shown in Table 6.

（實施例2-9） 於上述「（使暫時固定材硬化後之雷射加工深度）」、「（使暫時固定材硬化後於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率）」、及「（積層體之製作）」中，使用LED代替超高壓水銀燈，以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之紫外線，除此以外，以與實施例2-1～2-2、2-7～2-8、2-10～2-16、比較例2-1～2-2相同之方式製作暫時固定材、及積層體，並進行評價。將結果示於表5中。 (Example 2-9) In the above-mentioned "(Laser processing depth after hardening of temporary fixing material)", "(Weight reduction rate when heating at 290°C for 30 minutes in nitrogen environment after hardening of temporary fixing material)", and "(Fabrication of laminated body)", LED was used instead of ultrahigh pressure mercury lamp, and ultraviolet light with a wavelength of 365 nm was irradiated in such a way that the accumulated light amount became 20000 mJ/ cm2 . Otherwise, temporary fixing material and laminated body were prepared and evaluated in the same manner as Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2. The results are shown in Table 5.

（實施例2-17） 使用具有已硬化之暫時固定材及支持體之積層體進行使暫時固定材硬化後之雷射加工深度之測定。使用熱壓機（LAMI CORPORATION公司製造，「Leon13DX」），以100℃、速度刻度3將所獲得之暫時固定材加熱層壓於石英。其後，以與實施例2-1～2-2、2-7～2-8、2-10～2-16、比較例2-1～2-2相同之方法使暫時固定材硬化，自石英側對所獲得之積層體照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光後，以與上述相同之方法測定雷射加工深度。 又，照射照射能量密度為400 mJ/cm 2之雷射光時之雷射加工深度亦以相同方法進行測定。 再者，關於暫時固定材、及積層體之製作、使暫時固定材硬化後之重量減少率之測定、以及雷射剝離評價，以與實施例2-1～2-2、2-7～2-8、2-10～2-16、比較例2-1～2-2相同之方法進行。將結果示於表6中。 (Example 2-17) The laser processing depth after the temporary fixing material is hardened is measured using a laminate having a hardened temporary fixing material and a support. The obtained temporary fixing material is heated and pressed against quartz at 100°C and a speed scale of 3 using a hot press (manufactured by LAMI CORPORATION). Thereafter, the temporary fixing material is hardened by the same method as in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2, and the obtained laminate is irradiated from the quartz side with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 , and the laser processing depth is measured by the same method as above. The laser processing depth when irradiating with laser light having an irradiation energy density of 400 mJ/ cm2 was also measured in the same manner. Furthermore, the preparation of the temporary fixing material and the laminate, the measurement of the weight reduction rate after the temporary fixing material was hardened, and the laser peeling evaluation were performed in the same manner as in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2. The results are shown in Table 6.

（實施例2-18～2-28） 於上述「（使暫時固定材硬化後之雷射加工深度）」、「（使暫時固定材硬化後於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率）」、及「（積層體之製作）」中，使用超高壓水銀燈以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之紫外線，除此以外，以與實施例2-1～2-2、2-7～2-8、2-10～2-16、比較例2-1～2-2相同之方式製作暫時固定材、及積層體，並進行評價。將結果示於表6～7中。 (Examples 2-18 to 2-28) In the above-mentioned "(Laser processing depth after hardening of temporary fixing material)", "(Weight reduction rate when heating at 290°C for 30 minutes in a nitrogen environment after hardening of temporary fixing material)", and "(Fabrication of laminated body)", ultraviolet rays with a wavelength of 405 nm were irradiated using an ultrahigh pressure mercury lamp in such a manner that the accumulated light amount became 20000 mJ/ cm2. Temporary fixing materials and laminated bodies were prepared and evaluated in the same manner as Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2. The results are shown in Tables 6 to 7.

[表5] 實施例 2-1 實施例 2-2 實施例 2-3 實施例 2-4 實施例 2-5 實施例 2-6 實施例 2-7 實施例 2-8 暫時固定材 硬化型接著劑 之組成 （質量份） 硬化性樹脂 聚醯亞胺A - 60 100 - - - - - 聚醯亞胺B 70 - - 100 100 70 - 60 雙馬來醯亞胺化合物C - 30 - - - 30 100 30 雙馬來醯亞胺化合物D 30 10 - - - - - 10 光聚合起始劑 雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物 （IGM Resins公司製造，「Omnirad819」） - 2 - - - - - 2 1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮 （BASF公司製造，「Irgacure OXE02」） - - - - - - - - 離型劑 聚矽氧系離型劑 （BYK-Chemie公司製造，「BYK-UV 3500」） 1 1 - - 1 1 - 1 丙烯酸系離型劑 （BYK-Chemie公司製造，「BYK-394」） - - - - - - - - 紫外線吸收劑 三系紫外線吸收劑 2-[4,6-雙(1,1'-聯苯-4-基)-1,3,5-三-2-基]-5-[(2-乙基己基)氧基]苯酚 （BASF公司製造，「Tinuvin1600」） - - - - - - - - 羥基苯基三系紫外線吸收劑 （BASF公司製造，「Tinuvin 479」） - - - - - - - - 2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三-2-基]-5-[3-(十二烷基氧基)-2-羥基丙氧基]苯酚（BASF公司製造，「Tinuvin400」） - - - - - - - - 紫外線散射劑 氧化鈦 （石原產業公司製造，「TTO-55（S）」） - - - - - - - - 厚度（μm） 80 80 50 50 50 80 50 80 處理 紫外線照射（超高壓水銀燈、波長365 nm、累計光量20000 mJ/cm 2） 有 有 無 無 無 有 有 有 加熱（氮氣環境下、290℃、30分鐘） 有 有 有 有 有 無 有 有 硬化後於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率（%） 1.0 2.6 0.9 1.0 1.2 1.0 1.1 2.5 硬化後之雷射加工深度（μm） （波長308 nm，脈衝寬度10 nsec） 照射能量密度300 mJ/cm 2 0.25 0.25 0.32 0.32 0.26 0.15 0.35 0.15 照射能量密度400 mJ/cm 2 0.44 0.43 0.44 0.49 0.38 0.35 0.39 0.36 支持體 種類 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 波長308 nm下之光之穿透率（%） 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 評價 雷射剝離評價 （波長308 nm，脈衝寬度10 nsec， 照射能量密度300 mJ/cm 2） 剝離力（N/inch） 25 25 20 20 20 25 20 25 評價 ○ ○ ◎ ◎ ◎ ○ ◎ ○ [Table 5] Example 2-1 Example 2-2 Embodiment 2-3 Embodiment 2-4 Embodiment 2-5 Embodiment 2-6 Embodiment 2-7 Embodiment 2-8 Temporary fixing material Composition of curing adhesive (by weight) Hardening resin Polyimide A - 60 100 - - - - - Polyimide B 70 - - 100 100 70 - 60 Bismaleimide Compound C - 30 - - - 30 100 30 Bismaleimide D 30 10 - - - - - 10 Photopolymerization initiator Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (manufactured by IGM Resins, "Omnirad819") - 2 - - - - - 2 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone (manufactured by BASF, "Irgacure OXE02") - - - - - - - - Release agent Silicone release agent (BYK-Chemie, "BYK-UV 3500") 1 1 - - 1 1 - 1 Acrylic release agent (BYK-Chemie, "BYK-394") - - - - - - - - UV absorber three UV absorber 2-[4,6-Bis(1,1'-biphenyl-4-yl)-1,3,5-tri -2-yl]-5-[(2-ethylhexyl)oxy]phenol (produced by BASF, "Tinuvin 1600") - - - - - - - - Hydroxyphenyltrimethoxy Ultraviolet light absorber (produced by BASF, "Tinuvin 479") - - - - - - - - 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri -2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol (produced by BASF, "Tinuvin 400") - - - - - - - - UV scattering agent Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., "TTO-55 (S)") - - - - - - - - Thickness (μm) 80 80 50 50 50 80 50 80 handle Ultraviolet irradiation (ultra-high pressure mercury lamp, wavelength 365 nm, cumulative light intensity 20,000 mJ/cm 2 ) have have without without without have have have Heating (nitrogen atmosphere, 290°C, 30 minutes) have have have have have without have have Weight loss after curing at 290℃ for 30 minutes in nitrogen environment (%) 1.0 2.6 0.9 1.0 1.2 1.0 1.1 2.5 Laser processing depth after hardening (μm) (wavelength 308 nm, pulse width 10 nsec) Irradiation energy density 300 mJ/ cm2 0.25 0.25 0.32 0.32 0.26 0.15 0.35 0.15 Irradiation energy density 400 mJ/ cm2 0.44 0.43 0.44 0.49 0.38 0.35 0.39 0.36 Support Type Glass Glass Glass Glass Glass Glass Glass Glass Transmittance of light at a wavelength of 308 nm (%) 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 Reviews Laser ablation evaluation (wavelength 308 nm, pulse width 10 nsec, irradiation energy density 300 mJ/cm 2 ) Peeling force (N/inch) 25 25 20 20 20 25 20 25 Reviews ○ ○ ◎ ◎ ◎ ○ ◎ ○

[表6] 實施例 2-9 實施例 2-10 實施例 2-11 實施例 2-12 實施例 2-13 實施例 2-14 實施例 2-15 實施例 2-16 實施例 2-17 實施例 2-18 實施例 2-19 暫時固定材 硬化型接著劑 之組成 （質量份） 硬化性樹脂 聚醯亞胺A - - - - - - - - - 60 - 聚醯亞胺B 70 70 70 70 70 70 70 70 70 - 60 雙馬來醯亞胺化合物C - - 30 30 30 30 - 30 - 30 30 雙馬來醯亞胺化合物D 30 30 - - - - 30 - 30 10 10 光聚合起始劑 雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物 （IGM Resins公司製造，「Omnirad819」） - 2 2 - - - - - - 2 2 1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮 （BASF公司製造，「Irgacure OXE02」） - - - - - - - - - - - 離型劑 聚矽氧系離型劑 （BYK-Chemie公司製造，「BYK-UV 3500」） 1 1 1 1 1 1 1 1 1 1 1 丙烯酸系離型劑 （BYK-Chemie公司製造，「BYK-394」） - - - - - - - - - - - 紫外線吸收劑 三系紫外線吸收劑 2-[4,6-雙(1,1'-聯苯-4-基)-1,3,5-三-2-基]-5-[(2-乙基己基)氧基]苯酚 （BASF公司製造，「Tinuvin1600」） - 10 10 10 5 - - - - - - 羥基苯基三系紫外線吸收劑 （BASF公司製造，「Tinuvin 479」） - - - - - - - - - - - 2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三-2-基]-5-[3-(十二烷基氧基)-2-羥基丙氧基]苯酚（BASF公司製造，「Tinuvin400」） - - - - - 10 - - - - - 紫外線散射劑 氧化鈦 （石原產業公司製造，「TTO-55（S）」） - - - - - - 10 - - - - 厚度（μm） 80 80 80 80 80 80 80 80 80 80 80 處理 紫外線照射（超高壓水銀燈、波長365 nm、累計光量20000 mJ/cm 2） 無 有 有 有 有 有 有 有 有 無 無 紫外線照射（LED、波長365 nm、累計光量20000 mJ/cm 2） 有 無 無 無 無 無 無 無 無 無 無 紫外線照射（超高壓水銀燈、波長405 nm、累計光量20000 mJ/cm 2） 無 無 無 無 無 無 無 無 無 有 有 加熱 （氮氣環境下，290℃，30分鐘） 有 有 有 有 有 有 有 有 有 有 有 硬化後於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率（%） 1.0 1.8 2.0 1.0 0.9 1.1 1.0 0.9 1.0 2.5 2.4 硬化後之雷射加工深度（μm） （波長308 nm， 脈衝寬度10 nsec） 照射能量密度300 mJ/cm 2 0.10 0.51 0.35 0.29 0.20 0.22 0.12 0.17 0.25 0.26 0.16 照射能量密度400 mJ/cm 2 0.25 0.53 0.55 0.46 0.29 0.35 0.32 0.37 0.44 0.44 0.37 支持體 種類 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 石英 玻璃 玻璃 波長308 nm下之光之穿透率（%） 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 93.5 88.3 88.3 評價 雷射剝離評價 （波長308 nm，脈衝寬度10 nsec， 照射能量密度300 mJ/cm 2） 剝離力（N/inch） 25 5 5 10 15 15 25 25 20 25 25 評價 ○ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ○ ○ [Table 6] Embodiment 2-9 Embodiment 2-10 Embodiment 2-11 Embodiment 2-12 Embodiment 2-13 Embodiment 2-14 Embodiment 2-15 Embodiment 2-16 Embodiment 2-17 Embodiment 2-18 Embodiment 2-19 Temporary fixing material Composition of curing adhesive (by weight) Hardening resin Polyimide A - - - - - - - - - 60 - Polyimide B 70 70 70 70 70 70 70 70 70 - 60 Bismaleimide Compound C - - 30 30 30 30 - 30 - 30 30 Bismaleimide D 30 30 - - - - 30 - 30 10 10 Photopolymerization initiator Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (manufactured by IGM Resins, "Omnirad819") - 2 2 - - - - - - 2 2 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone (manufactured by BASF, "Irgacure OXE02") - - - - - - - - - - - Release agent Silicone release agent (BYK-Chemie, "BYK-UV 3500") 1 1 1 1 1 1 1 1 1 1 1 Acrylic release agent (BYK-Chemie, "BYK-394") - - - - - - - - - - - UV absorber three UV absorber 2-[4,6-Bis(1,1'-biphenyl-4-yl)-1,3,5-tri -2-yl]-5-[(2-ethylhexyl)oxy]phenol (produced by BASF, "Tinuvin 1600") - 10 10 10 5 - - - - - - Hydroxyphenyltrimethoxy Ultraviolet light absorber (produced by BASF, "Tinuvin 479") - - - - - - - - - - - 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri -2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol (produced by BASF, "Tinuvin 400") - - - - - 10 - - - - - UV scattering agent Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., "TTO-55 (S)") - - - - - - 10 - - - - Thickness (μm) 80 80 80 80 80 80 80 80 80 80 80 handle Ultraviolet irradiation (ultra-high pressure mercury lamp, wavelength 365 nm, cumulative light intensity 20,000 mJ/cm 2 ) without have have have have have have have have without without UV irradiation (LED, wavelength 365 nm, cumulative light intensity 20000 mJ/ cm2 ) have without without without without without without without without without without Ultraviolet irradiation (ultra-high pressure mercury lamp, wavelength 405 nm, cumulative light intensity 20,000 mJ/cm 2 ) without without without without without without without without without have have Heating (nitrogen environment, 290℃, 30 minutes) have have have have have have have have have have have Weight loss after curing at 290℃ for 30 minutes in nitrogen environment (%) 1.0 1.8 2.0 1.0 0.9 1.1 1.0 0.9 1.0 2.5 2.4 Laser processing depth after hardening (μm) (wavelength 308 nm, pulse width 10 nsec) Irradiation energy density 300 mJ/ cm2 0.10 0.51 0.35 0.29 0.20 0.22 0.12 0.17 0.25 0.26 0.16 Irradiation energy density 400 mJ/ cm2 0.25 0.53 0.55 0.46 0.29 0.35 0.32 0.37 0.44 0.44 0.37 Support Type Glass Glass Glass Glass Glass Glass Glass Glass quartz Glass Glass Transmittance of light at a wavelength of 308 nm (%) 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 93.5 88.3 88.3 Reviews Laser ablation evaluation (wavelength 308 nm, pulse width 10 nsec, irradiation energy density 300 mJ/cm 2 ) Peeling force (N/inch) 25 5 5 10 15 15 25 25 20 25 25 Reviews ○ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ○ ○

[表7] 實施例 2-19 實施例 2-20 實施例 2-21 實施例 2-22 實施例 2-23 實施例 2-24 實施例 2-25 實施例 2-26 實施例 2-27 實施例 2-28 暫時固定材 硬化型接著劑 之組成 （質量份） 硬化性樹脂 聚醯亞胺A - - - - - - - - - - 聚醯亞胺B 60 70 70 70 70 70 70 70 70 60 雙馬來醯亞胺化合物C 30 - - 30 - - - - - 30 雙馬來醯亞胺化合物D 10 30 30 - 30 30 30 30 30 10 光聚合起始劑 雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物 （IGM Resins公司製造，「Omnirad819」） 2 - 1.5 2 1.5 1.5 1.5 - 1.5 2 1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮 （BASF公司製造，「Irgacure OXE02」） - - - - - - - 1 - - 離型劑 聚矽氧系離型劑 （BYK-Chemie公司製造，「BYK-UV 3500」） 1 1 1 1 1 1 - 1 - 1 丙烯酸系離型劑 （BYK-Chemie公司製造，「BYK-394」） - - - - - - 1 - - - 紫外線吸收劑 三系紫外線吸收劑 2-[4,6-雙(1,1'-聯苯-4-基)-1,3,5-三-2-基]-5-[(2-乙基己基)氧基]苯酚（BASF公司製造，「Tinuvin1600」） - - 10 10 - - - 10 10 30 羥基苯基三系紫外線吸收劑 （BASF公司製造，「Tinuvin 479」） - - - - 5 10 10 - - - 2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三-2-基]-5-[3-(十二烷基氧基)-2-羥基丙氧基]苯酚 （BASF公司製造，「Tinuvin400」） - - - - - - - - - - 紫外線散射劑 氧化鈦 （石原產業公司製造，「TTO-55（S）」） - - - - - - - - - - 厚度（μm） 80 80 80 80 80 80 80 80 80 80 處理 紫外線照射（超高壓水銀燈、波長405 nm、累計光量20000 mJ/cm 2） 有 有 有 有 有 有 有 有 有 有 加熱（氮氣環境下、290℃、30分鐘） 有 有 有 有 有 有 有 有 有 有 硬化後於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率（%） 2.4 1.0 1.9 1.9 2.2 2.4 2.3 1.0 1.5 2.5 硬化後之雷射加工深度（μm） （波長308 nm，脈衝寬度10 nsec） 照射能量密度300 mJ/cm 2 0.16 0.24 0.52 0.36 0.34 0.45 0.43 0.27 0.50 0.69 照射能量密度400 mJ/cm 2 0.37 0.45 0.55 0.55 0.40 0.52 0.51 0.43 0.54 0.73 支持體 種類 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 波長308 nm下之光之穿透率（%） 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 評價 雷射剝離評價 （波長308 nm，脈衝寬度10 nsec， 照射能量密度300 mJ/cm 2） 剝離力（N/inch） 25 25 5 5 10 5 5 10 5 5 評價 ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ [Table 7] Embodiment 2-19 Embodiment 2-20 Embodiment 2-21 Example 2-22 Embodiment 2-23 Embodiment 2-24 Embodiment 2-25 Embodiment 2-26 Embodiment 2-27 Embodiment 2-28 Temporary fixing material Composition of curing adhesive (by weight) Hardening resin Polyimide A - - - - - - - - - - Polyimide B 60 70 70 70 70 70 70 70 70 60 Bismaleimide Compound C 30 - - 30 - - - - - 30 Bismaleimide D 10 30 30 - 30 30 30 30 30 10 Photopolymerization initiator Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (manufactured by IGM Resins, "Omnirad819") 2 - 1.5 2 1.5 1.5 1.5 - 1.5 2 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone (manufactured by BASF, "Irgacure OXE02") - - - - - - - 1 - - Release agent Silicone release agent (BYK-Chemie, "BYK-UV 3500") 1 1 1 1 1 1 - 1 - 1 Acrylic release agent (BYK-Chemie, "BYK-394") - - - - - - 1 - - - UV absorber three UV absorber 2-[4,6-Bis(1,1'-biphenyl-4-yl)-1,3,5-tri -2-yl]-5-[(2-ethylhexyl)oxy]phenol (produced by BASF, "Tinuvin 1600") - - 10 10 - - - 10 10 30 Hydroxyphenyltrimethoxy Ultraviolet light absorber (produced by BASF, "Tinuvin 479") - - - - 5 10 10 - - - 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri -2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol (produced by BASF, "Tinuvin 400") - - - - - - - - - - UV scattering agent Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., "TTO-55 (S)") - - - - - - - - - - Thickness (μm) 80 80 80 80 80 80 80 80 80 80 handle Ultraviolet irradiation (ultra-high pressure mercury lamp, wavelength 405 nm, cumulative light intensity 20,000 mJ/cm 2 ) have have have have have have have have have have Heating (nitrogen atmosphere, 290°C, 30 minutes) have have have have have have have have have have Weight loss after curing at 290℃ for 30 minutes in nitrogen environment (%) 2.4 1.0 1.9 1.9 2.2 2.4 2.3 1.0 1.5 2.5 Laser processing depth after hardening (μm) (wavelength 308 nm, pulse width 10 nsec) Irradiation energy density 300 mJ/ cm2 0.16 0.24 0.52 0.36 0.34 0.45 0.43 0.27 0.50 0.69 Irradiation energy density 400 mJ/ cm2 0.37 0.45 0.55 0.55 0.40 0.52 0.51 0.43 0.54 0.73 Support Type Glass Glass Glass Glass Glass Glass Glass Glass Glass Glass Transmittance of light at a wavelength of 308 nm (%) 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 88.3 Reviews Laser ablation evaluation (wavelength 308 nm, pulse width 10 nsec, irradiation energy density 300 mJ/cm 2 ) Peeling force (N/inch) 25 25 5 5 10 5 5 10 5 5 Reviews ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

[表8] 比較例 2-1 比較例 2-2 暫時固定材 硬化型接著劑 之組成 （質量份） 硬化性樹脂 聚醯亞胺A - - 聚醯亞胺B 60 - 雙馬來醯亞胺化合物C 30 - 雙馬來醯亞胺化合物D 10 100 光聚合起始劑 雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物 （IGM Resins公司製造，「Omnirad819」） - - 1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮 （BASF公司製造，「Irgacure OXE02」） - - 離型劑 聚矽氧系離型劑 （BYK-Chemie公司製造，「BYK-UV 3500」） 1 - 丙烯酸系離型劑 （BYK-Chemie公司製造，「BYK-394」） - - 紫外線吸收劑 三系紫外線吸收劑 2-[4,6-雙(1,1'-聯苯-4-基)-1,3,5-三-2-基]-5-[(2-乙基己基)氧基]苯酚 （BASF公司製造，「Tinuvin1600」） - - 羥基苯基三系紫外線吸收劑 （BASF公司製造，「Tinuvin 479」） - - 2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三-2-基]-5-[3-(十二烷基氧基)-2-羥基丙氧基]苯酚 （BASF公司製造，「Tinuvin400」） - - 紫外線散射劑 氧化鈦 （石原產業公司製造，「TTO-55（S）」） - - 厚度（μm） 80 50 處理 紫外線照射（超高壓水銀燈、波長365 nm、累計光量20000 mJ/cm 2） 有 有 加熱（氮氣環境下，290℃，30分鐘） 有 有 硬化後於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率（%） 1.6 1.7 硬化後之雷射加工深度（μm） （波長308 nm，脈衝寬度10 nsec） 照射能量密度300 mJ/cm 2 0.08 未達0.01 照射能量密度400 mJ/cm 2 0.39 未達0.01 支持體 種類 玻璃 玻璃 波長308 nm下之光之穿透率（%） 88.3 88.3 評價 雷射剝離評價 （波長308 nm，脈衝寬度10 nsec， 照射能量密度300 mJ/cm 2） 剝離力（N/inch） 超過30 超過30 評價 × × [產業上之可利用性] [Table 8] Comparison Example 2-1 Comparison Example 2-2 Temporary fixing material Composition of curing adhesive (by weight) Hardening resin Polyimide A - - Polyimide B 60 - Bismaleimide Compound C 30 - Bismaleimide D 10 100 Photopolymerization initiator Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (manufactured by IGM Resins, "Omnirad819") - - 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone (manufactured by BASF, "Irgacure OXE02") - - Release agent Silicone release agent (BYK-Chemie, "BYK-UV 3500") 1 - Acrylic release agent (BYK-Chemie, "BYK-394") - - UV absorber three UV absorber 2-[4,6-Bis(1,1'-biphenyl-4-yl)-1,3,5-tri -2-yl]-5-[(2-ethylhexyl)oxy]phenol (produced by BASF, "Tinuvin 1600") - - Hydroxyphenyltrimethoxy Ultraviolet light absorber (produced by BASF, "Tinuvin 479") - - 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri -2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol (produced by BASF, "Tinuvin 400") - - UV scattering agent Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., "TTO-55 (S)") - - Thickness (μm) 80 50 handle Ultraviolet irradiation (ultra-high pressure mercury lamp, wavelength 365 nm, cumulative light intensity 20,000 mJ/cm 2 ) have have Heating (nitrogen environment, 290℃, 30 minutes) have have Weight loss after curing at 290℃ for 30 minutes in nitrogen environment (%) 1.6 1.7 Laser processing depth after hardening (μm) (wavelength 308 nm, pulse width 10 nsec) Irradiation energy density 300 mJ/ cm2 0.08 Less than 0.01 Irradiation energy density 400 mJ/ cm2 0.39 Less than 0.01 Support Type Glass Glass Transmittance of light at a wavelength of 308 nm (%) 88.3 88.3 Reviews Laser ablation evaluation (wavelength 308 nm, pulse width 10 nsec, irradiation energy density 300 mJ/cm 2 ) Peeling force (N/inch) Over 30 Over 30 Reviews × × [Industrial Availability]

根據本發明，能夠提供一種接著膜，其即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離，進而，即便於進行高溫加工處理之情形時，對被黏著體之剝離性亦優異。又，根據本發明，能夠提供一種該接著膜之硬化物。進而，根據本發明，能夠提供一種依序具有支持體、該接著膜、及半導體之積層體。進而，根據本發明，能夠提供一種電子零件之製造方法，其具有：使用該積層體，即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離之步驟；及即便於進行高溫加工處理之情形時，亦能夠容易地將被黏著體剝離之步驟。 又，根據本發明，能夠提供一種暫時固定材，其即便於硬化後照射低能量之雷射光之情形時，對雷射加工性能亦優異，從而能夠效率良好地將支持體剝離。又，根據本發明，能夠提供一種該暫時固定材之硬化物。進而，根據本發明，能夠提供一種具有該硬化物之積層體。進而，根據本發明，能夠提供一種電子零件之製造方法，其具有如下步驟：即便於照射低能量之雷射光之情形時，亦能夠效率良好地將支持體剝離。 According to the present invention, a bonding film can be provided, which can efficiently peel off a support even when irradiated with low-energy laser light, and has excellent peeling properties from an adherend even when subjected to high-temperature processing. In addition, according to the present invention, a cured product of the bonding film can be provided. Furthermore, according to the present invention, a laminate having a support, the bonding film, and a semiconductor in sequence can be provided. Furthermore, according to the present invention, a method for manufacturing electronic components can be provided, which has: using the laminate, even when irradiated with low-energy laser light, the step of efficiently peeling off the support body can be carried out; and even when high-temperature processing is carried out, the step of easily peeling off the adhered body can be carried out. Furthermore, according to the present invention, a temporary fixing material can be provided, which has excellent laser processing performance even when irradiated with low-energy laser light after curing, so that the support body can be peeled off efficiently. Furthermore, according to the present invention, a cured product of the temporary fixing material can be provided. Furthermore, according to the present invention, a laminate having the cured product can be provided. Furthermore, according to the present invention, a method for manufacturing electronic components can be provided, which has the following steps: even when irradiated with low-energy laser light, the support body can be efficiently peeled off.

無without

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Claims (33)

一種接著膜，其係包含含有硬化型接著劑之接著層者，其特徵在於： 該硬化型接著劑為光硬化型接著劑， 該接著層以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後的凝膠分率為65質量%以上， 該接著層以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後對波長308 nm之光的消光係數為1.0×10 -4以上。 A bonding film, comprising a bonding layer containing a curable bonding agent, characterized in that: the curable bonding agent is a light curable bonding agent, the gel fraction of the bonding layer after being irradiated with light of a wavelength of 405 nm in a manner such that the cumulative light amount becomes 20,000 mJ/cm 2 is 65% by mass or more, and the extinction coefficient of the bonding layer to light of a wavelength of 308 nm after being irradiated with light of a wavelength of 405 nm in a manner such that the cumulative light amount becomes 20,000 mJ/cm 2 is 1.0×10 -4 or more. 一種接著膜，其係包含含有硬化型接著劑之接著層者，其特徵在於： 該硬化型接著劑為光硬化型接著劑， 該接著層照射光後之凝膠分率為65質量%以上， 該接著層照射光後對波長308 nm之光之消光係數為1.0×10 -4以上。 A bonding film includes a bonding layer containing a curable bonding agent, wherein: the curable bonding agent is a light curable bonding agent, the gel fraction of the bonding layer after irradiation with light is 65 mass % or more, and the extinction coefficient of the bonding layer to light with a wavelength of 308 nm after irradiation with light is 1.0×10 -4 or more. 如請求項1或2之接著膜，其中，該硬化型接著劑含有硬化性樹脂及光聚合起始劑。The adhesive film of claim 1 or 2, wherein the curable adhesive contains a curable resin and a photopolymerization initiator. 如請求項3之接著膜，其中，該硬化性樹脂含有雙馬來醯亞胺化合物。The adhesive film of claim 3, wherein the curable resin contains a bismaleimide compound. 如請求項3或4之接著膜，其中，該光聚合起始劑於波長405 nm之吸光係數為10 ml/（g・cm）以上。The adhesive film of claim 3 or 4, wherein the light absorption coefficient of the photopolymerization initiator at a wavelength of 405 nm is greater than 10 ml/(g·cm). 如請求項3、4或5之接著膜，其中，該光聚合起始劑之含量相對於該硬化性樹脂100質量份，為0.1質量份以上10質量份以下。The adhesive film of claim 3, 4 or 5, wherein the content of the photopolymerization initiator is not less than 0.1 parts by mass and not more than 10 parts by mass relative to 100 parts by mass of the curable resin. 如請求項3、4、5或6之接著膜，其中，該硬化型接著劑進而含有紫外線吸收劑。The adhesive film of claim 3, 4, 5 or 6, wherein the curable adhesive further contains a UV absorber. 如請求項7之接著膜，其中，該紫外線吸收劑包含三系紫外線吸收劑。As claimed in claim 7, the adhesive film, wherein the ultraviolet absorber comprises three It is a UV absorber. 如請求項7或8之接著膜，其中，該紫外線吸收劑之含量相對於該硬化性樹脂100質量份，為1質量份以上30質量份以下。The adhesive film of claim 7 or 8, wherein the content of the ultraviolet absorber is not less than 1 part by mass and not more than 30 parts by mass relative to 100 parts by mass of the curable resin. 如請求項3、4、5、6、7、8或9之接著膜，其中，該硬化型接著劑進而含有離型劑。The adhesive film of claim 3, 4, 5, 6, 7, 8 or 9, wherein the hardening adhesive further contains a release agent. 如請求項10之接著膜，其中，該離型劑包含選自由聚矽氧系離型劑及丙烯酸系離型劑所組成之群中之至少1種。The adhesive film of claim 10, wherein the release agent comprises at least one selected from the group consisting of a silicone release agent and an acrylic release agent. 如請求項10或11之接著膜，其中，該離型劑之含量相對於該硬化性樹脂100質量份，為0.1質量份以上20質量份以下。The adhesive film of claim 10 or 11, wherein the content of the release agent is not less than 0.1 parts by mass and not more than 20 parts by mass relative to 100 parts by mass of the curable resin. 如請求項1、2、3、4、5、6、7、8、9、10、11或12之接著膜，其中，該接著層照射光之前的凝膠分率為60質量%以下。The bonding film of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein the gel fraction of the bonding layer before irradiation with light is 60 mass % or less. 如請求項1、2、3、4、5、6、7、8、9、10、11、12或13之接著膜，其中，該接著層照射光之前對波長308 nm之光的消光係數為1.0×10 -4以上。 The bonding film of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, wherein the extinction coefficient of the bonding layer to light of a wavelength of 308 nm before irradiation is 1.0×10 -4 or more. 如請求項1、2、3、4、5、6、7、8、9、10、11、12、13或14之接著膜，其具有基材。The adhesive film of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, comprising a substrate. 如請求項1、2、3、4、5、6、7、8、9、10、11、12、13、14或15之接著膜，其以累計光量成為20000 mJ/cm 2之方式照射波長405 nm之光後，於氮氣環境下，經以升溫速度10℃/min加熱之情形時之5%重量減少溫度為300℃以上。 The adhesive film of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, after being irradiated with light having a wavelength of 405 nm in such a manner that the cumulative light amount becomes 20000 mJ/ cm2 , has a 5% weight loss temperature of 300°C or higher when heated at a heating rate of 10°C/min in a nitrogen environment. 如請求項1、2、3、4、5、6、7、8、9、10、11、12、13、14、15或16之接著膜，其用於電子零件之暫時固定。The adhesive film of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 is used for temporarily fixing electronic parts. 一種硬化物，其係使請求項1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16或17之接著膜硬化而成，且 經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上。 A cured product, which is obtained by curing the adhesive film of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, and the laser processing depth is 0.10 μm or more when pulse irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec and an irradiation energy density of 300 mJ/ cm2 . 一種積層體，其依序具有支持體、請求項1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16或17之接著膜及半導體裝置。A laminate having a support, a bonding film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, and a semiconductor device in sequence. 一種電子零件之製造方法，其使用請求項19之積層體，並具有下述步驟： 光照射步驟：自該支持體側對該積層體照射光； 高溫加工處理步驟：對該積層體實施加熱處理或伴有發熱之處理； 支持體剝離步驟：自該支持體側對該積層體照射波長200 nm以上355 nm以下之雷射光，而將該支持體自該接著膜剝離；及 接著膜剝離步驟：將該接著膜自該半導體裝置剝離。 A method for manufacturing an electronic component, which uses the laminate of claim 19 and has the following steps: Light irradiation step: irradiating the laminate with light from the support side; High temperature processing step: applying heat treatment or treatment accompanied by heating to the laminate; Support peeling step: irradiating the laminate with laser light having a wavelength of not less than 200 nm and not more than 355 nm from the support side to peel the support from the bonding film; and Bonding film peeling step: peeling the bonding film from the semiconductor device. 一種暫時固定材，其係含有硬化型接著劑者，其特徵在於： 該硬化型接著劑為光硬化型接著劑， 藉由以累計光量成為20000 mJ/cm 2之方式照射波長365 nm之光而硬化後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上。 A temporary fixing material containing a curable adhesive, characterized in that: the curable adhesive is a light curing adhesive, which is cured by irradiating light with a wavelength of 365 nm in a manner such that the cumulative light amount becomes 20,000 mJ/ cm2 , and then the laser processing depth is greater than 0.10 μm when pulsed with laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 . 一種暫時固定材，其係含有硬化型接著劑者，其特徵在於： 硬化後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為0.10 μm以上。 A temporary fixing material containing a curing adhesive, characterized in that after curing, the laser processing depth is greater than 0.10 μm when pulsed with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an energy density of 300 mJ/cm 2 . 如請求項21或22之暫時固定材，其中，該硬化後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度300 mJ/cm 2之雷射光時之雷射加工深度為1.0 μm以下。 A temporary fixing material as claimed in claim 21 or 22, wherein after hardening, the laser processing depth when pulsed with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ/ cm2 is less than 1.0 μm. 如請求項21、22或23之暫時固定材，其中，該硬化後，經脈衝照射波長308 nm、脈衝寬度10 nsec、照射能量密度400 mJ/cm 2之雷射光時之雷射加工深度為1.0 μm以下。 A temporary fixing material as claimed in claim 21, 22 or 23, wherein after hardening, the laser processing depth when pulsed with laser light having a wavelength of 308 nm, a pulse width of 10 nsec and an irradiation energy density of 400 mJ/ cm2 is less than 1.0 μm. 如請求項21、22、23或24之暫時固定材，其中，該硬化型接著劑含有硬化性樹脂，該硬化性樹脂包含在主鏈之重複單元具有醯亞胺骨架之樹脂。The temporary fixing material of claim 21, 22, 23 or 24, wherein the curable adhesive contains a curable resin, and the curable resin contains a resin having an imide skeleton in the repeating units of the main chain. 如請求項25之暫時固定材，其中，於該硬化性樹脂100質量份中，該在主鏈之重複單元具有醯亞胺骨架之樹脂的含量為65質量份以上。The temporary fixing material of claim 25, wherein the content of the resin having an imide skeleton in the repeating units of the main chain is 65 parts by mass or more in 100 parts by mass of the curable resin. 如請求項21、22、23、24、25或26之暫時固定材，其中，該硬化型接著劑含有紫外線吸收劑或紫外線散射劑。The temporary fixing material of claim 21, 22, 23, 24, 25 or 26, wherein the curing adhesive contains an ultraviolet absorber or an ultraviolet scatterer. 如請求項27之暫時固定材，其中，該紫外線吸收劑或該紫外線散射劑包含三系紫外線吸收劑或氧化鈦。The temporary fixing material of claim 27, wherein the ultraviolet absorber or the ultraviolet scatterer comprises three It is a UV absorber or titanium oxide. 如請求項21、22、23、24、25、26、27或28之暫時固定材，其中，該硬化型接著劑含有光聚合起始劑。The temporary fixing material of claim 21, 22, 23, 24, 25, 26, 27 or 28, wherein the curing adhesive contains a photopolymerization initiator. 如請求項21、22、23、24、25、26、27、28或29之暫時固定材，其於硬化後，於氮氣環境下，經以290℃加熱30分鐘之情形時之重量減少率為7%以下。The temporary fixing material of claim 21, 22, 23, 24, 25, 26, 27, 28 or 29 has a weight loss rate of 7% or less when heated at 290°C for 30 minutes in a nitrogen environment after hardening. 一種硬化物，其係使請求項21、22、23、24、25、26、27、28、29或30之暫時固定材硬化而成。A hardened material obtained by hardening the temporary fixing material of claim 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. 一種積層體，其依序具有支持體、請求項31之硬化物及半導體裝置， 該支持體之波長300 nm以上400 nm以下之光的穿透率為50%以上。 A laminate having a support, a hardened material of claim 31, and a semiconductor device in order, wherein the transmittance of the support for light having a wavelength of 300 nm to 400 nm is 50% or more. 一種電子零件之製造方法，其特徵在於具有： 支持體剝離步驟：對依序含有支持體、暫時固定材之硬化物及半導體裝置的積層體自該支持體側脈衝照射波長308 nm以上355 nm以下、脈衝寬度100 nsec以下、照射能量密度500 mJ/cm 2以下之雷射光，藉此，將該支持體自該積層體剝離。 A method for manufacturing electronic components is characterized by having: a support stripping step: a laminate containing a support, a hardened temporary fixing material, and a semiconductor device is pulsed from the support side with laser light having a wavelength of 308 nm to 355 nm, a pulse width of 100 nsec or less, and an irradiation energy density of 500 mJ/cm2 or less , thereby stripping the support from the laminate.
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