TWI403568B - Thin film for fabrication of semiconductor and method of fabricating semiconductor apparatus - Google Patents
Thin film for fabrication of semiconductor and method of fabricating semiconductor apparatus Download PDFInfo
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- TWI403568B TWI403568B TW100103127A TW100103127A TWI403568B TW I403568 B TWI403568 B TW I403568B TW 100103127 A TW100103127 A TW 100103127A TW 100103127 A TW100103127 A TW 100103127A TW I403568 B TWI403568 B TW I403568B
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- Prior art keywords
- adhesive layer
- film
- semiconductor device
- pressure
- sensitive adhesive
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
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- 229920000306 polymethylpentene Polymers 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000010558 suspension polymerization method Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRLMGCBZYFFRED-UHFFFAOYSA-N undecyl prop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C=C RRLMGCBZYFFRED-UHFFFAOYSA-N 0.000 description 1
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- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/27—Manufacturing methods
-
- 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
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
-
- 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
- H01L21/6835—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 using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01029—Copper [Cu]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/156—Material
- H01L2924/157—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2924/15738—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950 C and less than 1550 C
- H01L2924/15747—Copper [Cu] as principal constituent
Landscapes
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Dicing (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本發明涉及半導體裝置的製造中使用的半導體裝置製造用薄膜,更具體地,涉及將半導體晶片切割而形成半導體晶片後,直到將該半導體晶片膠粘固定到被粘物上為止的一系列製程等中使用的半導體裝置製造用薄膜。另外,本發明涉及使用所述半導體裝置製造用薄膜製造半導體裝置的方法。The present invention relates to a thin film for semiconductor device manufacturing used in the manufacture of a semiconductor device, and more particularly to a series of processes, such as cutting a semiconductor wafer to form a semiconductor wafer, and then adhering the semiconductor wafer to an adherend. A thin film for manufacturing a semiconductor device used in the present invention. Further, the present invention relates to a method of manufacturing a semiconductor device using the thin film for semiconductor device manufacturing.
形成有電路圖案的半導體晶片,根據需要通過背面研磨調節厚度後,切割為半導體晶片(切割製程)。在切割製程中,為了除去切割層,一般以適度的液壓(通常為約2kg/cm2 )清洗半導體晶片。然後,利用膠粘劑將所述半導體晶片接合到引線框等被粘物上。在該製程中,將膠粘劑塗布到引線框(lead frame)或半導體晶片上。但是,通過該方法難以實現膠粘劑層的均勻化,另外膠粘劑的塗布需要特殊裝置或者需要長時間。因此,提出了在切割製程中膠粘保持半導體晶片的同時也提供晶片接合(die bonding)所需的晶片固著用膠粘劑層的切割/晶片接合薄膜(dicing‧bonding film)(例如,參考日本特開昭60-57642號公報)。The semiconductor wafer on which the circuit pattern is formed is diced into a semiconductor wafer (cutting process) by adjusting the thickness by back grinding as needed. In the cutting process, in order to remove the cut layer, the semiconductor wafer is typically cleaned with a moderate hydraulic pressure (typically about 2 kg/cm 2 ). Then, the semiconductor wafer is bonded to an adherend such as a lead frame with an adhesive. In this process, the adhesive is applied to a lead frame or semiconductor wafer. However, it is difficult to achieve uniformization of the adhesive layer by this method, and the application of the adhesive requires special equipment or takes a long time. Therefore, a dicing/bonding film for a wafer fixing adhesive layer required for die bonding is provided while adhering and holding a semiconductor wafer in a dicing process (for example, refer to Japanese special Kai-kai 60-57642).
在專利文獻1中記載的切割/晶片接合薄膜中,在支撐薄膜(基材層)上設置有粘合性剝離層(粘合劑層)及導電性膠粘劑層。即,在膠粘劑層的保持下切割半導體晶片後,將支撐薄膜拉伸而將半導體晶片與膠粘劑層一同剝離,將其每個進行回收,然後經由該膠粘劑層固著到引線框等被粘物上。In the dicing/wafer bonding film described in Patent Document 1, an adhesive release layer (pressure-sensitive adhesive layer) and a conductive adhesive layer are provided on a support film (base material layer). That is, after the semiconductor wafer is cut under the holding of the adhesive layer, the support film is stretched, the semiconductor wafer is peeled off together with the adhesive layer, each of which is recovered, and then fixed to the adherend such as a lead frame via the adhesive layer. .
這種切割/晶片接合薄膜的膠粘劑層,為了不產生不能切割或尺寸誤差等,希望具有對半導體晶片的良好保持力、以及能夠將切割後的半導體晶片與膠粘劑層一體地從支撐基材上剝離的良好剝離性。另外,希望切割/晶片接合薄膜的粘合劑層具有,對引線框的良好保持力、用於防止切割時小片化的半導體晶片的飛散的與膠粘劑的密合性、以及切割時產生的切削屑不附著到帶有膠粘劑層的半導體晶片上的低污染性。The adhesive layer of the dicing/wafer bonding film is desired to have a good holding force for the semiconductor wafer and to peel the diced semiconductor wafer and the adhesive layer integrally from the supporting substrate in order not to cause dicing or dimensional error or the like. Good peelability. Further, it is desirable that the adhesive layer of the dicing/wafer bonding film has a good holding force for the lead frame, adhesion to the adhesive for preventing scattering of the semiconductor wafer which is diced during dicing, and chipping generated during cutting. It is not attached to the low contamination of the semiconductor wafer with the adhesive layer.
但是,要想以良好的平衡發揮這些特性並不容易,特別是近年來,半導體晶片以高容量化為目的而進行薄型化和大面積化發展,因此使基材層和粘合劑層滿足各種要求變得更加困難。即,由於現有的切割/晶片接合薄膜沒有分別按功能對應各種要求的特性,因此不能以良好的平衡發揮所述特性。However, it is not easy to exhibit these characteristics in a good balance. In particular, in recent years, semiconductor wafers have been thinned and expanded in size for the purpose of increasing the capacity, so that the substrate layer and the adhesive layer are satisfied. The requirements have become more difficult. That is, since the conventional dicing/wafer bonding film does not have various characteristics corresponding to functions, it is not possible to exhibit the characteristics in a good balance.
因此,為了解決這些問題,提出了各種改良方法。例如,在專利文獻2中,公開了切割片、剝離薄膜、晶片貼附薄膜及脫模薄膜依次層疊而得到的切割用粘合帶。該切割用粘合帶中,在切割片上重新設置剝離薄膜,並且使剝離薄膜與晶片貼附薄膜的剝離力小於剝離薄膜與切割片的剝離力,由此在半導體晶片的拾取(pick up)時,可以容易地將晶片貼附薄膜與半導體晶片一同剝離。另外,由於具有切割框架(切割環)粘貼到切割片上的構成,因此得以確保切割環的固定功能。即,專利文獻2中記載的切割用粘合帶,通過在切割片與晶片貼附薄膜之間設置剝離薄膜,而得到一直以來尋求的切割/晶片接合薄膜的性能,即將具有將切割時的膠粘性和拾取時的剝離性這樣的不同的功能分離的結構。Therefore, in order to solve these problems, various improvements have been proposed. For example, Patent Document 2 discloses a dicing adhesive tape obtained by laminating a dicing sheet, a release film, a wafer attaching film, and a release film in this order. In the adhesive tape for dicing, the release film is newly provided on the dicing sheet, and the peeling force of the release film and the wafer-attached film is smaller than the peeling force of the release film and the dicing sheet, thereby being picked up at the time of picking up the semiconductor wafer The wafer attaching film can be easily peeled off together with the semiconductor wafer. Further, since the cutting frame (cutting ring) is attached to the cutting piece, the fixing function of the cutting ring is ensured. In other words, in the adhesive tape for dicing described in Patent Document 2, by providing a release film between the dicing sheet and the wafer-attached film, the performance of the dicing/wafer bonding film which has been conventionally sought is obtained, that is, the glue at the time of cutting A structure with different functions such as viscosity and peelability at the time of picking.
但是,即使是專利文獻2中記載的切割用粘合帶,在半導體晶片的切割時也從切割片上產生切削屑,該切削屑以毛刺(,burr)或細須(,beard)的形態附著到半導體晶片的側面等,由此存在半導體裝置的製造產率(fabrication yield)下降的問題。However, even in the dicing adhesive tape described in Patent Document 2, chips are generated from the dicing sheet at the time of dicing of the semiconductor wafer, and the chips are burred ( , burr) or fine whiskers ( The form of the beard is attached to the side surface of the semiconductor wafer or the like, whereby there is a problem that the manufacturing yield of the semiconductor device is lowered.
專利文獻1:日本特開昭60-57642號公報Patent Document 1: Japanese Laid-Open Patent Publication No. 60-57642
專利文獻2:日本特開2006-203000號公報Patent Document 2: Japanese Laid-Open Patent Publication No. 2006-203000
本發明為了解決所述問題而做出,其目的在於提供即使半導體晶片為薄型的情況下,在切割該薄型半導體晶片時的保持力、在將通過切割得到的半導體晶片與其膠粘劑層一體地剝離時的剝離性、以及在所述半導體晶片上不附著切削屑的低污染性中的平衡特性優良的且半導體晶片的污染防止優良的新型半導體裝置製造用薄膜及半導體裝置的製造方法。The present invention has been made to solve the above problems, and an object of the invention is to provide a holding force when cutting a thin semiconductor wafer even when a semiconductor wafer is thin, and to integrally peel a semiconductor wafer obtained by cutting from an adhesive layer thereof. A thin film and a method for producing a semiconductor device which are excellent in the balance property of the low-contamination property in which the chips are not adhered to the semiconductor wafer, and which are excellent in contamination prevention of the semiconductor wafer.
本申請人等為了解決上述問題對半導體裝置製造用薄膜及半導體裝置的製造方法進行了研究。結果發現,通過採用下述構成,可以實現上述目的,從而完成了本發明。In order to solve the above problems, the applicant and the like have studied a thin film for semiconductor device manufacturing and a method for manufacturing a semiconductor device. As a result, it has been found that the above object can be attained by adopting the following constitution, and the present invention has been completed.
本發明的半導體製造用薄膜,為了解決上述課題,在半導體的製造時所使用的半導體製造用薄膜,其特徵在於,其包含:基材層;設置在所述基材層上的第一粘合劑層;設置在所述第一粘合劑層上,且預先通過照射輻射線而固化的輻射線固化型的第二粘合劑層;以及設置在所述第二粘合劑層上的膠粘劑層。In order to solve the above problems, a film for semiconductor production used in the production of a semiconductor is characterized in that the film for semiconductor manufacturing of the present invention comprises: a substrate layer; and a first bond provided on the substrate layer a radiation-curable second adhesive layer disposed on the first adhesive layer and previously cured by irradiation with radiation; and an adhesive disposed on the second adhesive layer Floor.
半導體裝置的製造中使用的現有切割/晶片接合薄膜,一般具有在基材層上依次層疊粘合劑層和膠粘劑層的結構。而且,所述粘合劑層要求具有在半導體晶片的切割時能夠防止半導體晶片的晶片飛散的粘合性、以及要求在所述半導體晶片的拾取時能夠容易地與膠粘劑層剝離的剝離性。即,粘合劑層在切割製程和拾取製程中要求相反的性能。A conventional dicing/wafer bonding film used for the manufacture of a semiconductor device generally has a structure in which a pressure-sensitive adhesive layer and an adhesive layer are sequentially laminated on a substrate layer. Further, the pressure-sensitive adhesive layer is required to have adhesiveness capable of preventing wafer scattering of the semiconductor wafer at the time of dicing of the semiconductor wafer, and peeling property which can be easily peeled off from the adhesive layer at the time of picking up the semiconductor wafer. That is, the adhesive layer requires the opposite performance in the cutting process and the picking process.
另一方面,本發明中,按照上述結構,通過在基材層上依次設置第一粘合劑層和第二粘合劑層,可以實現對現有切割/晶片接合薄膜的粘合劑層所要求的切割時的粘合性與拾取時的剝離性的功能分離。即,第一粘合劑層將第二粘合劑層膠粘固定,因此對膠粘劑層上粘貼的半導體晶片進行切割時,能夠防止半導體晶片的晶片飛散。對於第一粘合劑層不要求拾取時的剝離性,因此在基材層上設置有第一粘合劑層的結構發揮了作為一種載帶的功能。另一方面,第二粘合劑層通過照射輻射線而預先固化,因此對膠粘劑層顯示良好的剝離性。因此,能夠良好地進行半導體晶片的拾取。另外,也可以省略拾取前照射輻射線的製程。On the other hand, in the present invention, according to the above configuration, by sequentially providing the first adhesive layer and the second adhesive layer on the substrate layer, it is possible to achieve the adhesive layer of the conventional dicing/wafer bonding film. The adhesiveness at the time of cutting is separated from the function of the peeling property at the time of picking. That is, since the first pressure-sensitive adhesive layer is used to adhere and fix the second pressure-sensitive adhesive layer, it is possible to prevent the wafer of the semiconductor wafer from scattering when the semiconductor wafer bonded to the adhesive layer is diced. Since the first adhesive layer does not require peeling property at the time of picking up, the structure in which the first adhesive layer is provided on the base material layer functions as a carrier tape. On the other hand, the second adhesive layer is preliminarily cured by irradiation with radiation, and thus exhibits good peelability to the adhesive layer. Therefore, picking up of the semiconductor wafer can be performed favorably. In addition, the process of irradiating the radiation before picking up may also be omitted.
另外,現有的切割/晶片接合薄膜中,半導體晶片的切割時,將切割刀片等的切入深度進行到達粘合劑層或基材層。但是,切割進行到粘合劑層的一部分時,有時在切割面上粘合劑層的一部分成為毛刺或細須從而附著到粘合劑層與膠粘劑層的邊界。另外,切割進行到基材層時,有時產生絲狀的切削屑,污染半導體晶片。但是,本發明中,由於是在基材層上層疊有第一粘合劑層和第二粘合劑層的結構,因此切割刀片等的切入深度不必進行到第一粘合劑層,可以在第二粘合劑層停止。另外,第二粘合劑層通過照射輻射線而預先固化,因此可以抑制在切割面上第二粘合劑層的一部分成為毛刺從而附著到第二粘合劑層與膠粘劑層的邊界。結果,可以良好地拾取帶有膠粘劑層的半導體晶片。另外,切割不必進行到基材層,因此也不產生絲狀的切削屑。因此,本發明的半導體裝置製造用薄膜,可以實現對半導體晶片的低污染性。Further, in the conventional dicing/wafer bonding film, when the semiconductor wafer is diced, the dicing depth of the dicing blade or the like is advanced to reach the pressure-sensitive adhesive layer or the substrate layer. However, when the cutting proceeds to a part of the adhesive layer, a part of the adhesive layer on the cut surface sometimes becomes a burr or a whisker to adhere to the boundary between the adhesive layer and the adhesive layer. Further, when the cutting proceeds to the base material layer, filamentous chips may be generated to contaminate the semiconductor wafer. However, in the present invention, since the first adhesive layer and the second adhesive layer are laminated on the base material layer, the cutting depth of the cutting blade or the like does not have to proceed to the first adhesive layer, and The second adhesive layer stops. Further, the second adhesive layer is preliminarily cured by irradiation with radiation, so that it is possible to suppress a part of the second adhesive layer from being burred on the cut surface to adhere to the boundary between the second adhesive layer and the adhesive layer. As a result, the semiconductor wafer with the adhesive layer can be picked up well. In addition, the cutting does not have to be carried out to the substrate layer, so that no filament-like chips are produced. Therefore, the film for semiconductor device manufacturing of the present invention can achieve low contamination of the semiconductor wafer.
所述構成中,優選:所述第二粘合劑層和膠粘劑層以至少落入到所述第一粘合劑層中的切割環粘貼部分的內側的方式進行設置,所述膠粘劑層的平面形狀大於所述第二粘合劑層,並且所述膠粘劑層以覆蓋整個第二粘合劑層的方式進行設置,另外,所述膠粘劑層中不位於所述第二粘合劑層上的周邊部,設置在所述第一粘合劑層上。In the above configuration, preferably, the second adhesive layer and the adhesive layer are disposed so as to fall at least inside the cutting ring sticking portion in the first adhesive layer, the plane of the adhesive layer The shape is larger than the second adhesive layer, and the adhesive layer is disposed to cover the entire second adhesive layer, and further, the adhesive layer is not located on the periphery of the second adhesive layer And disposed on the first adhesive layer.
根據所述構成,由於可以在不要求拾取時的剝離性的第一粘合劑層上粘貼切割環,因此在切割時能夠可靠地固定該切割環。另外,與在膠粘劑層上粘貼切割環的情況相比,將使用後的切割環進行剝離時,也可以抑制膠糊附著的產生。另外,膠粘劑層的平面形狀大於第二粘合劑層,並且以覆蓋整個第二粘合劑層的方式進行設置。另外,膠粘劑層的周邊部不是設置在第二粘合劑層上而是設置在第一粘合劑層上,為牢固膠粘的構成,因此例如能夠防止切割時膠粘劑從第二粘合劑層上剝離而產生捲縮。According to this configuration, since the cutting ring can be attached to the first pressure-sensitive adhesive layer which is not required to be peeled off during picking up, the cutting ring can be reliably fixed at the time of cutting. Further, when the dicing ring after use is peeled off as compared with the case where the dicing ring is attached to the adhesive layer, the occurrence of adhesive adhesion can be suppressed. In addition, the planar shape of the adhesive layer is larger than that of the second adhesive layer, and is disposed in such a manner as to cover the entire second adhesive layer. Further, the peripheral portion of the adhesive layer is not provided on the second adhesive layer but on the first adhesive layer, and is a firmly adhesive structure, so that, for example, the adhesive can be prevented from being cut from the second adhesive layer. The upper peeling causes curling.
所述構成中,優選:將所述基材層、所述第一粘合劑層和所述第二粘合劑層堆疊而成的結構物(例如切割薄膜),藉由E×I所計算的彎曲剛性S在5.0×104 ~7.0×105 的範圍內。(其中,I為以b×T3 /12表示的截面二次矩(secondary moment),b為所述結構物的試驗片的寬度10(mm),T為所述結構物的厚度(mm),E為所述結構物的25℃下的拉伸儲能彈性模量(Pa))。通過將所述彎曲剛性S設定為5.0×104 以上,能夠保持所述結構物的剛性,在晶片粘貼時可以在不產生褶皺的情況下進行粘貼。另一方面,通過將所述彎曲剛性S設定為7.0×105 以下,拾取時所述結構物適當地彎曲,可以實現穩定的拾取。In the above configuration, preferably, a structure (for example, a dicing film) in which the base material layer, the first pressure-sensitive adhesive layer, and the second pressure-sensitive adhesive layer are stacked is calculated by E×I The bending rigidity S is in the range of 5.0 × 10 4 to 7.0 × 10 5 . (wherein I is a secondary moment represented by b × T 3 /12, b is a width of the test piece of the structure of 10 (mm), and T is a thickness (mm) of the structure) E is the tensile storage elastic modulus (Pa) at 25 ° C of the structure. By setting the bending rigidity S to 5.0 × 10 4 or more, the rigidity of the structure can be maintained, and the wafer can be pasted without wrinkles. On the other hand, by setting the bending rigidity S to 7.0 × 10 5 or less, the structure is appropriately bent at the time of picking up, and stable picking can be achieved.
所述構成中,優選所述第二粘合劑層和膠粘劑層之間的剝離強度X在0.01N/20mm~0.2N/20mm的範圍內。通過將第二粘合劑層和膠粘劑層之間的剝離強度X設定為0.01N/20mm以上,例如,在半導體晶片的切割時,可以防止兩者間產生剝離、以及防止半導體晶片產生晶片飛散。另一方面,通過將所述剝離強度X設定為0.2N/20mm以下,即使省略輻射線的照射製程,也可以良好地拾取半導體晶片。In the above configuration, the peel strength X between the second pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer is preferably in the range of 0.01 N/20 mm to 0.2 N/20 mm. By setting the peeling strength X between the second pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer to 0.01 N/20 mm or more, for example, at the time of dicing of the semiconductor wafer, peeling between the two can be prevented, and wafer scattering can be prevented from occurring in the semiconductor wafer. On the other hand, by setting the peeling strength X to 0.2 N/20 mm or less, even if the irradiation process of the radiation is omitted, the semiconductor wafer can be picked up favorably.
所述構成中,優選所述第一粘合劑層和第二粘合劑層之間的剝離強度Y在0.2N/20mm~10N/20mm的範圍內。通過將第一粘合劑層和第二粘合劑層之間的剝離強度Y設定為0.2N/20mm以上,例如,切割時能夠可靠地固定半導體晶片或半導體晶片。另外,通過將所述剝離強度Y設定為10N/20mm以下,可以將第二粘合劑層從第一粘合劑層上剝離,可以將作為由基材層和第一粘合劑層構成的載帶的層疊薄膜再利用。In the above configuration, it is preferable that the peel strength Y between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is in the range of 0.2 N/20 mm to 10 N/20 mm. By setting the peeling strength Y between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer to 0.2 N/20 mm or more, for example, the semiconductor wafer or the semiconductor wafer can be reliably fixed at the time of cutting. Further, by setting the peeling strength Y to 10 N/20 mm or less, the second adhesive layer can be peeled off from the first adhesive layer, and can be composed of the base material layer and the first adhesive layer. The laminated film of the carrier tape is reused.
所述構成中,優選所述第二粘合劑層和膠粘劑層之間的剝離強度X與所述第一粘合劑層和第二粘合劑層之間的剝離強度Y之比(Y/X)在3~500的範圍內。通過將所述剝離強度X與剝離強度Y之比(Y/X)設定為3以上,可以使半導體晶片的拾取時的剝離介面位於第二粘合劑層與膠粘劑層的邊界。另一方面通過將所述比(Y/X)設定為500以下,可以抑制切割時的晶片飛散或膠粘劑層的捲縮,可以穩定地切割。In the above configuration, a ratio of the peeling strength X between the second adhesive layer and the adhesive layer to the peel strength Y between the first adhesive layer and the second adhesive layer is preferable (Y/ X) is in the range of 3 to 500. By setting the ratio (Y/X) of the peeling strength X to the peeling strength Y to 3 or more, the peeling interface at the time of picking up the semiconductor wafer can be located at the boundary between the second adhesive layer and the adhesive layer. On the other hand, by setting the ratio (Y/X) to 500 or less, it is possible to suppress wafer scattering at the time of dicing or curling of the adhesive layer, and it is possible to stably cut.
所述構成中,優選所述第二粘合劑層的厚度在10μm~100μm的範圍內。通過將第二粘合劑層的厚度設定為10μm以上,能夠防止切割時切割刀片的切入深度達到第一粘合劑層。另一方面,通過將第二粘合劑層的厚度設定為100μm以下,可以進行半導體晶片的穩定拾取。In the above configuration, it is preferable that the thickness of the second pressure-sensitive adhesive layer is in the range of 10 μm to 100 μm. By setting the thickness of the second pressure-sensitive adhesive layer to 10 μm or more, it is possible to prevent the cutting depth of the cutting blade from reaching the first pressure-sensitive adhesive layer at the time of cutting. On the other hand, by setting the thickness of the second pressure-sensitive adhesive layer to 100 μm or less, stable pickup of the semiconductor wafer can be performed.
所述構成中,優選所述第一粘合劑層和SUS304-BA板之間的剝離強度在0.2N/20mm~11N/20mm的範圍內。通過將第一粘合劑層和SUS304-BA板之間的剝離強度設定為0.2N/20mm以上,能夠將切割環可靠地膠粘固定,從而能夠良好地進行拾取。另一方面,通過將所述剝離強度設定為11N/20mm以下,在將使用後的切割環從第一粘合劑層上剝離時,能夠減少在切割環上產生膠糊殘留的現象。In the above configuration, it is preferable that the peel strength between the first pressure-sensitive adhesive layer and the SUS304-BA plate is in the range of 0.2 N/20 mm to 11 N/20 mm. By setting the peeling strength between the first pressure-sensitive adhesive layer and the SUS304-BA plate to 0.2 N/20 mm or more, the cutting ring can be reliably adhered and fixed, and the pick-up can be performed satisfactorily. On the other hand, by setting the peeling strength to 11 N/20 mm or less, when the dicing ring after use is peeled off from the first pressure-sensitive adhesive layer, it is possible to reduce the occurrence of adhesive residue on the dicing ring.
所述構成中,優選所述第二粘合劑層是通過照射輻射線將該第二粘合劑層的前驅物(precursor)固化後而形成在所述第一粘合劑層上的粘合劑層。In the above configuration, preferably, the second adhesive layer is formed by curing a precursor of the second adhesive layer by irradiation of radiation to form a bond on the first adhesive layer. Agent layer.
所述構成中,優選所述第二粘合劑層是通過將該第二粘合劑層的前驅物設置在所述第一粘合劑層上之後通過照射輻射線進行固化而形成的粘合劑層。In the above configuration, preferably, the second adhesive layer is a bond formed by curing the radiation by irradiating radiation after the precursor of the second adhesive layer is disposed on the first adhesive layer. Agent layer.
所述構成中,優選所述膠粘劑層是在預先通過照射輻射線而固化的第二粘合劑層上形成的膠粘劑層。In the above configuration, it is preferable that the adhesive layer is an adhesive layer formed on a second adhesive layer which is previously cured by irradiation with radiation.
所述構成中,優選所述膠粘劑層設置在通過照射輻射線進行固化之前的第二粘合劑層的前驅物上。In the above configuration, it is preferable that the adhesive layer is provided on a precursor of the second adhesive layer before curing by irradiation with radiation.
所述構成中,優選所述膠粘劑層至少由環氧樹脂、酚樹脂和丙烯酸類樹脂形成。In the above configuration, it is preferable that the adhesive layer is formed of at least an epoxy resin, a phenol resin, and an acrylic resin.
所述構成中,優選所述丙烯酸類樹脂的玻璃化轉變溫度在-30℃~10℃的範圍內。通過將丙烯酸類樹脂的玻璃化轉變溫度設定為-30℃以上,能夠保持膠粘劑層的高溫時(例如,100℃~200℃)的儲能彈性模量(storage elastic modulus)。另一方面,通過將所述玻璃化轉變溫度設定為10℃以下,能夠實現對半導體晶片的良好的密合性、粘貼性。In the above configuration, it is preferred that the acrylic resin has a glass transition temperature in the range of -30 ° C to 10 ° C. By setting the glass transition temperature of the acrylic resin to -30 ° C or higher, it is possible to maintain a storage elastic modulus at a high temperature (for example, 100 ° C to 200 ° C) of the adhesive layer. On the other hand, by setting the glass transition temperature to 10 ° C or lower, good adhesion and adhesion to a semiconductor wafer can be achieved.
所述構成中,優選所述第二粘合劑層至少由丙烯酸類聚合物形成。In the above configuration, it is preferable that the second pressure-sensitive adhesive layer is formed of at least an acrylic polymer.
本發明的半導體裝置的製造方法,為了解決所述課題,為使用所述中記載的半導體裝置製造用薄膜製造半導體裝置的方法,其特徵在於,所述方法至少包含以下製程:在所述半導體裝置製造用薄膜的所述膠粘劑層上壓接半導體晶片的製程,將所述半導體晶片與所述膠粘劑層一起進行切割從而形成半導體晶片的製程,其中,切割的切入深度在所述第二粘合劑層停止,和將所述半導體晶片與所述膠粘劑層一起從所述第二粘合劑層上剝離的製程,並且,從所述半導體晶片的壓接製程到半導體晶片的剝離製程,不對所述第二粘合劑層照射輻射線。In the method for manufacturing a semiconductor device according to the present invention, in order to solve the above problems, a method for manufacturing a semiconductor device using the thin film for semiconductor device manufacturing described above is characterized in that the method includes at least the following process: a process of crimping a semiconductor wafer on the adhesive layer of a film for manufacturing, cutting the semiconductor wafer together with the adhesive layer to form a process of forming a semiconductor wafer, wherein a dicing depth of the cut is at the second adhesive Stopping the layer, and a process of peeling the semiconductor wafer from the second adhesive layer together with the adhesive layer, and from the crimping process of the semiconductor wafer to the stripping process of the semiconductor wafer, The second adhesive layer illuminates the radiation.
所述方法中,使用在基材層上依次層疊有第一粘合劑層、第二粘合劑層和膠粘劑層的結構的半導體裝置製造用薄膜來進行半導體裝置的製造。在此,所述第一粘合劑層將第二粘合劑層膠粘固定,因此在半導體晶片的切割時,能夠防止半導體晶片的晶片飛散。另外,在半導體晶片的切割中,由於切割刀片的切入深度在第二粘合劑層停止,因此能夠防止在切割基材層時產生的切削屑成為毛刺或細須而附著到半導體晶片上。另外,第二粘合劑層通過預先照射輻射線而固化,因此能夠抑制在切割面上第二粘合劑層的一部分成為毛刺或細須而附著到第二粘合劑層與膠粘劑層的邊界。結果,能夠良好地拾取帶有膠粘劑層的半導體晶片。In the above method, a semiconductor device is produced by using a film for semiconductor device manufacturing in which a first pressure-sensitive adhesive layer, a second pressure-sensitive adhesive layer, and an adhesive layer are laminated in this order on a base material layer. Here, the first adhesive layer adhesively fixes the second adhesive layer, so that the wafer of the semiconductor wafer can be prevented from scattering when the semiconductor wafer is diced. Further, in the dicing of the semiconductor wafer, since the dicing depth of the dicing blade is stopped at the second adhesive layer, it is possible to prevent the chips generated when the substrate layer is diced from becoming burrs or whiskers and adhering to the semiconductor wafer. In addition, the second adhesive layer is cured by irradiating the radiation in advance, so that it is possible to suppress a part of the second adhesive layer on the cut surface from becoming a burr or a whisker and adhering to the boundary between the second adhesive layer and the adhesive layer. . As a result, the semiconductor wafer with the adhesive layer can be picked up well.
另外,第二粘合劑層通過照射輻射線而預先固化,因此對膠粘劑層顯示良好的剝離性。因此,能夠良好地進行半導體晶片的拾取。另外,在從半導體晶片的壓接製程到半導體晶片的剝離製程,不必對所述第二粘合劑層照射輻射線,因此可以減少製程數。Further, since the second pressure-sensitive adhesive layer is previously cured by irradiation with radiation, it exhibits good peelability to the adhesive layer. Therefore, picking up of the semiconductor wafer can be performed favorably. In addition, in the process from the crimping process of the semiconductor wafer to the stripping process of the semiconductor wafer, it is not necessary to irradiate the second adhesive layer with radiation, and thus the number of processes can be reduced.
通過所述中說明的手段,本發明實現下述效果。即,根據本發明的半導體裝置製造用薄膜,通過採用在基材層上依次設置第一粘合劑層、第二粘合劑層和膠粘劑層的結構,對第一粘合劑層賦予將第二粘合劑層可靠地膠粘固定的功能,並通過對第二粘合劑層預先照射輻射線使其固化,從而賦予了與膠粘劑層的良好剝離性。即,將對現有的切割/晶片接合薄膜的粘合劑層所要求的、切割時的粘合性與拾取時的剝離性進行了功能分離。結果,即使半導體晶片為薄型化、大型化的情況下,也可以得到切割半導體晶片時的保持力和拾取半導體晶片時的剝離性優良的半導體裝置製造用薄膜。另外,切割時,可以不必將切入深度進行到基材層,而是在第二粘合劑層停止,因此可以抑制切削屑的產生,可以減少該切削屑附著到半導體晶片上。即,根據本發明,可以提供低污染性優良的半導體裝置製造用薄膜。另外,根據本發明的半導體裝置的製造方法,通過使用所述半導體裝置製造用薄膜來進行半導體裝置的製造,可以提高成品率。The present invention achieves the following effects by the means described above. In other words, according to the film for producing a semiconductor device of the present invention, the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer are sequentially disposed on the base material layer, and the first pressure-sensitive adhesive layer is provided. The two adhesive layers reliably adhere to the fixing function and are cured by irradiating the second adhesive layer with radiation, thereby imparting good peeling property to the adhesive layer. That is, the adhesiveness at the time of cutting required for the adhesive layer of the conventional dicing/wafer bonding film and the peeling property at the time of picking were functionally separated. As a result, even when the semiconductor wafer is made thinner and larger, it is possible to obtain a film for semiconductor device production which is excellent in the holding force when the semiconductor wafer is diced and the peelability at the time of picking up the semiconductor wafer. Further, at the time of cutting, it is not necessary to carry out the cutting depth to the base material layer, but to stop the second adhesive layer, so that generation of chips can be suppressed, and the chips can be reduced from adhering to the semiconductor wafer. That is, according to the present invention, it is possible to provide a film for semiconductor device production which is excellent in low contamination. Further, according to the method of manufacturing a semiconductor device of the present invention, the semiconductor device can be manufactured by using the thin film for semiconductor device manufacturing, and the yield can be improved.
為讓本發明之上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。The above described features and advantages of the present invention will be more apparent from the following description.
具體實施方式detailed description
(半導體裝置製造用薄膜)(film for semiconductor device manufacturing)
以下參考圖1和圖2對本發明的實施方式的半導體裝置製造用薄膜進行說明。圖1是表示本發明的一個實施方式的半導體裝置製造用薄膜的剖面示意圖。圖2是從隔片一側觀看所述半導體裝置製造用薄膜時的俯視圖。Hereinafter, a film for semiconductor device manufacturing according to an embodiment of the present invention will be described with reference to FIGS. 1 and 2. 1 is a schematic cross-sectional view showing a film for manufacturing a semiconductor device according to an embodiment of the present invention. FIG. 2 is a plan view of the semiconductor device manufacturing film viewed from the side of the spacer.
如圖1所示,半導體裝置製造用薄膜10具有在基材層11上至少依次設置有第一粘合劑層12、第二粘合劑層13和膠粘劑層14的構成。另外,本發明的半導體裝置製造用薄膜11,如圖1所示,可以設置有用於保護第一粘合劑層12和膠粘劑層14的表面的隔片15。另外,所述基材層11和第一粘合劑層12用於將第二粘合劑層13和後述的切割環膠粘固定,發揮作為載帶的作用。As shown in FIG. 1, the film 10 for semiconductor device production has a configuration in which at least the first pressure-sensitive adhesive layer 12, the second pressure-sensitive adhesive layer 13, and the pressure-sensitive adhesive layer 14 are provided on the base material layer 11 in this order. Further, as shown in FIG. 1, the film 11 for semiconductor device manufacturing of the present invention may be provided with a separator 15 for protecting the surfaces of the first pressure-sensitive adhesive layer 12 and the pressure-sensitive adhesive layer 14. Further, the base material layer 11 and the first pressure-sensitive adhesive layer 12 are used to adhere and fix the second pressure-sensitive adhesive layer 13 and a dicing ring to be described later, and function as a carrier tape.
[基材層][Substrate layer]
所述基材層11的構成材料沒有特別限制,可以列舉例如:由低密度聚乙烯、線性聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚聚丙烯、聚丁烯、聚甲基戊烯等聚烯烴、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯共聚物、離聚物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚氨酯、聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯等聚酯、聚碳酸酯、聚醯亞胺、聚醚醚酮、聚醯亞胺、聚醚醯亞胺、聚醯胺、全芳香族聚醯胺、聚苯硫醚、芳族聚醯胺(紙)、玻璃、玻璃布、含氟樹脂、聚氯乙烯、聚偏二氯乙烯、纖維素類樹脂、聚矽氧烷樹脂、它們的混合物等構成的塑膠薄膜。另外,作為基材層11的材料,可以列舉所述樹脂的交聯物等聚合物。所述塑膠薄膜,可以不拉伸而使用,也可以根據需要進行單軸或雙軸拉伸處理後使用。The constituent material of the base material layer 11 is not particularly limited, and examples thereof include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, and embedded. Polyolefin, homopolypropylene, polybutene, polymethylpentene, etc., ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymerization , ethylene-(meth) acrylate (random, alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate Polyesters such as glycol esters, polycarbonates, polyimines, polyetheretherketones, polyimines, polyetherimine, polyamines, wholly aromatic polyamines, polyphenylene sulfides, aromatics A plastic film composed of polyamide (paper), glass, glass cloth, fluorine-containing resin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, polyoxyalkylene resin, a mixture thereof, or the like. Moreover, as a material of the base material layer 11, a polymer such as a crosslinked product of the above resin may be mentioned. The plastic film may be used without stretching, or may be used after uniaxial or biaxial stretching treatment as needed.
為了提高與第一粘合劑層12的密合性和保持性等,所述基材層11的表面可以進行慣用的表面處理。作為該方法,可以列舉例如:鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、電離射線(ionizing radiation)處理等化學或物理處理、底塗劑(例如,後述的粘合物質)塗布處理。In order to improve adhesion to the first pressure-sensitive adhesive layer 12, retention, and the like, the surface of the base material layer 11 may be subjected to a conventional surface treatment. Examples of the method include chemical or physical treatment such as chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, and ionizing radiation treatment, and a primer (for example, a binder described later) coating treatment.
所述基材層11的構成材料可以適當選擇同種或異種材料來使用。另外,根據需要也可以將多種材料混合使用。另外,為了賦予抗靜電能力,基材層11也可以使用在所述塑膠薄膜上設置有由金屬、合金或它們的氧化物等形成的、厚度為約30埃~約500埃的導電物質的蒸鍍層的薄膜。另外,也可以使用所述薄膜之間、或者與其他薄膜粘貼而得到的層壓體等。另外,基材層11可是單層或者是將兩層以上使用所述材料的薄膜等進行兩層以上的多層化而得到的層疊薄膜。The constituent material of the base material layer 11 can be appropriately selected from the same or different materials. In addition, a plurality of materials may be used in combination as needed. Further, in order to impart antistatic ability, the base material layer 11 may be formed by steaming a conductive material having a thickness of about 30 angstroms to about 500 angstroms formed of a metal, an alloy, or an oxide thereof on the plastic film. Plated film. Further, a laminate or the like obtained by laminating the films or other films may be used. In addition, the base material layer 11 may be a single layer or a laminated film obtained by laminating two or more layers of a film or the like using the above-mentioned materials.
基材層11的厚度,只要是在後述的擴展時不斷裂的程度則沒有特別限制,可以適當設定。一般優選在約5μm~約200μm的範圍內。The thickness of the base material layer 11 is not particularly limited as long as it does not break at the time of expansion described later, and can be appropriately set. It is generally preferably in the range of from about 5 μm to about 200 μm.
[第一粘合劑層][First adhesive layer]
第一粘合劑層12設置在基材層11上,是用於將第二粘合劑層13和切割環膠粘固定的層。圖1中,第一粘合劑層12設置在整個矩形的基材層11上,平面形狀為矩形,但是,也可以是圓形。另外,後述的半導體晶片的拾取時,在第二粘合劑層13與膠粘劑層14之間進行剝離,因此對於第一粘合劑層12不特別要求拾取時的剝離性能。即,第一粘合劑層12的基本性能是粘合性。因此,第一粘合劑層12的構成材料沒有特別限制,可以採用現有公知的材料。The first adhesive layer 12 is provided on the substrate layer 11, and is a layer for adhesively fixing the second adhesive layer 13 and the dicing ring. In Fig. 1, the first adhesive layer 12 is provided on the entire rectangular substrate layer 11, and the planar shape is rectangular, but may be circular. Further, at the time of picking up the semiconductor wafer to be described later, since the second pressure-sensitive adhesive layer 13 and the pressure-sensitive adhesive layer 14 are peeled off, the first pressure-sensitive adhesive layer 12 is not particularly required to have peeling properties at the time of picking up. That is, the basic property of the first adhesive layer 12 is adhesiveness. Therefore, the constituent material of the first pressure-sensitive adhesive layer 12 is not particularly limited, and a conventionally known material can be employed.
作為構成第一粘合劑層12的粘合劑,可以使用一般使用的壓敏(pressure sensitivity)粘合劑。具體而言,可以列舉例如:丙烯酸類粘合劑、橡膠類粘合劑、聚矽氧烷類粘合劑、聚乙烯基醚類粘合劑等各種粘合劑。其中,從對於作為被切割物的半導體晶片或半導體封裝的膠粘性、剝離後的半導體晶片等的利用超純水或醇等有機溶劑進行清洗的清洗性等觀點考慮,優選以(甲基)丙烯酸類聚合物作為基礎聚合物的(甲基)丙烯酸類粘合劑。另外,所謂(甲基),例如(甲基)丙烯酸類聚合物的情況下,是指丙烯酸類聚合物和甲基丙烯酸類聚合物雙方。此時,以下例示的化合物也同樣。As the binder constituting the first pressure-sensitive adhesive layer 12, a pressure sensitivity adhesive which is generally used can be used. Specific examples thereof include various binders such as an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a polyoxyalkylene-based pressure-sensitive adhesive, and a polyvinyl ether-based pressure-sensitive adhesive. In view of the cleaning property of the semiconductor wafer or the semiconductor package as the object to be cut, the semiconductor wafer after peeling, and the organic solvent such as ultrapure water or alcohol, it is preferable to use (meth) Acrylic polymer as a (meth)acrylic binder for a base polymer. Further, the term "(meth)", for example, a (meth)acrylic polymer means both an acrylic polymer and a methacrylic polymer. In this case, the compounds exemplified below are also the same.
作為所述(甲基)丙烯酸類聚合物,可以列舉例如(甲基)丙烯酸烷基酯(例如,甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、仲丁酯(s-butyl ester)、叔丁酯(t-butyl ester)、戊酯、異戊酯、己酯、庚酯、辛酯、2-乙基己酯、異辛酯、異壬酯、癸酯、異癸酯、十一烷酯、十二烷酯、十三烷酯、十四烷酯、十六烷酯、十八烷酯、二十烷酯等碳原子數1~30的烷基、特別是碳原子數4~18的直鏈或支鏈烷基酯等)、(甲基)丙烯酸環烷酯(例如,環戊酯、環己酯等)、(甲基)丙烯酸羥烷酯(例如,羥乙酯、羥丁酯、羥己酯等)、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸、衣康酸、馬來酸酐、(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、(甲基)丙烯酸烷氨基烷基酯(例如,甲基丙烯酸二甲氨基乙酯、甲基丙烯酸叔丁氨基乙酯等)、乙酸乙烯酯、苯乙烯的一種或兩種以上作為單體成分的(甲基)丙烯酸類聚合物等。Examples of the (meth)acrylic polymer include alkyl (meth)acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, and sec-butyl ester). S-butyl ester), t-butyl ester, amyl ester, isoamyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, isodecyl ester, decyl ester, Isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, cetyl ester, octadecyl ester, eicosyl ester, etc., having 1 to 30 carbon atoms, especially It is a linear or branched alkyl ester having 4 to 18 carbon atoms, a cycloalkyl (meth)acrylate (for example, cyclopentyl ester, cyclohexyl ester, etc.), or a hydroxyalkyl (meth)acrylate (for example). , hydroxyethyl ester, hydroxybutyl ester, hydroxyhexyl ester, etc.), glycidyl (meth)acrylate, (meth)acrylic acid, itaconic acid, maleic anhydride, (meth)acrylamide, N-hydroxyl a (meth) acrylamide, an alkylaminoalkyl (meth) acrylate (for example, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, etc.), a vinyl acetate, a styrene Or two or more (meth) propylene as a monomer component Acid polymers, etc.
所述(甲基)丙烯酸類聚合物,為了改善凝聚力和膠粘性等,根據需要也可以含有與能夠與所述(甲基)丙烯酸烷基酯或環烷酯共聚的其他單體成分對應的單元。作為這樣的單體成分,可以列舉例如:丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸、巴豆酸等含羧基單體;馬來酸酐、衣康酸酐等酸酐單體;(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-10-羥基癸酯、(甲基)丙烯酸-12-羥基十二烷酯、(甲基)丙烯酸(4-羥甲基環己基)甲酯等含羥基單體;苯乙烯磺酸、烯丙磺酸、2-(甲基)丙烯醯胺基-2-甲基丙磺酸、(甲基)丙烯醯胺基丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體;丙烯醯磷酸-2-羥基乙酯等含磷酸基單體;丙烯醯胺、丙烯腈等。這些可共聚單體成分可以使用一種或兩種以上。這些可共聚單體的使用量優選為全部單體成分的30重量%以下,進一步優選15重量%以下。The (meth)acrylic polymer may contain a monomer component which is copolymerizable with the alkyl (meth)acrylate or the cycloalkyl ester, as needed, in order to improve cohesive force, adhesiveness, and the like. unit. Examples of such a monomer component include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. Carboxyl group-containing monomer; anhydride monomer such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxyl (meth)acrylate Butyl ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxy-12 (meth)acrylate a hydroxyl group-containing monomer such as an alkyl ester or (4-hydroxymethylcyclohexyl)methyl (meth)acrylate; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylamidoamino-2-methyl a sulfonic acid group-containing monomer such as propanesulfonic acid, (meth) propylene decyl propyl sulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid; A phosphate group-containing monomer such as hydroxyethyl ester; acrylamide or acrylonitrile. These copolymerizable monomer components may be used alone or in combination of two or more. The amount of these copolymerizable monomers used is preferably 30% by weight or less, and more preferably 15% by weight or less based on the total of the monomer components.
另外,為了進行交聯,所述(甲基)丙烯酸類聚合物根據需要也可以含有多官能單體等作為共聚用單體成分。通過將基礎聚合物交聯,粘合劑層的自支撐性改善,因此可以防止粘合片的顯著變形,容易保持第一粘合劑層12的平板狀態。Moreover, in order to carry out crosslinking, the (meth)acrylic polymer may contain a polyfunctional monomer or the like as a comonomer component as needed. By crosslinking the base polymer, the self-supporting property of the pressure-sensitive adhesive layer is improved, so that significant deformation of the pressure-sensitive adhesive sheet can be prevented, and the flat state of the first pressure-sensitive adhesive layer 12 can be easily maintained.
作為多官能單體,可以列舉例如:己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、胺甲酸酯(甲基)丙烯酸酯等。這些多官能單體也是可以使用一種或者兩種以上。多官能單體的使用量從粘合特性等觀點考慮優選為全部單體成分的30重量%以下。Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and neopentyl Alcohol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, and the like. These polyfunctional monomers may also be used alone or in combination of two or more. The amount of use of the polyfunctional monomer is preferably 30% by weight or less based on the total of the monomer components from the viewpoint of adhesion properties and the like.
所述(甲基)丙烯酸類聚合物可以通過將單一單體或兩種以上單體的混合物聚合而得到。聚合可以通過溶液聚合、乳液聚合、本體聚合、懸浮聚合、光聚合等的任意方式進行。特別是在照射紫外線或電子射線等輻射線的情況下,優選通過將在胺甲酸酯(甲基)丙烯酸酯類低聚物中配合單體成分和光聚合引發劑而得到的液狀組合物進行流延並進行光聚合來合成(甲基)丙烯酸類聚合物。The (meth)acrylic polymer can be obtained by polymerizing a single monomer or a mixture of two or more monomers. The polymerization can be carried out by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization or the like. In particular, when a radiation such as an ultraviolet ray or an electron beam is irradiated, it is preferred to carry out a liquid composition obtained by mixing a monomer component and a photopolymerization initiator with a urethane (meth) acrylate oligomer. The (meth)acrylic polymer is synthesized by casting and photopolymerizing.
所述胺甲酸酯(甲基)丙烯酸酯類低聚物,是數均分子量為約500~約10萬,優選1000~3萬,並且以酯‧二醇為主骨架的雙官能化合物。另外,作為單體成分,可以列舉嗎啉(甲基)丙烯酸酯、(甲基)丙烯酸異冰片酯、雙環戊烷基(甲基)丙烯酸酯(dicyclopentanyl(metha)acrylate)、雙環戊烯基(甲基)丙烯酸酯(dicyclopentenyl(metha) acrylate)、甲氧基化環癸三烯(甲基)丙烯酸酯等。胺甲酸酯(甲基)丙烯酸酯類低聚物與單體成分的混合比,優選低聚物:單體成分=95~5:5~95(重量%),更優選50~70:50~30(重量%)。胺甲酸酯(甲基)丙烯酸酯類低聚物的含量高時,液狀組合物的粘度變高,因此具有難以聚合的傾向。The urethane (meth) acrylate oligomer is a bifunctional compound having a number average molecular weight of from about 500 to about 100,000, preferably from 1,000 to 30,000, and an ester ‧ diol as a main skeleton. Further, examples of the monomer component include morpholine (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl ( Dicyclopentenyl (metha) acrylate, methoxylated cyclotriene (meth) acrylate, and the like. The mixing ratio of the urethane (meth) acrylate oligomer to the monomer component is preferably oligomer: monomer component = 95 to 5: 5 to 95 (% by weight), more preferably 50 to 70: 50 ~30 (% by weight). When the content of the urethane (meth) acrylate oligomer is high, the viscosity of the liquid composition becomes high, and thus it tends to be difficult to polymerize.
從凝聚力的觀點考慮,所述(甲基)丙烯酸類聚合物的重量平均分子量(weight-average molecular weight)優選為約10萬~約100萬,更優選約15萬~約90萬。The weight-average molecular weight of the (meth)acrylic polymer is preferably from about 100,000 to about 1,000,000, more preferably from about 150,000 to about 900,000, from the viewpoint of cohesive force.
另外,為了提高作為基礎聚合物的(甲基)丙烯酸類聚合物等的數均分子量,所述粘合劑中也可以適當使用外部交聯劑。作為外部交聯方法的具體手段,可以列舉:添加多異氰酸酯化合物、三聚氰胺型樹脂、脲樹脂、環氧樹脂、多胺、含羧基聚合物等所謂的交聯劑進行反應的方法。使用外部交聯劑的情況下,其使用量根據與欲交聯的基礎聚合物的平衡以及作為粘合劑的使用用途進行適當確定。一般相對於所述基礎聚合物100重量份優選配合約1重量份~約5重量份。另外,粘合劑中根據需要除所述成分之外還可以使用現有公知的各種增粘劑、抗老化劑等添加劑。Further, in order to increase the number average molecular weight of the (meth)acrylic polymer or the like as the base polymer, an external crosslinking agent may be suitably used in the binder. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, a melamine resin, a urea resin, an epoxy resin, a polyamine or a carboxyl group-containing polymer. In the case of using an external crosslinking agent, the amount thereof to be used is appropriately determined depending on the balance with the base polymer to be crosslinked and the use as a binder. It is generally preferably blended in an amount of from about 1 part by weight to about 5 parts by weight based on 100 parts by weight of the base polymer. Further, as the binder, in addition to the above-mentioned components, additives such as various conventionally known tackifiers and anti-aging agents may be used.
第一粘合劑層12的厚度沒有特別限制,從粘合性的觀點考慮,優選在1μm~30μm的範圍內,更優選2μm~25μm的範圍,特別優選3μm~20μm的範圍。The thickness of the first pressure-sensitive adhesive layer 12 is not particularly limited, and is preferably in the range of 1 μm to 30 μm, more preferably in the range of 2 μm to 25 μm, and particularly preferably in the range of 3 μm to 20 μm from the viewpoint of adhesion.
第一粘合劑層12與切割環之間的剝離強度優選在0.2N/20mm~10N/20mm的範圍內,更優選在0.3N/20mm~9.5N/20mm的範圍內,特別優選在0.5N/20mm~9N/20mm的範圍內。通過將第一粘合劑層12與切割環之間的剝離強度設定為0.2N/20mm以上,可以將該切割環可靠地膠粘固定,良好地進行切割。另一方面,通過將所述剝離強度設定為10N/20mm以下,可以在抑制膠糊殘留產生的同時將使用後的切割環從第一粘合劑層上剝離。The peel strength between the first adhesive layer 12 and the dicing ring is preferably in the range of 0.2 N/20 mm to 10 N/20 mm, more preferably in the range of 0.3 N/20 mm to 9.5 N/20 mm, and particularly preferably 0.5 N. In the range of /20mm~9N/20mm. By setting the peeling strength between the first pressure-sensitive adhesive layer 12 and the cutting ring to 0.2 N/20 mm or more, the cutting ring can be reliably adhered and fixed, and the cutting can be performed favorably. On the other hand, by setting the peeling strength to 10 N/20 mm or less, it is possible to peel off the used cutting ring from the first pressure-sensitive adhesive layer while suppressing the occurrence of adhesive residue.
另外,在不損害本發明效果等的範圍內,第一粘合劑層12中也可以含有各種添加劑(例如,著色劑、增稠劑、增量劑、填充劑、增粘劑、增塑劑、抗老化劑、抗氧化劑、表面活性劑、交聯劑等)。Further, the first pressure-sensitive adhesive layer 12 may contain various additives (for example, a coloring agent, a thickener, an extender, a filler, a tackifier, a plasticizer) insofar as the effects of the present invention are not impaired. , anti-aging agents, antioxidants, surfactants, cross-linking agents, etc.).
[第二粘合劑層][Second adhesive layer]
第二粘合劑層13設置在第一粘合劑層12上。第二粘合劑層13發揮在切割半導體晶片時防止切割刀片等的切入深度達到基材層11或第一粘合劑層12的功能。因此,能夠防止基材層11被切割時產生的絲狀切削屑的產生。結果,能夠減少半導體晶片的污染。另外,也能夠防止將第一粘合劑層12切割時產生的毛刺的產生。The second adhesive layer 13 is disposed on the first adhesive layer 12. The second adhesive layer 13 functions to prevent the cutting depth of the dicing blade or the like from reaching the base material layer 11 or the first adhesive layer 12 when the semiconductor wafer is diced. Therefore, it is possible to prevent the generation of the filamentous chips generated when the base material layer 11 is cut. As a result, contamination of the semiconductor wafer can be reduced. In addition, it is also possible to prevent the occurrence of burrs generated when the first adhesive layer 12 is cut.
另外,第二粘合劑層13至少由輻射線固化型粘合劑形成,並且通過照射輻射線而預先固化。因此,第二粘合劑層13的粘合力比通常的粘合劑層降低,從而對膠粘劑層14的剝離性優良。即,第二粘合劑層13發揮提高半導體晶片的拾取性的功能。另外,切割時即使部分被切割刀片切割,也能夠減少毛刺的產生。結果,不會產生在第二粘合劑層13與膠粘劑14的邊界附著粘合劑從而阻礙在拾取時兩者的剝離。另外,作為所述輻射線,可以列舉X射線、紫外線、電子射線等。In addition, the second adhesive layer 13 is formed of at least a radiation curable adhesive and is preliminarily cured by irradiation of radiation. Therefore, the adhesive force of the second adhesive layer 13 is lower than that of the usual adhesive layer, and the peeling property to the adhesive layer 14 is excellent. That is, the second pressure-sensitive adhesive layer 13 functions to improve the pick-up property of the semiconductor wafer. In addition, the burr can be reduced even if it is partially cut by the cutting blade during cutting. As a result, no adhesive is attached to the boundary between the second adhesive layer 13 and the adhesive 14 to hinder peeling of both at the time of picking up. Further, examples of the radiation include X-rays, ultraviolet rays, and electron beams.
設置有第二粘合劑層13的區域,優選為第一粘合劑層12上的切割環的粘貼部分18的內側。例如,如圖2所示,在第二粘合劑層13的平面形狀為圓形的情況下,其直徑優選小於切割環的內徑。由此,第一粘合劑層12具有可靠地將第二粘合劑層13和切割環固定的性能(即粘合性)就足夠了,不必考慮拾取時的剝離性。The area where the second adhesive layer 13 is provided is preferably the inner side of the pasting portion 18 of the cutting ring on the first adhesive layer 12. For example, as shown in FIG. 2, in the case where the planar shape of the second adhesive layer 13 is circular, the diameter thereof is preferably smaller than the inner diameter of the cutting ring. Thereby, it is sufficient that the first adhesive layer 12 has a property of reliably fixing the second adhesive layer 13 and the dicing ring (i.e., adhesiveness), regardless of the peeling property at the time of pickup.
第二粘合劑層13可以設置在整個第一粘合劑層12上,但是,如圖1所示,優選以落入到切割環粘貼部分的內側的方式進行設置。由此,可將切割環粘貼到第一粘合劑層12上,而不必設置在第二粘合劑層13上。由此,第二粘合劑層13的半導體晶片拾取時的剝離性良好就足夠了,不要求對切割環的粘合性能。The second adhesive layer 13 may be disposed on the entire first adhesive layer 12, but as shown in Fig. 1, it is preferably disposed so as to fall inside the bonded portion of the cutting ring. Thereby, the cutting ring can be attached to the first adhesive layer 12 without being disposed on the second adhesive layer 13. Thereby, it is sufficient that the peeling property at the time of picking up the semiconductor wafer of the second adhesive layer 13 is good, and the adhesive property to the dicing ring is not required.
第二粘合劑層13是在第一粘合劑層12上設置的通過照射輻射線而預先固化的粘合劑層。通過照射紫外線使第二粘合劑層13輻射線固化時,由於交聯結構的形成,第二粘合劑層13的體積縮小。因此,例如,在與第一粘合劑層12粘貼後進行第二粘合劑層13的輻射線固化時,由於第二粘合劑層13的體積收縮而對基材層11和第一粘合劑層12施加應力,有時產生翹曲。但是,如果預先通過輻射線進行固化,則可以防止對基材層11等施加不需要的應力,可以得到無翹曲的半導體裝置製造用薄膜。The second adhesive layer 13 is an adhesive layer which is provided on the first adhesive layer 12 and which is previously cured by irradiation of radiation. When the second adhesive layer 13 is radiation-cured by irradiation of ultraviolet rays, the volume of the second adhesive layer 13 is reduced due to the formation of the crosslinked structure. Therefore, for example, when the radiation curing of the second adhesive layer 13 is performed after bonding with the first adhesive layer 12, the substrate layer 11 and the first paste are adhered due to the volume shrinkage of the second adhesive layer 13. The mixture layer 12 applies stress, sometimes causing warpage. However, if it is previously cured by radiation, it is possible to prevent unnecessary stress from being applied to the base layer 11 and the like, and it is possible to obtain a film for manufacturing a semiconductor device without warpage.
但是,也可以在第一粘合劑層12上層疊第二粘合劑層13的前驅物(以下稱為“第二粘合劑層前驅物”)後,對該第二粘合劑層前驅物照射輻射線使其固化,而形成第二粘合劑層13。此時,可以保持第一粘合劑層12與第二粘合劑層13之間的密合性未受到過度損害的層疊狀態。結果,能夠抑制第二粘合劑13的粘合性過度降低。另外,也可以在第二粘合劑層前驅物上層疊膠粘劑層14後,對該第二粘合劑層前驅物照射輻射線使其固化,而形成第二粘合劑層13。However, the precursor of the second adhesive layer 13 (hereinafter referred to as "second adhesive layer precursor") may be laminated on the first adhesive layer 12, and the second adhesive layer precursor may be applied. The object is irradiated with radiation to cure it to form a second adhesive layer 13. At this time, the laminated state in which the adhesion between the first adhesive layer 12 and the second adhesive layer 13 is not excessively damaged can be maintained. As a result, it is possible to suppress an excessive decrease in the adhesion of the second adhesive 13 . Alternatively, after the adhesive layer 14 is laminated on the second adhesive layer precursor, the second adhesive layer precursor may be irradiated with radiation to be cured to form the second adhesive layer 13.
作為所述輻射線固化型(radiation curable type)粘合劑,可以沒有特別限制地使用具有碳碳雙鍵等輻射線固化性官能團並且顯示粘合性的粘合劑。更具體而言,作為輻射線固化型粘合劑,可以例示例如在所述丙烯酸類粘合劑、橡膠類粘合劑、聚矽氧烷類粘合劑、聚乙烯基醚類粘合劑等一般的壓敏膠粘劑中配合輻射線固化性單體成分或輻射線固化性低聚物成分而得到的添加型輻射線固化型粘合劑。作為所述輻射線固化型粘合劑,從半導體晶片或玻璃等藉由超純水或醇等有機溶劑進行清洗的清潔洗淨性等忌避污染的電子構件的觀點考慮,優選以丙烯酸類聚合物作為基礎聚合物或聚合物主成分的丙烯酸類粘合劑。As the radiation curable type binder, a binder having a radiation curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation. More specifically, as the radiation curable pressure-sensitive adhesive, for example, the acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive, polyoxyalkylene-based pressure-sensitive adhesive, polyvinyl ether-based pressure-sensitive adhesive, or the like can be exemplified. A radiation-curable adhesive obtained by blending a radiation curable monomer component or a radiation curable oligomer component in a general pressure-sensitive adhesive. The radiation-curable pressure-sensitive adhesive is preferably an acrylic polymer from the viewpoints of cleaning, such as semiconductor wafer or glass, which are cleaned and washed by an organic solvent such as ultrapure water or alcohol, and which is resistant to contamination. An acrylic adhesive as a base polymer or a polymer main component.
作為所述丙烯酸類聚合物,優選由相對於丙烯酸類聚合物的總量含有由CH2 =CHCOOR(式中,R為碳原子數6~10、更優選8~9的烷基)表示的丙烯酸烷基酯和含羥基單體並且不含有含羧基單體的單體組合物構成的丙烯酸類聚合物。所述丙烯酸烷基酯中,所述烷基的碳原子數低於6時,剝離力變得過大從而有時拾取性下降。另一方面,所述烷基的碳原子數超過10時,與膠粘劑層14的膠粘性或密合性下降,結果有時在切割時產生晶片飛散。The acrylic polymer preferably contains acrylic acid represented by CH 2 =CHCOOR (wherein R is an alkyl group having 6 to 10 carbon atoms, more preferably 8 to 9 carbon atoms) with respect to the total amount of the acrylic polymer. An acrylic polymer composed of an alkyl ester and a monomer composition containing a hydroxyl group-containing monomer and containing no carboxyl group-containing monomer. In the alkyl acrylate, when the number of carbon atoms of the alkyl group is less than 6, the peeling force is excessively increased and the pick-up property may be lowered. On the other hand, when the number of carbon atoms of the alkyl group exceeds 10, the adhesiveness or adhesion to the adhesive layer 14 is lowered, and as a result, wafer scattering occurs at the time of dicing.
丙烯酸烷基酯,具體地可以列舉例如:丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸異辛酯、丙烯酸-2-乙基己酯、丙烯酸壬酯、丙烯酸異壬酯、丙烯酸癸酯、丙烯酸異癸酯等烷基的碳原子數為6~10(特別是碳原子數為8~9)的直鏈或支鏈的丙烯酸烷基酯等。這些單體可以單獨使用或者兩種以上組合使用。另外,丙烯酸烷基酯中,特別優選烷基的碳原子數為8~9的丙烯酸烷基酯,更具體而言,從拾取性的觀點考慮,丙烯酸-2-乙基己酯、丙烯酸異辛酯、丙烯酸異壬酯最合適。The alkyl acrylate may specifically be exemplified by hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isodecyl acrylate, decyl acrylate, A linear or branched alkyl acrylate having an alkyl group having 6 to 10 carbon atoms (particularly, 8 to 9 carbon atoms) such as isodecyl acrylate. These monomers may be used singly or in combination of two or more. Further, among the alkyl acrylates, an alkyl acrylate having an alkyl group having 8 to 9 carbon atoms is particularly preferable, and more specifically, 2-ethylhexyl acrylate or isobutyl acrylate is used from the viewpoint of pick-up property. Ester, isodecyl acrylate is most suitable.
所述丙烯酸烷基酯的配合量,相對於丙烯酸類聚合物總量優選為50重量%以上,更優選70重量%~90重量%。丙烯酸烷基酯的所述配合量低於50重量%時,剝離力變得過大,有時拾取性下降。The compounding amount of the alkyl acrylate is preferably 50% by weight or more, and more preferably 70% by weight to 90% by weight based on the total amount of the acrylic polymer. When the compounding amount of the alkyl acrylate is less than 50% by weight, the peeling force becomes excessively large, and the pick-up property may be lowered.
所述丙烯酸類聚合物中,優選使用能夠與所述丙烯酸烷基酯共聚的含羥基單體作為必要成分。作為含羥基單體,可以列舉例如:(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-10-羥基癸酯、(甲基)丙烯酸-12-羥基十二烷酯、(甲基)丙烯酸(4-羥甲基環己基)甲酯等。所述含羥基單體可以單獨使用或者兩種以上組合使用。Among the acrylic polymers, a hydroxyl group-containing monomer copolymerizable with the alkyl acrylate is preferably used as an essential component. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (methyl). 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, (methyl) Acrylic acid (4-hydroxymethylcyclohexyl) methyl ester or the like. The hydroxyl group-containing monomers may be used singly or in combination of two or more.
所述含羥基單體的配合量,相對於單體成分的總量優選在1重量%~30重量%的範圍內,更優選3重量%~10重量%的範圍內。含羥基單體的配合量低於1重量%時,有時粘合劑的凝聚力下降,拾取性下降。另一方面,所述含量超過30重量%時,有時粘合劑的極性提高,與膠粘劑層的相互作用提高,由此拾取性下降。The compounding amount of the hydroxyl group-containing monomer is preferably in the range of 1% by weight to 30% by weight, and more preferably in the range of 3% by weight to 10% by weight based on the total amount of the monomer component. When the amount of the hydroxyl group-containing monomer is less than 1% by weight, the cohesive force of the binder may be lowered, and the pick-up property may be lowered. On the other hand, when the content exceeds 30% by weight, the polarity of the binder may increase, and the interaction with the adhesive layer may increase, whereby the pickup property may be lowered.
在此,丙烯酸類聚合物中,可以使用所述化學式表示的丙烯酸烷基酯以外的丙烯酸酯作為單體成分。作為這樣的丙烯酸酯,可以列舉所述化學式表示的丙烯酸烷基酯以外的其他丙烯酸烷基酯、以及具有芳香環的丙烯酸酯(丙烯酸苯酯等丙烯酸芳基酯等)、具有脂環烴基的丙烯酸酯(丙烯酸環戊酯、丙烯酸環己酯等丙烯酸環烷酯、丙烯酸異冰片酯等)等。這樣的丙烯酸酯可以單獨使用或者兩種以上組合使用。另外,這些物質中,所述的其他丙烯酸烷基酯、丙烯酸環烷酯是適合的,特別地可以適合使用其他丙烯酸烷基酯。Here, as the monomer component, an acrylate other than the alkyl acrylate represented by the above chemical formula can be used for the acrylic polymer. Examples of such an acrylate include an alkyl acrylate other than the alkyl acrylate represented by the chemical formula, an acrylate having an aromatic ring (such as an aryl acrylate such as phenyl acrylate), and an acrylic acid having an alicyclic hydrocarbon group. An ester (cycloalkyl acrylate such as cyclopentyl acrylate or cyclohexyl acrylate, isobornyl acrylate or the like). Such acrylates may be used singly or in combination of two or more. Further, among these, the other alkyl acrylate and cycloalkyl acrylate are suitable, and in particular, other alkyl acrylates may be suitably used.
作為所述其他丙烯酸烷基酯,可以列舉例如:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸異丙酯、丙烯酸丁酯、丙烯酸異丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸戊酯、丙烯酸異戊酯等烷基的碳原子數為5以下的丙烯酸烷基酯;丙烯酸十一烷酯、丙烯酸十二烷酯、丙烯酸十三烷酯、丙烯酸十四烷酯、丙烯酸十六烷酯、丙烯酸十八烷酯、丙烯酸二十烷酯等烷基的碳原子數為11以上(優選11~30)的丙烯酸烷基酯等。As the other alkyl acrylate, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, acrylic acid may be mentioned. An alkyl acrylate having an alkyl group having 5 or less carbon atoms such as amyl ester or isoamyl acrylate; undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, and acrylic acid An alkyl acrylate having an alkyl group having an alkyl group such as an alkyl ester, octadecyl acrylate or an amyl acrylate such as 11 or more (preferably 11 to 30).
所述丙烯酸酯的配合量相對於單體成分總量優選為50重量%以上,更優選在70重量%~90重量%的範圍內。丙烯酸酯的配合量低於50重量%時,有時第二粘合劑層13的剝離力過度增大。The compounding amount of the acrylate is preferably 50% by weight or more, and more preferably 70% by weight to 90% by weight based on the total amount of the monomer components. When the amount of the acrylate is less than 50% by weight, the peeling force of the second pressure-sensitive adhesive layer 13 may excessively increase.
所述丙烯酸類聚合物,為了改善凝聚力和耐熱性等,根據需要也可以含有與能夠與所述丙烯酸烷基酯或含羥基單體共聚的其他單體成分對應的單元。作為能夠共聚的其他單體成分,可以列舉例如:甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸異丙酯、甲基丙烯酸丁酯、甲基丙烯酸異丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸叔丁酯等甲基丙烯酸酯;馬來酸酐、衣康酸酐等酸酐單體;苯乙烯磺酸、烯丙磺酸、2-(甲基)丙烯醯胺基-2-甲基丙磺酸、(甲基)丙烯醯胺基丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體;丙烯醯磷酸-2-羥基乙酯等含磷酸基單體;苯乙烯、乙烯基甲苯、α-甲基苯乙烯等苯乙烯類單體;乙烯、丁二烯、異戊二烯、異丁烯等烯烴或二烯類;氯乙烯等含鹵素原子單體;含氟(甲基)丙烯酸酯等含氟原子單體;丙烯醯胺、丙烯腈等。這些可共聚單體成分可以使用一種或兩種以上。這些可共聚單體的使用量優選為全部單體成分的40重量%以下。The acrylic polymer may contain a unit corresponding to another monomer component copolymerizable with the alkyl acrylate or the hydroxyl group-containing monomer, as needed, in order to improve cohesive force, heat resistance, and the like. Examples of other monomer components copolymerizable include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, and isobutyl methacrylate. , methacrylate such as sec-butyl methacrylate or t-butyl methacrylate; anhydride monomers such as maleic anhydride and itaconic anhydride; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylic acid hydrazine A sulfonic acid group-containing monomer such as amino-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, or (meth)acryloxynaphthalenesulfonic acid ; phosphine-based monomer such as acrylofluorene-2-hydroxyethyl phosphate; styrene monomer such as styrene, vinyl toluene or α-methyl styrene; ethylene, butadiene, isoprene, isobutylene, etc. An olefin or a diene; a halogen atom-containing monomer such as vinyl chloride; a fluorine atom-containing monomer such as a fluorine-containing (meth) acrylate; acrylamide or acrylonitrile. These copolymerizable monomer components may be used alone or in combination of two or more. The amount of these copolymerizable monomers used is preferably 40% by weight or less based on the total of the monomer components.
但是,本實施方式中,不使用含羧基單體是很重要的。當使用含羧基單體時,該羧基與膠粘劑層14中的環氧樹脂中的環氧基反應,而使第二粘合劑層13與膠粘劑層14的膠粘性提高,兩者的剝離性下降。作為這樣的含羧基單體,可以列舉丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸、巴豆酸等。However, in the present embodiment, it is important not to use a carboxyl group-containing monomer. When a carboxyl group-containing monomer is used, the carboxyl group reacts with the epoxy group in the epoxy resin in the adhesive layer 14, and the adhesiveness of the second adhesive layer 13 and the adhesive layer 14 is improved, and the peeling property of both is improved. decline. Examples of such a carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.
所述丙烯酸類聚合物可以通過將單一單體或兩種以上單體的混合物聚合而得到。聚合也可以通過溶液聚合(例如,自由基聚合、陰離子聚合、陽離子聚合等)、乳液聚合、本體聚合、懸浮聚合、光聚合(例如,紫外線(UV)聚合等)等的任意方式進行。從防止污染潔淨的被粘物等觀點考慮,優選低分子量物質的含量少。從這點考慮,丙烯酸類聚合物的重量平均分子量優選為約35萬~約100萬,更優選約45萬~約80萬。The acrylic polymer can be obtained by polymerizing a single monomer or a mixture of two or more monomers. The polymerization can also be carried out by any means such as solution polymerization (for example, radical polymerization, anionic polymerization, cationic polymerization, etc.), emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization (for example, ultraviolet (UV) polymerization, etc.). From the viewpoint of preventing contamination of a clean adherend or the like, the content of the low molecular weight substance is preferably small. From this point of view, the weight average molecular weight of the acrylic polymer is preferably from about 350,000 to about 1,000,000, more preferably from about 450,000 to about 800,000.
另外,為了提高作為基礎聚合物的丙烯酸類聚合物等的重量平均分子量,所述第二粘合劑層13中也可以適當使用外部交聯劑。作為外部交聯方法的具體手段,可以列舉:添加多異氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺類交聯劑等所謂的交聯劑進行反應的方法。使用外部交聯劑的情況下,其使用量根據與欲交聯的基礎聚合物的平衡以及作為粘合劑的使用用途進行適當確定。一般相對於所述基礎聚合物100重量份優選10重量份以下,更優選0.1重量份~8重量份。另外,粘合劑中根據需要除所述成分之外還可以使用各種增粘劑、抗老化劑等添加劑。Further, in order to increase the weight average molecular weight of the acrylic polymer or the like as the base polymer, an external crosslinking agent may be suitably used in the second pressure-sensitive adhesive layer 13. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound or a melamine crosslinking agent to carry out a reaction. In the case of using an external crosslinking agent, the amount thereof to be used is appropriately determined depending on the balance with the base polymer to be crosslinked and the use as a binder. It is preferably 10 parts by weight or less, more preferably 0.1 parts by weight to 8 parts by weight, per 100 parts by weight of the base polymer. Further, in the binder, various additives such as a tackifier or an anti-aging agent may be used in addition to the components as needed.
作為配合的所述紫外線固化性單體成分,可以列舉例如:胺甲酸酯低聚物、胺甲酸酯(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。另外,紫外線固化性的低聚物成分可以列舉:胺甲酸酯(urethane)類、聚醚類、聚酯類、聚碳酸酯類、聚丁二烯類等各種低聚物,其重量平均分子量在約100~約30000的範圍內的低聚物是適合的。紫外線固化性的單體成分或低聚物成分的配合量可以根據所述第二粘合劑層13的種類適當確定能夠降低粘合力的量。一般而言,相對於構成粘合劑的丙烯酸類聚合物等基礎聚合物100重量份,例如優選在約5重量份~約500重量份的範圍內,更優選約40重量份~約150重量份。Examples of the ultraviolet curable monomer component to be blended include a urethane oligomer, a urethane (meth) acrylate, a trimethylolpropane tri(meth) acrylate, and a tetrahydroxy group. Methyl methane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , 1,4-butanediol di(meth)acrylate, and the like. Further, examples of the ultraviolet curable oligomer component include various oligomers such as urethanes, polyethers, polyesters, polycarbonates, and polybutadienes, and the weight average molecular weight thereof. Oligomers in the range of from about 100 to about 30,000 are suitable. The blending amount of the ultraviolet curable monomer component or the oligomer component can be appropriately determined according to the type of the second pressure-sensitive adhesive layer 13 to reduce the adhesive strength. In general, it is preferably in the range of about 5 parts by weight to about 500 parts by weight, more preferably about 40 parts by weight to about 150 parts by weight, based on 100 parts by weight of the base polymer such as an acrylic polymer constituting the binder. .
另外,作為輻射線固化型粘合劑,除了前面說明過的添加型輻射線固化型粘合劑以外,還可以列舉使用在聚合物側鏈或主鏈中或者主鏈末端具有碳碳雙鍵的聚合物作為基礎聚合物的內在型輻射線固化型粘合劑。內在型輻射線固化型粘合劑,不必含有為低分子量成分的低聚物成分等或者含量不多,因此低聚物成分不會隨時間推移在粘合劑中遷移,可以形成穩定的層結構的第二粘合劑層13,因此優選。Further, as the radiation curable pressure-sensitive adhesive, in addition to the addition type radiation-curable pressure-sensitive adhesive described above, it is also possible to use a carbon-carbon double bond in a polymer side chain or a main chain or at a main chain terminal. An intrinsic radiation curable adhesive with a polymer as the base polymer. The intrinsic type radiation-curable adhesive does not need to contain an oligomer component or the like which is a low molecular weight component, or has a small content, so that the oligomer component does not migrate in the binder over time, and a stable layer structure can be formed. The second adhesive layer 13 is therefore preferred.
所述具有碳碳雙鍵的基礎聚合物,可以沒有特別限制地使用具有碳碳雙鍵並且具有粘合性的基礎聚合物。作為這樣的基礎聚合物,優選以丙烯酸類聚合物為基本骨架的基礎聚合物。作為丙烯酸類聚合物的基本骨架,可以列舉所述例示的(甲基)丙烯酸類聚合物。The base polymer having a carbon-carbon double bond can be a base polymer having a carbon-carbon double bond and having adhesiveness without particular limitation. As such a base polymer, a base polymer having an acrylic polymer as a basic skeleton is preferable. The basic skeleton of the acrylic polymer may, for example, be the above-exemplified (meth)acrylic polymer.
在所述丙烯酸類聚合物中引入碳碳雙鍵的方法沒有特別限制,可以採用各種方法,從分子設計方面而言在聚合物側鏈中引入碳碳雙鍵是容易的。例如可以列舉例如:預先將具有官能團的單體與丙烯酸類聚合物共聚後,使具有能夠與該官能團反應的官能團及碳碳雙鍵的化合物在保持碳碳雙鍵的紫外線固化性的情況下與所得共聚物進行縮合或加成反應的方法。The method of introducing the carbon-carbon double bond in the acrylic polymer is not particularly limited, and various methods can be employed, and it is easy to introduce a carbon-carbon double bond in the polymer side chain from the viewpoint of molecular design. For example, when a monomer having a functional group is copolymerized with an acrylic polymer in advance, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is maintained in the ultraviolet curable property of maintaining a carbon-carbon double bond. The obtained copolymer is subjected to a condensation or addition reaction.
作為這些官能團的組合例,可以列舉:羧酸基與環氧基、羧酸基與氮丙啶基、羥基與異氰酸酯基等。這些官能團的組合中,從容易跟蹤反應的觀點考慮,優選羥基與異氰酸酯基的組合。另外,如果是通過這些官能團的組合生成所述具有碳碳雙鍵的(甲基)丙烯酸類聚合物的組合,則官能團可以在丙烯酸類聚合物和所述化合物的任意一個上,在為所述優選組合的情況下,優選丙烯酸類聚合物具有羥基、所述化合物具有異氰酸酯基。此時,作為具有碳碳雙鍵的異氰酸酯化合物,可以列舉例如:甲基丙烯醯異氰酸酯、2-甲基丙烯醯氧乙基異氰酸酯、間異丙烯基-α,α-二甲基苄基異氰酸酯等。另外,作為丙烯酸類聚合物,可以使用將所述例示的含羥基單體或2-羥基乙基乙烯基醚、4-羥基丁基乙烯基醚、二乙二醇單乙烯基醚這樣的醚類化合物等共聚而得到的(甲基)丙烯酸類聚合物。Examples of the combination of these functional groups include a carboxylic acid group and an epoxy group, a carboxylic acid group and an aziridine group, a hydroxyl group and an isocyanate group. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferred from the viewpoint of easily tracking the reaction. Further, if a combination of the (meth)acrylic polymer having a carbon-carbon double bond is produced by a combination of these functional groups, the functional group may be on any one of the acrylic polymer and the compound, In the case of a preferred combination, it is preferred that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryl oxime isocyanate, 2-methacryl oxirane ethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. . Further, as the acrylic polymer, an ether such as the above-exemplified hydroxyl group-containing monomer or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or diethylene glycol monovinyl ether can be used. A (meth)acrylic polymer obtained by copolymerization of a compound or the like.
所述內在型紫外線固化型粘合劑,可以單獨使用所述具有碳碳雙鍵的基礎聚合物(特別是丙烯酸類聚合物),也可以在不損害特性的範圍內配合所述紫外線固化性的單體成分或低聚物成分。紫外線固化性的低聚物成分等通常相對於基礎聚合物100重量份在30重量份的範圍內,優選0重量份~10重量份的範圍內。The intrinsic type ultraviolet curable adhesive may be a base polymer (especially an acrylic polymer) having a carbon-carbon double bond, or may be blended with the ultraviolet curable property within a range not impairing properties. Monomer component or oligomer component. The ultraviolet curable oligomer component or the like is usually in the range of 30 parts by weight, preferably 0 parts by weight to 10 parts by weight, per 100 parts by weight of the base polymer.
在通過紫外線等固化時,所述紫外線固化型粘合劑中含有光聚合引發劑。作為光聚合引發劑,可以列舉例如:4-(2-羥基乙氧基)苯基-(2-羥基-2-丙基)酮、α-羥基-α,α’-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮等α-酮醇類化合物;甲氧基苯乙酮、2,2’-二甲氧基-2-苯基苯乙酮、2,2’-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)苯基]-2-(N-嗎啉基)丙烷-1-酮等苯乙酮類化合物;苯偶姻***、苯偶姻異丙醚、茴香偶姻甲醚等苯偶姻醚類化合物;聯苯醯二甲基縮酮等縮酮類化合物;2-萘磺醯氯等芳香族磺醯氯類化合物;1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟等光活性肟類化合物;二苯甲酮、苯甲醯基苯甲酸、3,3’-二甲基-4-甲氧基二苯甲酮等二苯甲酮類化合物;噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮類化合物;樟腦醌;鹵代酮;醯基氧化膦;醯基膦酸酯等。光聚合引發劑的配合量相對於構成粘合劑的(甲基)丙烯酸類聚合物等基礎聚合物100重量份例如為約0.05重量份~約20重量份。When curing by ultraviolet rays or the like, the ultraviolet curable pressure-sensitive adhesive contains a photopolymerization initiator. The photopolymerization initiator may, for example, be 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one or α-hydroxy-α,α'-dimethylacetophenone. , α-keto alcohol compounds such as 2-methyl-2-hydroxypropiophenone and 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2'-dimethoxy-2-phenylbenzene Ethyl ketone, 2,2'-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-(N-morpholinyl)propan-1-one, etc. Acetophenone compounds; benzoin ethyl ether, benzoin isopropyl ether, fenthene methyl ether and other benzoin ether compounds; biphenyl dimethyl ketal and other ketal compounds; 2-naphthoquinone An aromatic sulfonium chloride compound such as chlorine; a photoactive quinone compound such as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) hydrazine; benzophenone or benzamidine a benzophenone compound such as benzoic acid or 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like Tons of ketones; camphorquinone; halogenated ketone; Phosphine; fluorenylphosphonate. The blending amount of the photopolymerization initiator is, for example, about 0.05 part by weight to about 20 parts by weight based on 100 parts by weight of the base polymer such as a (meth)acrylic polymer constituting the binder.
另外,作為紫外線固化型粘合劑,可以列舉例如:日本特開昭60-196956號公報中公開的、包含具有兩個以上不飽合鍵的加聚性化合物、具有環氧基的烷氧基矽烷等光聚合性化合物和羰基化合物、有機硫化合物、過氧化物、胺、鎓鹽(onium salt)類化合物等光聚合引發劑的丙烯酸類粘合劑等。另外,在照射輻射線時,在氧引起阻礙固化的情況下,優選從輻射線固化型第二粘合劑層13的表面隔絕氧(空氣)。其方法可以列舉例如:用隔片將所述第二粘合劑層13的表面覆蓋的方法或者在氮氣氛圍中進行紫外線等輻射線的照射的方法等。In addition, examples of the ultraviolet-curable pressure-sensitive adhesive include an addition-polymerizable compound having two or more unsaturated bonds and an alkoxydecane having an epoxy group, which is disclosed in JP-A-60-196956. An acrylic binder such as a photopolymerization initiator such as a photopolymerizable compound and a carbonyl compound, an organic sulfur compound, a peroxide, an amine or an onium salt compound. Further, in the case where the radiation is irradiated, it is preferable to isolate oxygen (air) from the surface of the radiation-curable second pressure-sensitive adhesive layer 13 in the case where oxygen causes hindered solidification. The method may, for example, be a method of covering the surface of the second pressure-sensitive adhesive layer 13 with a separator or a method of irradiating radiation such as ultraviolet rays in a nitrogen atmosphere.
第二粘合劑層13的厚度沒有特別限制,從防止晶片切割面缺口或膠粘劑層14的固定保持、減少切削屑的觀點考慮,優選約10μm~約100μm,更優選15μm~80μm,進一步優選20μm~50μm。另外,第二粘合劑層13可以是單層或者多層。The thickness of the second pressure-sensitive adhesive layer 13 is not particularly limited, and is preferably from about 10 μm to about 100 μm, more preferably from 15 μm to 80 μm, further preferably from 20 μm, from the viewpoint of preventing chip cut surface notch or fixing of the adhesive layer 14 and reducing chipping. ~50μm. In addition, the second adhesive layer 13 may be a single layer or a plurality of layers.
第二粘合劑層13的剪切儲能模量在23℃和150℃下優選為5×104 Pa~1×1010 Pa,更優選1×105 Pa~1×108 Pa。剪切儲能模量低於5×104 Pa時,有時第二粘合劑層13與膠粘劑層14的剝離變得困難。另一方面,剪切儲能模量超過1×1010 Pa時,有時第二粘合劑層13與膠粘劑層14之間的密合性下降。第二粘合劑層13的剪切儲能模量是通過如下方法得到的值。即,首先將粘合劑層成形為厚約1.5mm、直徑7.9mm的圓筒狀。然後,使用Rheometric Scientific公司製造的ARES粘彈性測定裝置作為動態粘彈性測定裝置,將第二粘合劑層13安裝到平行板夾具上,在剪切模式施加應變0.1%(23℃)、0.3%(150℃)、頻率1Hz的剪切應變,同時使溫度以5℃/分鐘的升溫速度在23℃至150℃的溫度範圍變化。通過測定此時的彈性模量,可以得到23℃和150℃下的剪切儲能模量。另外,第二粘合劑層13為輻射線固化型的情況下,所述剪切儲能模量的值為輻射線固化後的值。另外,剪切儲能模量例如可以通過添加外部交聯劑來適當調節。The shear storage modulus of the second adhesive layer 13 is preferably 5 × 10 4 Pa to 1 × 10 10 Pa at 23 ° C and 150 ° C, more preferably 1 × 10 5 Pa to 1 × 10 8 Pa. When the shear storage modulus is less than 5 × 10 4 Pa, peeling of the second pressure-sensitive adhesive layer 13 from the adhesive layer 14 may become difficult. On the other hand, when the shear storage modulus exceeds 1 × 10 10 Pa, the adhesion between the second pressure-sensitive adhesive layer 13 and the pressure-sensitive adhesive layer 14 may be lowered. The shear storage modulus of the second adhesive layer 13 is a value obtained by the following method. That is, first, the pressure-sensitive adhesive layer was formed into a cylindrical shape having a thickness of about 1.5 mm and a diameter of 7.9 mm. Then, using the ARES viscoelasticity measuring apparatus manufactured by Rheometric Scientific Co., Ltd. as a dynamic viscoelasticity measuring device, the second adhesive layer 13 was attached to the parallel plate jig, and strain was applied in a shear mode by 0.1% (23 ° C), 0.3%. (150 ° C), shear strain at a frequency of 1 Hz, while changing the temperature at a temperature increase rate of 5 ° C / min in the temperature range of 23 ° C to 150 ° C. The shear storage modulus at 23 ° C and 150 ° C can be obtained by measuring the elastic modulus at this time. Further, in the case where the second pressure-sensitive adhesive layer 13 is of a radiation curing type, the value of the shear storage modulus is a value after radiation curing. In addition, the shear storage modulus can be appropriately adjusted, for example, by adding an external crosslinking agent.
第二粘合劑層13與膠粘劑層14的粘貼面的表面自由能優選為30mJ/m2 以下,更優選1mJ/m2 ~30mJ/m2 ,進一步優選15mJ/m2 ~30mJ/m2 ,特別優選20mJ/m2 ~28mJ/m2 。表面自由能超過30mJ/m2 時,第二粘合劑層13對於膠粘劑層14的膠粘性過大,有時拾取性下降。另外,第二粘合劑層前驅物與膠粘劑層14的粘貼面的表面自由能優選為30mJ/m2 以下,更優選1mJ/m2 ~30mJ/m2 ,進一步優選15mJ/m2 ~30mJ/m2 ,特別優選20mJ/m2 ~28mJ/m2 。表面自由能超過30mJ/m2 時,第二粘合劑層13對於膠粘劑層14的膠粘性過大,有時拾取性下降。第二粘合劑層13或第二粘合劑層前驅物的表面自由能,例如可以通過添加外部交聯劑適當調節。另外,表面自由能可以通過以下方法計算。即,對於第二粘合劑層13的表面,使用水及二碘甲烷分別測定接觸角(θ(rad))。然後,使用該測定值及文獻記載的接觸角測定液體的表面自由能值,由下式計算表面自由能(γs )。The surface free energy of the bonding surface of the second pressure-sensitive adhesive layer 13 and the pressure-sensitive adhesive layer 14 is preferably 30 mJ/m 2 or less, more preferably 1 mJ/m 2 to 30 mJ/m 2 , still more preferably 15 mJ/m 2 to 30 mJ/m 2 , It is particularly preferably 20 mJ/m 2 to 28 mJ/m 2 . When the surface free energy exceeds 30 mJ/m 2 , the adhesiveness of the second pressure-sensitive adhesive layer 13 to the adhesive layer 14 is excessively large, and the pick-up property may be lowered. Further, the surface free energy of the bonding surface of the second pressure-sensitive adhesive layer precursor and the pressure-sensitive adhesive layer 14 is preferably 30 mJ/m 2 or less, more preferably 1 mJ/m 2 to 30 mJ/m 2 , still more preferably 15 mJ/m 2 to 30 mJ/ m 2 is particularly preferably 20 mJ/m 2 to 28 mJ/m 2 . When the surface free energy exceeds 30 mJ/m 2 , the adhesiveness of the second pressure-sensitive adhesive layer 13 to the adhesive layer 14 is excessively large, and the pick-up property may be lowered. The surface free energy of the second adhesive layer 13 or the second adhesive layer precursor can be appropriately adjusted, for example, by adding an external crosslinking agent. In addition, the surface free energy can be calculated by the following method. That is, the contact angle (θ(rad)) was measured for each surface of the second pressure-sensitive adhesive layer 13 using water and diiodomethane. Then, the surface free energy value of the liquid was measured using the measured value and the contact angle described in the literature, and the surface free energy (γ s ) was calculated from the following formula.
γs =γs d +γs p (1)γ s =γ s d +γ s p (1)
γL =γL d +γL p (2)γ L =γ L d +γ L p (2)
(1+cosθ)γL =2(γs d γL d )1/2 +2(γs p γL p )1/2 (3)(1+cosθ)γ L =2(γ s d γ L d ) 1/2 +2(γ s p γ L p ) 1/2 (3)
其中,式(1)~式(3)中的各符號分別具有如下含義。Here, each symbol in the formulas (1) to (3) has the following meanings.
θ:由水或二碘甲烷的液滴測定的接觸角(rad)θ: contact angle (rad) determined from water or droplets of diiodomethane
γs :第二粘合劑層13的表面自由能(mJ/m2 )γ s : surface free energy of the second adhesive layer 13 (mJ/m 2 )
γs d :第二粘合劑層13的表面自由能中的分散成分(mJ/m2 )γ s d : a dispersed component (mJ/m 2 ) in the surface free energy of the second adhesive layer 13
γs p :第二粘合劑層13的表面自由能中的極性成分(mJ/m2 )γ s p : polar component (mJ/m 2 ) in the surface free energy of the second adhesive layer 13
γL :水或二碘甲烷的表面自由能(mJ/m2 )γ L : surface free energy of water or diiodomethane (mJ/m 2 )
γL d :水或二碘甲烷的表面自由能中的分散成分(mJ/m2 )γ L d : dispersion component in the surface free energy of water or diiodomethane (mJ/m 2 )
γL p :水或二碘甲烷的表面自由能中的極性成分(mJ/m2 )γ L p : polar component in the surface free energy of water or diiodomethane (mJ/m 2 )
另外,文獻記載的表面自由能的值如下所述。Further, the values of the surface free energy described in the literature are as follows.
水:分散成分(γL d )21.8mJ/m2 、極性成分(γL p )51.0 mJ/m2 Water: dispersed component (γ L d ) 21.8 mJ/m 2 , polar component (γ L p ) 51.0 mJ/m 2
二碘甲烷:分散成分(γL d )49.5mJ/m2 、極性成分(γL p )1.3mJ/m2 Diiodomethane: dispersed component (γ L d ) 49.5 mJ/m 2 , polar component (γ L p ) 1.3 mJ/m 2
另外,第二粘合劑層13與膠粘劑層14的粘貼面上的水及二碘甲烷的接觸角的測定是通過以下得到的值。即,根據JIS Z8703,在溫度23±2℃、相對濕度50±5%Rh的環境下,向第二粘合劑層13的表面滴加約1μL的水(蒸餾水)或二碘甲烷的液滴。然後,使用表面接觸角計“CA-X”(FACE公司製造)在滴加30秒後通過3點法(使用平均值)測定接觸角。Further, the measurement of the contact angle between the second pressure-sensitive adhesive layer 13 and the water and methylene iodide on the surface of the adhesive layer 14 was measured by the following values. That is, according to JIS Z8703, about 1 μL of water (distilled water) or droplets of diiodomethane are dropped onto the surface of the second pressure-sensitive adhesive layer 13 in an environment of a temperature of 23 ± 2 ° C and a relative humidity of 50 ± 5% Rh. . Then, the contact angle was measured by a 3-point method (using an average value) after 30 seconds of dropping using a surface contact angle meter "CA-X" (manufactured by FACE Co., Ltd.).
另外,在不損害本發明效果的範圍內,第二粘合劑層13中也可以包含各種添加劑(例如,著色劑、增稠劑、增量劑、填充劑、增粘劑、增塑劑、抗老化劑、抗氧化劑、表面活性劑、交聯劑等)。Further, the second adhesive layer 13 may contain various additives (for example, a colorant, a thickener, a bulking agent, a filler, a tackifier, a plasticizer, or the like) within a range not impairing the effects of the present invention. Anti-aging agents, antioxidants, surfactants, cross-linking agents, etc.).
將基材層11、第一粘合劑層12和第二粘合劑層13堆疊而成的結構物,藉由E×I計算的彎曲剛性S優選在5.0×104 ~7.0×105 的範圍內(其中,I為以b×T3 /12表示的截面二次矩,b為所述結構物的試驗片的寬度10(mm),T為所述結構物的厚度(mm),E為所述結構物的25℃下的拉伸儲能彈性模量(Pa))。所述彎曲剛性S更優選在6.0×104 ~6.0×105 的範圍內,進一步優選在7.0×104 ~5.0×105 的範圍內。通過將所述彎曲剛性S設定為5.0×104 以上,可以保持所述結構物的剛性,在晶片粘貼時可以在不產生褶折的情況下進行粘貼。另一方面,通過將所述彎曲剛性S設定為7.0×105 以下,在拾取時所述結構物恰當地彎曲,能夠實現穩定的拾取。在此,所述結構物的25℃下的拉伸彈性模量(Pa)是使用動態粘彈性測定裝置(RSA-III,Rheometrics Scientific公司製造)以5℃/分鐘進行升溫測定得到的值。The structure in which the base material layer 11, the first pressure-sensitive adhesive layer 12, and the second pressure-sensitive adhesive layer 13 are stacked, the bending rigidity S calculated by E × I is preferably 5.0 × 10 4 to 7.0 × 10 5 In the range (where I is the second moment of the section indicated by b×T 3 /12, b is the width of the test piece of the structure of 10 (mm), and T is the thickness (mm) of the structure, E It is the tensile storage elastic modulus (Pa) at 25 ° C of the structure. The bending rigidity S is more preferably in the range of 6.0 × 10 4 to 6.0 × 10 5 , still more preferably in the range of 7.0 × 10 4 to 5.0 × 10 5 . By setting the bending rigidity S to 5.0 × 10 4 or more, the rigidity of the structure can be maintained, and when the wafer is pasted, the bonding can be performed without wrinkles. On the other hand, by setting the bending rigidity S to 7.0 × 10 5 or less, the structure is appropriately bent at the time of picking up, and stable pickup can be realized. Here, the tensile elastic modulus (Pa) at 25 ° C of the structure is a value obtained by measuring the temperature at 5 ° C /min using a dynamic viscoelasticity measuring apparatus (RSA-III, manufactured by Rheometrics Scientific Co., Ltd.).
[膠粘劑層][Adhesive layer]
膠粘劑層14設置在第二粘合劑層13上,是對半導體晶片等具有膠粘功能的層。如圖2所示,圓形的第二粘合劑層13設置於第一粘合劑層12上的切割環粘貼部分18的內側的情況下,優選膠粘劑層14的平面形狀也為圓形,並且相對於第二粘合劑層13的中心設置在基本成為同心圓的位置。另外,優選膠粘劑層14的平面形狀大於第二粘合劑層13,並且以覆蓋整個第二粘合劑層13的方式設置。由此,膠粘劑層14的周邊部14a(圖2中的斜線部區域)可以層疊在第一粘合劑層12上。如果是這樣的層疊結構,則得到膠粘劑層14的周邊部不是在輕易剝離的第二粘合劑層13上而是在第一粘合劑層12上牢固地膠粘的結構。結果,例如,切割時可以防止膠粘劑層14從第二粘合劑層13上剝離而產生捲縮。The adhesive layer 14 is provided on the second adhesive layer 13, and is a layer having an adhesive function to a semiconductor wafer or the like. As shown in FIG. 2, in the case where the circular second adhesive layer 13 is provided on the inner side of the cut ring pasting portion 18 on the first adhesive layer 12, it is preferable that the planar shape of the adhesive layer 14 is also circular. Further, it is disposed at a position substantially concentric with respect to the center of the second adhesive layer 13. Further, it is preferable that the planar shape of the adhesive layer 14 is larger than that of the second adhesive layer 13, and is provided so as to cover the entire second adhesive layer 13. Thereby, the peripheral portion 14a (the hatched portion region in FIG. 2) of the adhesive layer 14 can be laminated on the first adhesive layer 12. In the case of such a laminated structure, the peripheral portion of the adhesive layer 14 is obtained not to be adhered to the second adhesive layer 13 which is easily peeled off but to be firmly adhered to the first adhesive layer 12. As a result, for example, the adhesive layer 14 can be prevented from being peeled off from the second adhesive layer 13 at the time of cutting to cause curling.
作為膠粘劑層14的構成材料,可以列舉將熱塑性樹脂和熱固性樹脂併用的材料。另外,熱塑性樹脂或熱固性樹脂也可以單獨使用。另外,膠粘劑層14的層疊結構沒有特別限制,例如可以列舉:僅由單層構成的結構,或者在芯材的單面或兩面上形成膠粘劑層的多層結構的結構。作為所述芯材,可以列舉薄膜(例如,聚醯亞胺薄膜、聚酯薄膜、聚對苯二甲酸乙二醇酯薄膜、聚萘二甲酸乙二醇酯薄膜、聚碳酸酯薄膜等)、由玻璃纖維或塑膠制無紡纖維增強的樹脂基板、矽基板或玻璃基板等。The constituent material of the adhesive layer 14 is a material in which a thermoplastic resin and a thermosetting resin are used in combination. Further, a thermoplastic resin or a thermosetting resin can also be used alone. Further, the laminated structure of the adhesive layer 14 is not particularly limited, and examples thereof include a structure composed of only a single layer, or a structure having a multilayer structure in which an adhesive layer is formed on one surface or both surfaces of a core material. Examples of the core material include a film (for example, a polyimide film, a polyester film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, etc.), A resin substrate reinforced by a glass fiber or a non-woven fabric made of plastic, a ruthenium substrate, a glass substrate, or the like.
作為所述熱塑性樹脂,可以列舉天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、尼龍6或尼龍6,6等聚醯胺樹脂、苯氧基樹脂、丙烯酸類樹脂、PET或PBT等飽和聚酯樹脂、聚醯胺醯亞胺樹脂或者含氟樹脂等。這些熱塑性樹脂可以單獨使用或者兩種以上組合使用。這些熱塑性樹脂中,特別優選離子性雜質少、耐熱性高、能夠確保半導體元件的可靠性的丙烯酸類樹脂。Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutadiene. Resin, polycarbonate resin, thermoplastic polyimide resin, nylon 6 or nylon 6,6, etc. Polyamide resin, phenoxy resin, acrylic resin, saturated polyester resin such as PET or PBT, polyamidoxime An amine resin or a fluorine-containing resin. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin having less ionic impurities, high heat resistance, and reliability of a semiconductor element can be particularly preferable.
作為所述丙烯酸類樹脂,可以列舉例如:以一種或兩種以上具有碳原子數30以下、特別是碳原子數4~18的直鏈或支鏈烷基的丙烯酸或甲基丙烯酸的酯為成分的聚合物等。作為所述烷基,可以列舉例如:甲基、乙基、丙基、異丙基、正丁基、叔丁基、異丁基、戊基、異戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基或者十二烷基等。The acrylic resin may, for example, be one or two or more esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. Polymers, etc. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, and a cyclohexyl group. 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octaalkyl or dodecyl and the like.
另外,作為形成所述聚合物的其他單體,沒有特別限制,可以列舉例如:丙烯酸、甲基丙烯酸、丙烯酸羧乙酯、丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸或巴豆酸等含羧基單體;馬來酸酐或衣康酸酐等酸酐單體;(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-10-羥基癸酯、(甲基)丙烯酸-12-羥基月桂酯或丙烯酸(4-羥甲基環己基)甲酯等含羥基單體;苯乙烯磺酸、烯丙磺酸、2-(甲基)丙烯醯胺基-2-甲基丙磺酸、(甲基)丙烯醯胺基丙磺酸、(甲基)丙烯酸磺丙酯或(甲基)丙烯醯氧基萘磺酸等含磺酸基單體;或者丙烯醯磷酸-2-羥基乙酯等含磷酸基單體。這些物質可以單獨使用或者可以兩種以上組合使用。Further, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid or croton. a carboxyl group-containing monomer such as an acid; an acid anhydride monomer such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or (meth)acrylic acid-4 -hydroxybutyl ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxyl (meth)acrylate a hydroxyl group-containing monomer such as lauryl ester or (4-hydroxymethylcyclohexyl)methyl acrylate; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylamido-2-methylpropanesulfonic acid, a sulfonic acid group-containing monomer such as (meth)acrylonitrile-propanesulfonic acid, sulfopropyl (meth)acrylate or (meth)acryloxynaphthalenesulfonic acid; or 2-hydroxyethyl phthalate Such as a phosphate-containing monomer. These may be used singly or in combination of two or more.
另外,作為所述丙烯酸類樹脂,優選丙烯酸類共聚物。作為該丙烯酸類共聚物中使用的單體成分沒有特別限制,可以列舉例如:丙烯酸丁酯、丙烯酸乙酯等。本發明中,優選相對於全部單體成分包含10重量%~60重量%範圍內的丙烯酸丁酯和40重量%~90重量%範圍內的丙烯酸乙酯而構成的共聚物。Further, as the acrylic resin, an acrylic copolymer is preferred. The monomer component used in the acrylic copolymer is not particularly limited, and examples thereof include butyl acrylate and ethyl acrylate. In the present invention, a copolymer composed of butyl acrylate in the range of 10% by weight to 60% by weight and ethyl acrylate in the range of 40% by weight to 90% by weight based on all the monomer components is preferably used.
另外,作為可以與所述單體成分共聚的其他單體成分沒有特別限制,可以列舉例如丙烯腈等。這些可共聚的單體成分的使用量,相對於全部單體成分優選在1重量%~20重量%的範圍內。通過含有該數值範圍內的其他單體成分,可以改變凝聚力、膠粘性等。Further, the other monomer component copolymerizable with the monomer component is not particularly limited, and examples thereof include acrylonitrile. The amount of these copolymerizable monomer components used is preferably in the range of 1% by weight to 20% by weight based on the total of the monomer components. Cohesive force, adhesiveness, and the like can be changed by including other monomer components within the range of values.
作為丙烯酸類共聚物的聚合方法,沒有特別限制,可以採用例如:溶液聚合法、本體聚合法、懸浮聚合法、乳液聚合法等現有公知的方法。The polymerization method of the acrylic copolymer is not particularly limited, and conventionally known methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method can be employed.
所述丙烯酸類共聚物的玻璃化轉變溫度(Tg)優選為-30℃~10℃,更優選-25℃~8℃。通過將所述玻璃化轉變溫度設定為-30℃以上,可以確保膠粘劑層14的高溫時(例如,100℃~200℃)的儲能彈性模量。另一方面,通過設定為10℃以下,可以對半導體晶片表現出良好的密合性、緊貼性。The glass transition temperature (Tg) of the acrylic copolymer is preferably from -30 ° C to 10 ° C, more preferably from -25 ° C to 8 ° C. By setting the glass transition temperature to -30 ° C or higher, the storage elastic modulus of the adhesive layer 14 at a high temperature (for example, 100 ° C to 200 ° C) can be ensured. On the other hand, by setting it as 10 ° C or less, it can exhibit favorable adhesiveness and adhesiveness with respect to a semiconductor wafer.
所述丙烯酸類共聚物的重量平均分子量優選為10萬以上,更優選60萬~120萬,特別優選70萬~100萬。通過將重量平均分子量設定為10萬以上,對佈線基板等被粘物或半導體元件、半導體晶片表面的高溫時的膠粘性優良,並且可以提高耐熱性。另外,通過將重量平均分子量設定為120萬以下,可以容易地溶於有機溶劑。重量平均分子量是通過凝膠滲透色譜法(GPC),使用標準聚苯乙烯的校準曲線的聚苯乙烯換算值。The weight average molecular weight of the acrylic copolymer is preferably 100,000 or more, more preferably 600,000 to 1,200,000, and particularly preferably 700,000 to 1,000,000. By setting the weight average molecular weight to 100,000 or more, the adhesion of the adherend such as a wiring board or the semiconductor element or the surface of the semiconductor wafer at a high temperature is excellent, and heat resistance can be improved. Further, by setting the weight average molecular weight to 1.2 million or less, it can be easily dissolved in an organic solvent. The weight average molecular weight is a polystyrene equivalent value by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene.
作為所述熱固性樹脂,可以列舉酚醛樹脂、氨基樹脂、不飽和聚酯樹脂、環氧樹脂、聚氨酯樹脂、矽樹脂(silicone樹脂)或熱固性聚醯亞胺樹脂等。這些樹脂可以單獨使用或者兩種以上組合使用。特別是優選腐蝕半導體元件的離子性雜質的含量少的環氧樹脂。另外,作為環氧樹脂的固化劑,優選酚醛樹脂。Examples of the thermosetting resin include a phenol resin, an amino resin, an unsaturated polyester resin, an epoxy resin, a urethane resin, a silicone resin, or a thermosetting polyimide resin. These resins may be used singly or in combination of two or more. In particular, an epoxy resin having a small content of ionic impurities that etch the semiconductor element is preferable. Further, as the curing agent for the epoxy resin, a phenol resin is preferred.
所述環氧樹脂,如果是一般作為膠粘劑組合物使用的環氧樹脂則沒有特別限制,可以使用例如:雙酚A型、雙酚F型、雙酚S型、溴化雙酚A型、氫化雙酚A型、雙酚AF型、聯苯型、萘型、芴型、苯酚酚醛清漆型、鄰甲酚酚醛清漆型、三羥苯基甲烷型、四羥苯基乙烷型等雙官能環氧樹脂或多官能環氧樹脂、或者乙內醯脲型、異氰脲酸三縮水甘油酯型或者縮水甘油胺型環氧樹脂。這些物質可以單獨使用或者兩種以上組合使用。這些環氧樹脂中,特別優選酚醛清漆型環氧樹脂、聯苯型環氧樹脂、三羥苯基甲烷型環氧樹脂或四羥苯基乙烷型環氧樹脂。這是因為:這些環氧樹脂與作為固化劑的酚醛樹脂的反應性高,並且耐熱性等優良。另外,環氧樹脂中腐蝕半導體元件的離子性雜質等的含量少。The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenation can be used. Bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, anthraquinone type, phenol novolac type, o-cresol novolac type, trishydroxyphenylmethane type, tetrahydroxyphenylethane type, etc. An oxy resin or a polyfunctional epoxy resin, or a carbendazole type, an isocyanuric acid triglycidyl ester type or a glycidylamine type epoxy resin. These may be used singly or in combination of two or more. Among these epoxy resins, a novolac type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type epoxy resin or a tetrahydroxyphenylethane type epoxy resin is particularly preferable. This is because these epoxy resins have high reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like. Further, the content of ionic impurities or the like which etch the semiconductor element in the epoxy resin is small.
另外,所述酚醛樹脂作為所述環氧樹脂的固化劑起作用,可以列舉例如:苯酚酚醛清漆樹脂、苯酚芳烷基樹脂、甲酚酚醛清漆酚醛樹脂、叔丁基苯酚酚醛清漆樹脂、壬基苯酚酚醛清漆樹脂等酚醛清漆型酚醛樹脂、可溶酚醛樹脂(resol)型酚醛樹脂、聚對羥基苯乙烯等聚羥基苯乙烯等。這些物質可以單獨使用或者兩種以上組合使用。這些酚醛樹脂中,優選下述化學式表示的聯苯型苯酚酚醛清漆樹脂或苯酚芳烷基樹脂。這是因為可以改善半導體裝置的連接可靠性。Further, the phenol resin acts as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolac phenol resin, a t-butyl phenol novolak resin, and a mercapto group. A novolac type phenol resin such as a phenol novolak resin, a resol type phenol resin, or a polyhydroxy styrene such as polyparaxyl styrene. These may be used singly or in combination of two or more. Among these phenol resins, a biphenyl type phenol novolak resin or a phenol aralkyl resin represented by the following chemical formula is preferable. This is because the connection reliability of the semiconductor device can be improved.
(所述n為0~10的自然數)。(The n is a natural number from 0 to 10).
另外,所述n優選為0~10的自然數,更優選0~5的自然數。通過在所述數值範圍內,可以確保膠粘劑層14的流動性。Further, the n is preferably a natural number of 0 to 10, and more preferably a natural number of 0 to 5. By being within the stated range, the fluidity of the adhesive layer 14 can be ensured.
所述環氧樹脂與酚醛樹脂的配合比例,例如,以所述酚醛樹脂中的羥基相對於所述環氧樹脂成分中的環氧基1當量為0.5當量~2.0當量的方式進行配合是優選的。另外,更優選0.8當量~1.2當量。即,這是因為:兩者的配合比例在所述範圍以外時,不能進行充分的固化反應,從而環氧樹脂固化物的特性易於劣化。The mixing ratio of the epoxy resin to the phenol resin is preferably, for example, such that the hydroxyl group in the phenol resin is 0.5 equivalent to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. . Further, it is more preferably 0.8 equivalents to 1.2 equivalents. That is, this is because when the mixing ratio of the two is outside the above range, a sufficient curing reaction cannot be performed, and the properties of the cured epoxy resin are liable to deteriorate.
另外,本發明中,特別優選使用環氧樹脂、酚醛樹脂和丙烯酸類樹脂的膠粘劑層。這些樹脂中的離子性雜質少、耐熱性高,因此可以確保半導體元件的可靠性。此時的配合比,相對於100重量份丙烯酸類樹脂成份,環氧樹脂與酚醛樹脂的混合量為10重量份~200重量份。Further, in the present invention, an adhesive layer of an epoxy resin, a phenol resin, and an acrylic resin is particularly preferably used. Since these resins have few ionic impurities and high heat resistance, the reliability of the semiconductor element can be ensured. In the mixing ratio at this time, the amount of the epoxy resin and the phenol resin is from 10 parts by weight to 200 parts by weight based on 100 parts by weight of the acrylic resin component.
預先對本發明的膠粘劑層14進行某種程度地交聯的情況下,在製作時添加與聚合物的分子鏈末端的官能團等反應的多官能化合物作為交聯劑就可以。由此,可以提高高溫下的膠粘特性,改善耐熱性。When the adhesive layer 14 of the present invention is crosslinked to some extent in advance, a polyfunctional compound which reacts with a functional group at the end of the molecular chain of the polymer or the like may be added as a crosslinking agent at the time of production. Thereby, the adhesive property at a high temperature can be improved and the heat resistance can be improved.
作為所述交聯劑,特別是更優選甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、對苯二異氰酸酯、1,5-萘二異氰酸酯、多元醇與二異氰酸酯的加成物等多異氰酸酯化合物。交聯劑的添加量,相對於所述聚合物100重量份,通常優選0.05重量份~7重量份。交聯劑的量超過7重量份時,膠粘力下降,因此不優選。另一方面,低於0.05重量份時,凝聚力不足,因此不優選。另外,根據需要,也可以與這樣的多異氰酸酯化合物一起含有環氧樹脂等其他多官能化合物。As the crosslinking agent, a polyisocyanate compound such as toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, or an adduct of a polyhydric alcohol and a diisocyanate is more preferable. The amount of the crosslinking agent to be added is usually preferably 0.05 parts by weight to 7 parts by weight based on 100 parts by weight of the polymer. When the amount of the crosslinking agent exceeds 7 parts by weight, the adhesive strength is lowered, which is not preferable. On the other hand, when it is less than 0.05 part by weight, the cohesive force is insufficient, which is not preferable. Further, other polyfunctional compounds such as an epoxy resin may be contained together with such a polyisocyanate compound as needed.
另外,膠粘劑層14中,可以適當配合無機填充劑。無機填充劑的配合對膠粘劑層14的表面賦予凹凸。另外,也可以賦予導電性或提高導熱性、調節儲能彈性模量等。Further, an inorganic filler may be appropriately blended in the adhesive layer 14. The blending of the inorganic filler imparts irregularities to the surface of the adhesive layer 14. Further, it is also possible to impart conductivity, improve thermal conductivity, adjust storage elastic modulus, and the like.
作為所述無機填充劑,可以列舉例如:包含二氧化矽、粘土、石膏、碳酸鈣、硫酸鋇、氧化鋁、氧化鈹、碳化矽、氮化矽等陶瓷類、鋁、銅、銀、金、鎳、鉻、鉛、錫、鋅、鈀、焊錫等金屬、或者合金類、以及碳等的各種無機粉末。這些物質可以單獨使用或者兩種以上組合使用。其中優選使用二氧化矽、特別優選使用熔融二氧化矽。Examples of the inorganic filler include ceramics such as ceria, clay, gypsum, calcium carbonate, barium sulfate, aluminum oxide, cerium oxide, cerium carbide, cerium nitride, aluminum, copper, silver, gold, and the like. Metals such as nickel, chromium, lead, tin, zinc, palladium, and solder, or various inorganic powders such as alloys and carbon. These may be used singly or in combination of two or more. Among them, cerium oxide is preferably used, and molten cerium oxide is particularly preferably used.
無機填充劑的平均粒徑優選在0.1μm~5μm的範圍內,更優選0.2μm~3μm的範圍內。無機填充劑的平均粒徑小於0.1μm時,難以使所述膠粘劑層的Ra為0.15μm以上。另一方面,所述平均粒徑超過5μm時,難以使Ra低於1μm。另外,本發明中,也可以將平均粒徑相互不同的無機填充劑之間組合使用。另外,平均粒徑是利用例如光度式粒度分佈計(HORIBA製造,裝置名LA-910)求出的值。The average particle diameter of the inorganic filler is preferably in the range of 0.1 μm to 5 μm, and more preferably in the range of 0.2 μm to 3 μm. When the average particle diameter of the inorganic filler is less than 0.1 μm, it is difficult to set Ra of the pressure-sensitive adhesive layer to 0.15 μm or more. On the other hand, when the average particle diameter exceeds 5 μm, it is difficult to make Ra less than 1 μm. Further, in the present invention, an inorganic filler having different average particle diameters may be used in combination. Further, the average particle diameter is a value obtained by, for example, a photometric particle size distribution meter (manufactured by HORIBA, device name LA-910).
所述無機填充劑的配合量,相對於有機樹脂成分100重量份優選設定為20重量份~80重量份。特別優選20重量份~70重量份。無機填充劑的配合量低於20重量份時,耐熱性下降,因此經受長時間高溫的熱歷程時,有時膠粘劑層14固化,流動性或掩埋性下降。另外,超過80重量份時,膠粘劑層14的儲能彈性模量增大。因此,有時固化的膠粘劑難以緩和應力,在密封製程中對凹凸的掩埋性下降。The amount of the inorganic filler to be added is preferably 20 parts by weight to 80 parts by weight based on 100 parts by weight of the organic resin component. It is particularly preferably 20 parts by weight to 70 parts by weight. When the amount of the inorganic filler is less than 20 parts by weight, the heat resistance is lowered. Therefore, when subjected to a heat history for a long period of time, the adhesive layer 14 may be solidified, and the fluidity or the burying property may be lowered. Further, when it exceeds 80 parts by weight, the storage elastic modulus of the adhesive layer 14 is increased. Therefore, sometimes the cured adhesive is difficult to alleviate the stress, and the burying property of the unevenness in the sealing process is lowered.
另外,膠粘劑層14中,除了所述無機填充劑以外,根據需要可以適當配合其他添加劑。作為其他添加劑,可以列舉例如:阻燃劑、矽烷偶聯劑或離子捕獲劑等。作為所述阻燃劑,可以列舉例如:三氧化二銻、五氧化二銻、溴化環氧樹脂等。這些阻燃劑可以單獨使用或者兩種以上組合使用。作為所述矽烷偶聯劑,可以列舉例如:β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷等。這些化合物可以單獨使用或者兩種以上組合使用。作為所述離子捕獲劑,可以列舉例如:水滑石類、氫氧化鉍等。這些離子捕獲劑可以單獨使用或者兩種以上組合使用。Further, in the adhesive layer 14, in addition to the inorganic filler, other additives may be appropriately blended as needed. Examples of other additives include a flame retardant, a decane coupling agent, an ion trapping agent, and the like. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. These flame retardants may be used singly or in combination of two or more. As the decane coupling agent, for example, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-epoxypropyl Oxypropylmethyldiethoxydecane, and the like. These compounds may be used singly or in combination of two or more. Examples of the ion trapping agent include hydrotalcites and barium hydroxide. These ion trapping agents may be used singly or in combination of two or more.
膠粘劑層14根據需要也可以被著色。膠粘劑層14中,通過著色而呈現的顏色沒有特別限制,優選例如:黑色、藍色、紅色、綠色等。膠粘劑層14在作為晶片接合薄膜使用時,通常不著色(但是也可以著色),在作為覆晶(flip-chip)型半導體背面用薄膜使用時,通常著色。著色時,可以從顏料、染料等公知的著色劑中適當選擇使用。The adhesive layer 14 can also be colored as needed. In the adhesive layer 14, the color which is exhibited by coloring is not particularly limited, and is preferably, for example, black, blue, red, green, or the like. When the adhesive layer 14 is used as a wafer bonding film, it is usually not colored (but may be colored), and is usually colored when used as a film for a flip-chip type semiconductor back surface. In the case of coloring, it can be suitably selected from known coloring agents such as pigments and dyes.
膠粘劑層14的厚度(層疊體的情況下為總厚度)沒有特別限制,例如,為約5μm~約100μm,優選約5μm~約50μm。The thickness of the adhesive layer 14 (the total thickness in the case of the laminate) is not particularly limited, and is, for example, about 5 μm to about 100 μm, preferably about 5 μm to about 50 μm.
另外,本發明的膠粘劑層可以作為晶片接合薄膜或者覆晶型半導體背面用薄膜使用。在此,覆晶型半導體背面用薄膜,是在通過覆晶接合方式將半導體晶片安裝到基板時用於保護半導體晶片的背面(露出的背面)的薄膜。Further, the adhesive layer of the present invention can be used as a wafer bonding film or a film for a flip chip type semiconductor back surface. Here, the film for flip chip type semiconductor back surface is a film for protecting the back surface (exposed back surface) of the semiconductor wafer when the semiconductor wafer is mounted on the substrate by flip chip bonding.
[各層間的剝離力][Peel force between layers]
所述第二粘合劑層13和膠粘劑層14之間的剝離強度X優選在0.01N/20mm~0.2N/20mm的範圍內,更優選0.015N/20mm~0.18N/20mm的範圍內。通過將所述剝離強度X設定為0.01N/20mm以上,例如在半導體晶片的切割時,可以防止兩者間產生剝離,防止產生半導體晶片的晶片飛散。另一方面,通過將所述剝離強度X設定為0.2N/20mm以下,即使省略輻射線的照射製程,也可以良好地拾取半導體晶片。The peeling strength X between the second adhesive layer 13 and the adhesive layer 14 is preferably in the range of 0.01 N/20 mm to 0.2 N/20 mm, more preferably in the range of 0.015 N/20 mm to 0.18 N/20 mm. By setting the peeling strength X to 0.01 N/20 mm or more, for example, at the time of dicing of a semiconductor wafer, peeling between the two can be prevented, and scattering of the wafer in which the semiconductor wafer is generated can be prevented. On the other hand, by setting the peeling strength X to 0.2 N/20 mm or less, even if the irradiation process of the radiation is omitted, the semiconductor wafer can be picked up favorably.
另外,所述第一粘合劑層12和第二粘合劑層13之間的剝離強度Y優選在0.2N/20mm~10N/20mm的範圍內,更優選0.3N/20mm~9.5N/20mm的範圍內。通過將所述剝離強度Y設定為0.2N/20mm以上,例如,在切割時,可以將半導體晶片或半導體晶片可靠地固定。另外,通過將所述剝離強度Y設定為10N/20mm以下,可以將第二粘合劑層13從第一粘合劑層12上剝離,可以實現作為由基材層11和第一粘合劑層構成的載帶的層疊薄膜的再利用。Further, the peeling strength Y between the first adhesive layer 12 and the second adhesive layer 13 is preferably in the range of 0.2 N/20 mm to 10 N/20 mm, more preferably 0.3 N/20 mm to 9.5 N/20 mm. In the range. By setting the peel strength Y to 0.2 N/20 mm or more, for example, at the time of dicing, the semiconductor wafer or the semiconductor wafer can be reliably fixed. Further, by setting the peeling strength Y to 10 N/20 mm or less, the second adhesive layer 13 can be peeled off from the first adhesive layer 12, and it can be realized as the base material layer 11 and the first adhesive. Recycling of a laminated film of a carrier tape composed of layers.
所述第二粘合劑層13和膠粘劑層14之間的剝離強度X與第一粘合劑層12和第二粘合劑層13之間的剝離強度Y之比(Y/X),優選在3~500的範圍內,更優選4~400的範圍內。通過將所述剝離強度X與剝離強度Y之比(Y/X)設定為3以上,可以使半導體晶片的拾取時的剝離介面為第二粘合劑層13和膠粘劑層14的邊界。另一方面,通過將所述比(Y/X)設定為500以下,可以抑制切割時的晶片飛散或膠粘劑層的捲縮,可以進行穩定的切割。The ratio (Y/X) of the peeling strength X between the second adhesive layer 13 and the adhesive layer 14 to the peel strength Y between the first adhesive layer 12 and the second adhesive layer 13 is preferably In the range of 3 to 500, more preferably in the range of 4 to 400. By setting the ratio (Y/X) of the peeling strength X to the peeling strength Y to 3 or more, the peeling interface at the time of picking up the semiconductor wafer can be made the boundary between the second adhesive layer 13 and the adhesive layer 14. On the other hand, by setting the ratio (Y/X) to 500 or less, it is possible to suppress wafer scattering at the time of dicing or curling of the adhesive layer, and stable cutting can be performed.
所述第一粘合劑層12與SUS304-BA板之間的剝離強度,優選在0.2N/20mm~11N/20mm的範圍內,更優選0.3N/20mm~9.5N/20mm的範圍內。通過將所述剝離強度設定為0.2N/20mm以上,可以將該切割環可靠地膠粘固定,良好地進行切割。另一方面,通過將所述剝離強度設定為11N/20mm以下,在將使用後的切割環從第一粘合劑層12剝離時,可以抑制在切割環上產生膠糊殘留。The peel strength between the first adhesive layer 12 and the SUS304-BA plate is preferably in the range of 0.2 N/20 mm to 11 N/20 mm, more preferably in the range of 0.3 N/20 mm to 9.5 N/20 mm. By setting the peeling strength to 0.2 N/20 mm or more, the cutting ring can be reliably adhered and fixed, and the cutting can be performed favorably. On the other hand, by setting the peeling strength to 11 N/20 mm or less, when the dicing ring after use is peeled off from the first pressure-sensitive adhesive layer 12, generation of adhesive residue on the dicing ring can be suppressed.
[隔片][bead]
所述隔片15,具有在供給實際應用之前作為保護膠粘劑層14的保護材料的功能。其中,如圖2所示,第二粘合劑層13和膠粘劑層14設置於切割環的粘貼部分18的內側的情況下,隔片15也保護第一粘合劑層12。另外,隔片15可以作為將膠粘劑層14轉印到第二粘合劑層13時的基材使用。隔片15在將半導體晶片粘貼到膠粘劑層14上時剝離。作為隔片15,也可以使用由聚對二甲酸乙二醇酯(PET)、聚乙烯、聚丙烯、以及含氟剝離劑、長鏈烷基丙烯酸酯類剝離劑等剝離劑進行表面塗布後的塑膠薄膜或紙等。The spacer 15 has a function as a protective material for protecting the adhesive layer 14 before being supplied to an actual application. Here, as shown in FIG. 2, in the case where the second adhesive layer 13 and the adhesive layer 14 are provided inside the bonding portion 18 of the dicing ring, the spacer 15 also protects the first adhesive layer 12. Further, the separator 15 can be used as a substrate when the adhesive layer 14 is transferred to the second pressure-sensitive adhesive layer 13. The spacer 15 is peeled off when the semiconductor wafer is pasted onto the adhesive layer 14. The separator 15 may be surface-coated with a release agent such as polyethylene terephthalate (PET), polyethylene, polypropylene, a fluorine-containing release agent, or a long-chain alkyl acrylate release agent. Plastic film or paper.
(半導體裝置製造用薄膜的製造方法)(Method of Manufacturing Thin Film for Semiconductor Device Manufacturing)
以下,以半導體裝置製造用薄膜1為例對本發明的半導體裝置製造用薄膜的製造方法進行說明。首先,基材層11可以通過現有公知的制膜方法製成膜。作為該制膜方法,可以例示例如:壓延制膜法、有機溶劑中的流延法、密閉體系中的吹塑擠出法、T形模頭擠出法、共擠出法、乾式層壓法等。Hereinafter, a method for producing a thin film for semiconductor device production of the present invention will be described by taking a thin film 1 for semiconductor device manufacturing as an example. First, the substrate layer 11 can be formed into a film by a conventionally known film forming method. Examples of the film forming method include a calender film forming method, a casting method in an organic solvent, a blow molding method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry lamination method. Wait.
然後,在基材層11上形成第一粘合劑層12。即,在基材層11上塗布粘合劑組合物形成塗膜後,在規定條件下使該塗膜乾燥(根據需要進行加熱交聯),從而形成第一粘合劑層12。作為塗布方法沒有特別限制,可以列舉:輥塗、絲網塗布、凹版塗布等。另外,乾燥條件可以根據塗膜的厚度或材料等進行各種設定。具體而言,例如,可以在80℃~150℃的乾燥溫度、0.5分鐘~5分鐘的乾燥時間的範圍內的條件下進行。另外,也可以在隔片上塗布粘合劑組合物形成塗膜後,在所述乾燥條件下乾燥塗膜而形成第一粘合劑層12。之後,將第一粘合劑層12轉印到基材層11上。Then, a first adhesive layer 12 is formed on the substrate layer 11. That is, after the pressure-sensitive adhesive composition is applied onto the base material layer 11 to form a coating film, the coating film is dried under predetermined conditions (heat-crosslinking if necessary) to form the first pressure-sensitive adhesive layer 12. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions can be variously set depending on the thickness of the coating film, the material, and the like. Specifically, for example, it can be carried out under the conditions of a drying temperature of 80 ° C to 150 ° C and a drying time of 0.5 minutes to 5 minutes. Alternatively, the first pressure-sensitive adhesive layer 12 may be formed by applying a pressure-sensitive adhesive composition to a separator to form a coating film, and then drying the coating film under the drying conditions. Thereafter, the first adhesive layer 12 is transferred onto the substrate layer 11.
然後,在第一粘合劑層12上形成第二粘合劑層13。即,在隔片上塗布輻射線固化型粘合劑組合物形成塗膜後,在規定條件下將該塗膜乾燥(根據需要進行加熱交聯),而形成第二粘合劑層前驅物。作為塗布方法沒有特別限制,可以列舉:輥塗、絲網塗布、凹版塗布等。另外,乾燥條件可以根據塗膜的厚度或材料等進行各種設定。具體而言,例如,可以在80℃~150℃的乾燥溫度、0.5分鐘~5分鐘的乾燥時間的範圍內的條件下進行。另外,也可以在隔片上塗布粘合劑組合物形成塗膜後,在所述乾燥條件下乾燥塗膜而形成第二粘合劑層前驅物。Then, a second adhesive layer 13 is formed on the first adhesive layer 12. That is, after the radiation-curable pressure-sensitive adhesive composition is applied onto the separator to form a coating film, the coating film is dried under predetermined conditions (heat-crosslinking if necessary) to form a second pressure-sensitive adhesive layer precursor. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions can be variously set depending on the thickness of the coating film, the material, and the like. Specifically, for example, it can be carried out under the conditions of a drying temperature of 80 ° C to 150 ° C and a drying time of 0.5 minutes to 5 minutes. Alternatively, the coating composition may be formed by applying a pressure-sensitive adhesive composition to the separator, and then drying the coating film under the drying conditions to form a second pressure-sensitive adhesive layer precursor.
對這樣形成的第二粘合劑層前驅物照射輻射線,由此形成第二粘合劑層13。使用紫外線作為輻射線的情況下,其照射條件優選使得其累積光量在50mJ/cm2 ~1000mJ/cm2 的範圍內,更優選在100mJ/cm2 ~800mJ/cm2 的範圍內。紫外線的照射低於50mJ/cm2 時,有時第二粘合劑層13的固化不充分。結果,與膠粘劑層14的密合性增大,導致拾取性下降。另外,拾取後在膠粘劑層14上產生膠糊殘留。另一方面,紫外線的照射超過1000mJ/cm2 時,第二粘合劑層13的固化過度進行,從而拉伸彈性模量過度增大,導致擴展性下降。另外,粘合力過度下降,由此,在半導體晶片的切割時,有時產生晶片飛散。The second adhesive layer precursor thus formed is irradiated with radiation, thereby forming the second adhesive layer 13. In the case where ultraviolet rays are used as the radiation, the irradiation conditions are preferably such that the cumulative amount of light is in the range of 50 mJ/cm 2 to 1000 mJ/cm 2 , and more preferably in the range of 100 mJ/cm 2 to 800 mJ/cm 2 . When the irradiation of ultraviolet rays is less than 50 mJ/cm 2 , the curing of the second pressure-sensitive adhesive layer 13 may be insufficient. As a result, the adhesion to the adhesive layer 14 is increased, resulting in a decrease in pick-up property. In addition, a paste residue is generated on the adhesive layer 14 after picking up. On the other hand, when the irradiation of ultraviolet rays exceeds 1000 mJ/cm 2 , the curing of the second pressure-sensitive adhesive layer 13 is excessively performed, and the tensile modulus of elasticity is excessively increased to cause a decrease in expandability. Further, the adhesive strength is excessively lowered, whereby wafer scatter occurs sometimes during dicing of the semiconductor wafer.
之後,將通過照射輻射線而固化的第二粘合劑層13轉印到第一粘合劑層12上。另外,本實施方式中,也可以將第二粘合劑層前驅物轉印到第一粘合劑層12上後,對該第一粘合劑層前驅物進行輻射線照射而形成第二粘合劑層13。作為此時的照射條件,在使用紫外線作為輻射線的情況下,優選使得其累積光量在50mJ/cm2 ~1000mJ/cm2 的範圍內,更優選在100mJ/cm2 ~800mJ/cm2 的範圍內。紫外線的照射低於50mJ/cm2 時,有時第二粘合劑層13的固化不充分。結果,與膠粘劑層14的密合性增大,導致拾取性下降。另外,拾取後在膠粘劑層14上產生膠糊殘留。另一方面,紫外線的照射超過1000mJ/cm2 時,第二粘合劑層13的固化過度進行,從而拉伸彈性模量過度增大,擴展性下降。另外,粘合力過度下降,由此,在半導體晶片的切割時,有時產生晶片飛散。Thereafter, the second adhesive layer 13 cured by the irradiation of the radiation is transferred onto the first adhesive layer 12. Further, in the present embodiment, after the second pressure-sensitive adhesive layer precursor is transferred onto the first pressure-sensitive adhesive layer 12, the first pressure-sensitive adhesive layer precursor may be irradiated with radiation to form a second viscosity. Mixture layer 13. As the irradiation condition at this time, in the case where ultraviolet rays are used as the radiation, it is preferable that the cumulative amount of light is in the range of 50 mJ/cm 2 to 1000 mJ/cm 2 , and more preferably in the range of 100 mJ/cm 2 to 800 mJ/cm 2 . Inside. When the irradiation of ultraviolet rays is less than 50 mJ/cm 2 , the curing of the second pressure-sensitive adhesive layer 13 may be insufficient. As a result, the adhesion to the adhesive layer 14 is increased, resulting in a decrease in pick-up property. In addition, a paste residue is generated on the adhesive layer 14 after picking up. On the other hand, when the irradiation of ultraviolet rays exceeds 1000 mJ/cm 2 , the curing of the second pressure-sensitive adhesive layer 13 is excessively performed, whereby the tensile modulus of elasticity is excessively increased and the expandability is lowered. Further, the adhesive strength is excessively lowered, whereby wafer scatter occurs sometimes during dicing of the semiconductor wafer.
接著,在第二粘合劑層13上形成膠粘劑層14。即,將用於形成膠粘劑層14的膠粘劑組合物塗布到剝離紙上以達到規定的厚度,再在規定條件下進行乾燥而形成膠粘劑層14。通過將該膠粘劑層14轉印到第二粘合劑層13上,可以形成本實施方式的半導體裝置製造用薄膜1。另外,膠粘劑層14的轉印也可以對第二粘合劑層前驅物進行。此時,膠粘劑層14轉印後對第二粘合劑層前驅物照射輻射線,從而形成第二粘合劑層13。此時的輻射線的照射條件可以根據將第二粘合劑層前驅物轉印到第一粘合劑層12上的情況。Next, an adhesive layer 14 is formed on the second adhesive layer 13. That is, the adhesive composition for forming the adhesive layer 14 is applied onto a release paper to a predetermined thickness, and then dried under predetermined conditions to form the adhesive layer 14. By transferring the adhesive layer 14 onto the second pressure-sensitive adhesive layer 13, the film 1 for semiconductor device manufacturing of the present embodiment can be formed. Alternatively, the transfer of the adhesive layer 14 may be performed on the second adhesive layer precursor. At this time, the second adhesive layer precursor is irradiated with radiation after the adhesive layer 14 is transferred, thereby forming the second adhesive layer 13. The irradiation condition of the radiation at this time may be based on the case where the second adhesive layer precursor is transferred onto the first adhesive layer 12.
(半導體裝置的製造方法)(Method of Manufacturing Semiconductor Device)
以下參照圖3對使用所述半導體裝置製造用薄膜1製造半導體裝置的方法進行說明。圖3是表示對在所述半導體裝置製造用薄膜的膠粘劑層上粘貼的半導體晶片進行切割的形態的剖面示意圖。Next, a method of manufacturing a semiconductor device using the thin film 1 for semiconductor device manufacturing will be described with reference to FIG. 3 is a schematic cross-sectional view showing a state in which a semiconductor wafer attached to an adhesive layer of a film for manufacturing a semiconductor device is cut.
首先,如圖3(a)所示,在半導體裝置製造用薄膜1中的膠粘劑層14上壓接半導體晶片21,將其膠粘保持而固定(安裝製程)。本製程在利用壓接輥等擠壓手段進行擠壓的同時進行。粘貼條件沒有特別限制,通常可以在25℃~80℃的粘貼溫度、1mm/秒~100mm/秒的粘貼速度、0.05MPa~1MPa的粘貼壓力的條件下進行。First, as shown in FIG. 3(a), the semiconductor wafer 21 is pressure-bonded to the adhesive layer 14 in the thin film 1 for semiconductor device manufacturing, and is adhered and fixed (mounting process). This process is carried out while being extruded by a pressing means such as a pressure roller. The bonding conditions are not particularly limited, and can be usually carried out at a bonding temperature of 25 ° C to 80 ° C, a bonding speed of 1 mm / sec to 100 mm / sec, and a bonding pressure of 0.05 MPa to 1 MPa.
然後,如圖3(b)所示,進行半導體晶片21的切割。由此,將半導體晶片21切割為規定的尺寸而小片化,形成半導體晶片22。切割例如按照常規方法從半導體晶片21的電路面一側進行。第一粘合劑層12上的切割環的粘貼部分18上,設置有切割環23。另外,本製程中,將切割刀片24的切入進行到第二粘合劑層13的一部分,並且不達到第一粘合劑層12。第二粘合劑層13預先進行輻射線固化,因此即使通過切割而切斷,也可以減少該切割面上產生粘合劑的膠糊露出(毛刺)。結果,可以防止切割面之間再附著(粘連),從而後述的拾取可以更加良好地進行。另外,基材層11和第一粘合劑層12未被切割,因此可以防止由於基材層11的切割而產生的絲狀切削屑以毛刺或細須的形態附著到半導體晶片22的側面等,從而實現低污染性。另外,也可以防止由於第一粘合劑層12的切割而產生的毛刺等。本製程中使用的切割裝置沒有特別限制,可以使用現有公知的切割裝置。另外,半導體晶片21由膠粘劑層14膠粘固定,因此可以抑制晶片缺口或晶片飛散,並且也可以抑制半導體晶片21的破損。Then, as shown in FIG. 3(b), the dicing of the semiconductor wafer 21 is performed. Thereby, the semiconductor wafer 21 is diced into a predetermined size and diced to form the semiconductor wafer 22. The cutting is performed from the circuit surface side of the semiconductor wafer 21, for example, in accordance with a conventional method. On the pasting portion 18 of the cutting ring on the first adhesive layer 12, a cutting ring 23 is provided. Further, in the present process, the cutting of the cutting blade 24 is performed to a part of the second adhesive layer 13, and the first adhesive layer 12 is not reached. Since the second pressure-sensitive adhesive layer 13 is irradiated with radiation in advance, even if it is cut by cutting, it is possible to reduce the exposure (burr) of the adhesive which causes the adhesive on the cut surface. As a result, it is possible to prevent reattachment (adhesion) between the cut faces, so that the picking described later can be performed more satisfactorily. Further, since the base material layer 11 and the first pressure-sensitive adhesive layer 12 are not cut, it is possible to prevent the filament-like chips generated by the cutting of the base material layer 11 from adhering to the side surface of the semiconductor wafer 22 in the form of burrs or whiskers, and the like. To achieve low pollution. In addition, burrs or the like due to the cutting of the first adhesive layer 12 can also be prevented. The cutting device used in the present process is not particularly limited, and a conventionally known cutting device can be used. Further, since the semiconductor wafer 21 is adhered and fixed by the adhesive layer 14, it is possible to suppress wafer notch or wafer scattering, and it is also possible to suppress breakage of the semiconductor wafer 21.
然後,進行半導體裝置製造用薄膜1的擴展。擴展使用現有公知的擴展裝置進行。擴展裝置具有可以通過切割環將半導體裝置製造用薄膜1向下壓的圓環形狀(甜甜圈狀)的外環、和直徑小於該外環並且支撐半導體裝置製造用薄膜1的內環。Then, the expansion of the thin film 1 for semiconductor device manufacturing is performed. The expansion is carried out using a conventionally known expansion device. The expansion device has a ring-shaped (doughnut-shaped) outer ring that can press the film 1 for semiconductor device manufacturing down by a dicing ring, and an inner ring having a smaller diameter than the outer ring and supporting the film 1 for semiconductor device manufacturing.
接著,如圖3(c)所示,為了將半導體裝置製造用薄膜1上膠粘固定的半導體晶片22剝離,進行半導體晶片22的拾取。第二粘合劑層13預先通過照射輻射線而固化,因此拾取在不照射輻射線的情況下進行。拾取的方法沒有特別限制,可以採用現有公知的各種方法。可以列舉例如,用針將各個半導體晶片22從半導體裝置製造用薄膜1一側向上推,利用拾取裝置將被上推的半導體晶片22拾取的方法等。本發明的半導體裝置製造用薄膜1中,第二粘合劑層13與膠粘劑層14的剝離性良好,因此,例如即使減少針數,或者減少上推量,也可以提高成品率地進行拾取。Next, as shown in FIG. 3(c), in order to peel off the semiconductor wafer 22 adhered and fixed on the thin film 1 for semiconductor device manufacturing, the semiconductor wafer 22 is picked up. The second adhesive layer 13 is previously cured by irradiation of radiation, and thus the pickup is performed without irradiating the radiation. The method of picking up is not particularly limited, and various methods known in the art can be employed. For example, a method in which each semiconductor wafer 22 is pushed up from the side of the thin film 1 for semiconductor device manufacturing by a needle, and the semiconductor wafer 22 pushed up by the pick-up device is picked up. In the film 1 for semiconductor device manufacturing of the present invention, since the second adhesive layer 13 and the adhesive layer 14 have good peelability, for example, even if the number of stitches is reduced or the amount of push-up is reduced, the pick-up can be improved with a higher yield.
拾取的半導體晶片22,通過膠粘劑層14膠粘固定到被粘物上(晶片接合)。被粘物載置於加熱組合單元(heat block)9上。作為被粘物,可以列舉引線框、TAB薄膜、基板或另外製作的半導體晶片等。被粘物例如可以是容易變形的變形型被粘物,也可以是難以變形的非變形型被粘物(半導體晶片等)。The picked semiconductor wafer 22 is adhesively fixed to the adherend by the adhesive layer 14 (wafer bonding). The adherend is placed on a heat block 9. Examples of the adherend include a lead frame, a TAB film, a substrate, or a separately fabricated semiconductor wafer. The adherend may be, for example, a deformed adherend that is easily deformed, or a non-deformable adherend (such as a semiconductor wafer) that is difficult to deform.
作為所述基板,可以使用現有公知的基板。另外,作為所述引線框,可以使用Cu引線框、42合金引線框等金屬引線框或者包含玻璃環氧、BT(雙馬來醯亞胺-三嗪)、聚醯亞胺等的有機基板。但是,本發明不限於這些,也包括在安裝半導體元件、與半導體元件電連接後可以使用的電路基板。As the substrate, a conventionally known substrate can be used. Further, as the lead frame, a metal lead frame such as a Cu lead frame or a 42 alloy lead frame or an organic substrate containing glass epoxy, BT (bismaleimide-triazine), or polyimine may be used. However, the present invention is not limited to these, and includes a circuit board that can be used after mounting a semiconductor element and electrically connecting the semiconductor element.
膠粘劑層14為熱固型的情況下,通過加熱固化,將半導體晶片22膠粘固定到被粘物上,使耐熱強度提高。另外,半導體晶片22通過膠粘劑層14膠粘固定到基板等上而得到的材料,可以供給回流焊接製程。之後,進行用焊線將基板的端子部(內部引線)的前端與半導體晶片22上的電極焊盤電連接的絲焊,再用密封樹脂將半導體晶片密封,並將該密封樹脂後固化。由此,製作本實施方式的半導體裝置。When the adhesive layer 14 is a thermosetting type, the semiconductor wafer 22 is adhered and fixed to the adherend by heat curing, and the heat resistance is improved. Further, a material obtained by adhering and fixing the semiconductor wafer 22 to the substrate or the like by the adhesive layer 14 can be supplied to a reflow soldering process. Thereafter, wire bonding is performed to electrically connect the tip end of the terminal portion (internal lead) of the substrate to the electrode pad on the semiconductor wafer 22 by a bonding wire, and the semiconductor wafer is sealed with a sealing resin, and the sealing resin is post-cured. Thus, the semiconductor device of the present embodiment is produced.
實施例Example
以下,對本發明的優選實施例進行詳細的例示說明。但是,該實施例中記載的材料或配合量等只要沒有特別限定的記載則不將本發明的範圍僅限定於此。Hereinafter, preferred embodiments of the present invention will be described in detail. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the invention, unless otherwise specified.
(實施例1)(Example 1)
<第二粘合劑層的製作><Production of Second Adhesive Layer>
在具有冷凝管、氮氣導入管、溫度計和攪拌裝置的反應容器中,加入丙烯酸-2-乙基己酯(2EHA):80重量份、丙烯酸-2-羥基乙酯(HEA):20重量份和甲苯:65重量份,在氮氣流中在61℃進行6小時的聚合處理,得到丙烯酸類聚合物X。In a reaction vessel having a condenser tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 2-ethylhexyl acrylate (2EHA) was added: 80 parts by weight, 2-hydroxyethyl acrylate (HEA): 20 parts by weight, and Toluene: 65 parts by weight, and polymerization treatment was carried out at 61 ° C for 6 hours in a nitrogen stream to obtain an acrylic polymer X.
在該丙烯酸類聚合物X:100重量份中,加入2-甲基丙烯醯氧乙基異氰酸酯(MOI):24.1重量份(相對於HEA為90莫耳%(mol%)),在空氣氣流中在50℃進行48小時加成反應處理,得到丙烯酸類聚合物Y。In the acrylic polymer X: 100 parts by weight, 2-methylpropenyloxyethyl isocyanate (MOI) was added: 24.1 parts by weight (90 mol% (mol%) relative to HEA) in an air stream The addition reaction treatment was carried out at 50 ° C for 48 hours to obtain an acrylic polymer Y.
然后,在丙烯酸類聚合物Y:100重量份中,加入多異氰酸酯化合物(商品名“coronate L”,日本聚氨酯工業有限公司製造):3重量份以及光聚合引發劑(商品名“Irgacure 651”,汽巴精化有限公司製造)5重量份,製備粘合劑溶液。Then, a polyisocyanate compound (trade name "coronate L", manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to 100 parts by weight of the acrylic polymer Y: 3 parts by weight and a photopolymerization initiator (trade name "Irgacure 651", A binder solution was prepared in an amount of 5 parts by weight manufactured by Ciba Specialty Chemicals Co., Ltd.
將所述中製備的粘合劑溶液塗布到厚度50μm PET薄膜的經聚矽氧烷處理的面上,在80℃下加熱交聯3分鐘,形成厚度30μm的輻射線固化型的第二粘合劑層前驅物,之後,使用紫外線(UV)照射裝置(商品名“UM-810”,日東精機有限公司製造),以紫外線照射累積光量:300mJ/cm2 照射紫外線,製作第二粘合劑層。The binder solution prepared in the above was applied to a polysiloxane-treated surface of a PET film having a thickness of 50 μm, and cross-linked by heating at 80 ° C for 3 minutes to form a radiation-curable second bond having a thickness of 30 μm. After the agent layer precursor is used, an ultraviolet (UV) irradiation device (trade name "UM-810", manufactured by Nitto Seiki Co., Ltd.) is used, and ultraviolet light is irradiated with an accumulated amount of light: 300 mJ/cm 2 to irradiate ultraviolet rays to prepare a second adhesive layer. .
<膠粘劑層的製作><Production of Adhesive Layer>
將環氧樹脂(日本化藥有限公司製造,商品名:EPPN501HY)50重量份、酚醛樹脂(明和化成有限公司製造,商品名:MEH7800)50重量份、丙烯酸類共聚物(NOGAWA化學有限公司製造,商品名:Ravital AR31,重量平均分子量70萬,玻璃化轉變温度-15℃)100重量份和作為填料的球形二氧化矽(ADMATECHS有限公司製造,商品名:SO-25R,平均粒徑0.5μm)70重量份溶解於甲乙酮中,得到濃度23.6重量%的膠粘劑組合物溶液。50 parts by weight of an epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EPPN501HY), 50 parts by weight of a phenol resin (manufactured by Megumi Kasei Co., Ltd., trade name: MEH7800), and an acrylic copolymer (manufactured by NOGAWA Chemical Co., Ltd.) Trade name: Ravital AR31, weight average molecular weight 700,000, glass transition temperature -15 ° C) 100 parts by weight and spherical cerium oxide as a filler (manufactured by ADMATECHS Co., Ltd., trade name: SO-25R, average particle diameter 0.5 μm) 70 parts by weight was dissolved in methyl ethyl ketone to obtain a solution of the adhesive composition having a concentration of 23.6% by weight.
將該膠粘劑組合物溶液塗布到經聚矽氧烷脫膜處理後的厚度50μm的聚對苯二甲酸乙二醇酯薄膜構成的脫模處理薄膜(剝離襯墊)上,然後在130℃乾燥2分鐘。由此,製作厚度25μm的膠粘劑層。The adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm after the polysiloxane treatment, and then dried at 130 ° C. minute. Thus, an adhesive layer having a thickness of 25 μm was produced.
<半導體裝置製造用薄膜的製作><Production of Thin Film for Semiconductor Device Manufacturing>
作為在基材層上層疊有第一粘合劑層的載帶,使用日東電工有限公司製造的商品名S-400X。在該載帶的第一粘合劑層上,在常溫下粘貼切出為315mmΦ的第二粘合劑層。之後,以切出為330mmΦ的膠粘劑層完全覆蓋第二粘合劑層的方式在40℃進行粘貼,製作本實施例的半導體裝置製造用薄膜。As a carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer, a trade name of S-400X manufactured by Nitto Denko Corporation was used. On the first adhesive layer of the carrier tape, a second adhesive layer cut at 315 mmφ was attached at a normal temperature. Thereafter, the adhesive layer having a thickness of 330 mmφ was cut so as to completely cover the second pressure-sensitive adhesive layer, and the film was bonded at 40° C. to produce a film for producing a semiconductor device of the present example.
(實施例2)(Example 2)
在本實施例中,作為在基材層上層疊有第一粘合劑層的載帶(carrier tape),使用日東電工有限公司製造的商品名CB-700,除此以外,與實施例1同樣操作,製作本實施例的半導體裝置製造用薄膜。In the present embodiment, the carrier tape in which the first pressure-sensitive adhesive layer is laminated on the base material layer is the same as in the first embodiment except that the product name CB-700 manufactured by Nitto Denko Corporation is used. The film for semiconductor device production of this example was produced.
(實施例3)(Example 3)
在本實施例中,作為在基材層上層疊有第一粘合劑層的載帶,使用日東電工有限公司製造的商品名M-4001,除此以外,與實施例1同樣操作,製作本實施例的半導體裝置製造用薄膜。In the present embodiment, the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer was produced in the same manner as in Example 1 except that the product name M-4001 manufactured by Nitto Denko Corporation was used. A film for manufacturing a semiconductor device of the embodiment.
(實施例4)(Example 4)
在本實施例中,作為在基材層上層疊有第一粘合劑層的載帶,使用日東電工有限公司製造的商品名HR-4011,除此以外,與實施例1同樣操作,製作本實施例的半導體裝置製造用薄膜。In the present embodiment, the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer was produced in the same manner as in Example 1 except that the product name HR-4011 manufactured by Nitto Denko Corporation was used. A film for manufacturing a semiconductor device of the embodiment.
(實施例5)(Example 5)
在本實施例中,作為在基材層上層疊有第一粘合劑層的載帶,使用日東電工有限公司製造的商品名V8-S,除此以外,與實施例1同樣操作,製作本實施例的半導體裝置製造用薄膜。In the present embodiment, the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer was produced in the same manner as in Example 1 except that the product name V8-S manufactured by Nitto Denko Corporation was used. A film for manufacturing a semiconductor device of the embodiment.
(實施例6)(Example 6)
在本實施例中,作為在基材層上層疊有第一粘合劑層的載帶,使用日東電工有限公司製造的商品名UE-1088J,除此以外,與實施例1同樣操作,製作本實施例的半導體裝置製造用薄膜。In the present embodiment, the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer was produced in the same manner as in Example 1 except that the product name UE-1088J manufactured by Nitto Denko Corporation was used. A film for manufacturing a semiconductor device of the embodiment.
(實施例7)(Example 7)
在本實施例中,作為在基材層上層疊有第一粘合劑層的載帶,使用日東電工有限公司製造的商品名UB-2130E,除此以外,與實施例1同樣操作,製作本實施例的半導體裝置製造用薄膜。In the present embodiment, the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer was produced in the same manner as in Example 1 except that the product name UB-2130E manufactured by Nitto Denko Corporation was used. A film for manufacturing a semiconductor device of the embodiment.
(實施例8)(Example 8)
<第二粘合劑層的製作><Production of Second Adhesive Layer>
在具有冷凝管、氮氣導入管、溫度計和攪拌裝置的反應容器中,加入丙烯酸-2-乙基己酯(2EHA):80重量份、丙烯酸-2-羥基乙酯(HEA):20重量份和甲苯:65重量份,在氮氣流中在61℃進行6小時的聚合處理,得到丙烯酸類聚合物X。In a reaction vessel having a condenser tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 2-ethylhexyl acrylate (2EHA) was added: 80 parts by weight, 2-hydroxyethyl acrylate (HEA): 20 parts by weight, and Toluene: 65 parts by weight, and polymerization treatment was carried out at 61 ° C for 6 hours in a nitrogen stream to obtain an acrylic polymer X.
在該丙烯酸類聚合物X:100重量份中,加入2-甲基丙烯醯氧乙基異氰酸酯(MOI):24.1重量份(相對於HEA為90莫耳%),在空氣氣流中在50℃進行48小時加成反應處理,得到丙烯酸類聚合物Y。In the acrylic polymer X: 100 parts by weight, 2-methylpropenyloxyethyl isocyanate (MOI) was added: 24.1 parts by weight (90 mol% relative to HEA), and carried out in an air stream at 50 ° C The 48-hour addition reaction treatment gave an acrylic polymer Y.
然後,在丙烯酸類聚合物Y:100重量份中,加入多異氰酸酯化合物(商品名“coronate L”,日本聚氨酯工業有限公司製造):8重量份以及光聚合引發劑(商品名“Irgacure 651”,汽巴精化有限公司製造)5重量份,製備粘合劑溶液。Then, a polyisocyanate compound (trade name "coronate L", manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to 100 parts by weight of the acrylic polymer Y: 8 parts by weight and a photopolymerization initiator (trade name "Irgacure 651", A binder solution was prepared in an amount of 5 parts by weight manufactured by Ciba Specialty Chemicals Co., Ltd.
將所述中製備的粘合劑溶液塗布到厚度50μm PET薄膜的經聚矽氧烷處理的面上,在80℃下加熱交聯3分鐘,形成厚度30μm的輻射線固化型的第二粘合劑層前驅物,之後,使用紫外線(UV)照射裝置(商品名“UM-810”,日東精機有限公司製造),以紫外線照射累積光量:300mJ/cm2 照射紫外線,製作第二粘合劑層。The binder solution prepared in the above was applied to a polysiloxane-treated surface of a PET film having a thickness of 50 μm, and cross-linked by heating at 80 ° C for 3 minutes to form a radiation-curable second bond having a thickness of 30 μm. After the agent layer precursor is used, an ultraviolet (UV) irradiation device (trade name "UM-810", manufactured by Nitto Seiki Co., Ltd.) is used, and ultraviolet light is irradiated with an accumulated amount of light: 300 mJ/cm 2 to irradiate ultraviolet rays to prepare a second adhesive layer. .
<膠粘劑層的製作><Production of Adhesive Layer>
關於本實施例的膠粘劑層,使用與實施例1同樣的膠粘劑層。Regarding the adhesive layer of the present embodiment, the same adhesive layer as in Example 1 was used.
<半導體裝置製造用薄膜的製作><Production of Thin Film for Semiconductor Device Manufacturing>
作為在基材層上層疊有第一粘合劑層的載帶,使用與實施例1同樣的載帶。在該載帶的第一粘合劑層上,在常溫下粘貼切出為315mmΦ的第二粘合劑層。之後,以切出為330mmΦ的膠粘劑層完全覆蓋第二粘合劑層的方式在40℃進行粘貼,製作本實施例的半導體裝置製造用薄膜。As the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer, the same carrier tape as in Example 1 was used. On the first adhesive layer of the carrier tape, a second adhesive layer cut at 315 mmφ was attached at a normal temperature. Thereafter, the adhesive layer having a thickness of 330 mmφ was cut so as to completely cover the second pressure-sensitive adhesive layer, and the film was bonded at 40° C. to produce a film for producing a semiconductor device of the present example.
(實施例9)(Example 9)
<第二粘合劑層前驅物的製作><Preparation of second adhesive layer precursor>
在具有冷凝管、氮氣導入管、溫度計和攪拌裝置的反應容器中,加入丙烯酸-2-乙基己酯(2EHA):80重量份、丙烯酸-2-羥基乙酯(HEA):20重量份和甲苯:65重量份,在氮氣流中在61℃進行6小時的聚合處理,得到丙烯酸類聚合物X。In a reaction vessel having a condenser tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 2-ethylhexyl acrylate (2EHA) was added: 80 parts by weight, 2-hydroxyethyl acrylate (HEA): 20 parts by weight, and Toluene: 65 parts by weight, and polymerization treatment was carried out at 61 ° C for 6 hours in a nitrogen stream to obtain an acrylic polymer X.
在該丙烯酸類聚合物X:100重量份中,加入2-甲基丙烯醯氧乙基異氰酸酯(MOI):24.1重量份(相對於HEA為90莫耳%),在空氣氣流中在50℃進行48小時加成反應處理,得到丙烯酸類聚合物Y。In the acrylic polymer X: 100 parts by weight, 2-methylpropenyloxyethyl isocyanate (MOI) was added: 24.1 parts by weight (90 mol% relative to HEA), and carried out in an air stream at 50 ° C The 48-hour addition reaction treatment gave an acrylic polymer Y.
然後,在丙烯酸類聚合物Y:100重量份中,加入多異氰酸酯化合物(商品名“coronate L”,日本聚氨酯工業有限公司製造):5重量份以及光聚合引發劑(商品名“Irgacure 651”,汽巴精化有限公司製造)5重量份,製備粘合劑溶液。Then, a polyisocyanate compound (trade name "coronate L", manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to 100 parts by weight of the acrylic polymer Y: 5 parts by weight and a photopolymerization initiator (trade name "Irgacure 651", A binder solution was prepared in an amount of 5 parts by weight manufactured by Ciba Specialty Chemicals Co., Ltd.
將所述中製備的粘合劑溶液塗布到厚度50μm PET薄膜的經聚矽氧烷處理的面上,在80℃下加熱交聯3分鐘,形成厚度30μm的輻射線固化型的第二粘合劑層前驅物。The binder solution prepared in the above was applied to a polysiloxane-treated surface of a PET film having a thickness of 50 μm, and cross-linked by heating at 80 ° C for 3 minutes to form a radiation-curable second bond having a thickness of 30 μm. Agent layer precursor.
<膠粘劑層的製作><Production of Adhesive Layer>
關於本實施例的膠粘劑層,使用與實施例1同樣的膠粘劑層。Regarding the adhesive layer of the present embodiment, the same adhesive layer as in Example 1 was used.
<半導體裝置製造用薄膜的製作><Production of Thin Film for Semiconductor Device Manufacturing>
作為在基材層上層疊有第一粘合劑層的載帶,使用與實施例1同樣的載帶。在該載帶的第一粘合劑層上,在常溫下粘貼切出為315mmΦ的第二粘合劑層前驅物。之後,以切出為330mmΦ的膠粘劑層完全覆蓋第二粘合劑層前驅物的方式在40℃進行粘貼。然後,使用紫外線(UV)照射裝置(商品名“UM-810”,日東精機有限公司製造),從基材層一側以紫外線照射累積光量:300mJ/cm2 對第二粘合劑層前驅物照射紫外線,形成第二粘合劑層。由此,製作本實施例的半導體裝置製造用薄膜。As the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer, the same carrier tape as in Example 1 was used. On the first adhesive layer of the carrier tape, a second adhesive layer precursor cut out at 315 mmφ was attached at a normal temperature. Thereafter, the adhesive was applied at 40 ° C in such a manner that the adhesive layer cut out of 330 mm Φ completely covered the second adhesive layer precursor. Then, using an ultraviolet (UV) irradiation device (trade name "UM-810", manufactured by Nitto Seiki Co., Ltd.), the cumulative amount of light is irradiated with ultraviolet rays from the side of the substrate layer: 300 mJ/cm 2 for the second adhesive layer precursor The ultraviolet rays are irradiated to form a second adhesive layer. Thus, a film for semiconductor device production of the present example was produced.
(實施例10)(Embodiment 10)
<第二粘合劑層的製作><Production of Second Adhesive Layer>
關於本實施例的第二粘合劑層,使用與實施例1同樣的第二粘合劑層。Regarding the second pressure-sensitive adhesive layer of the present embodiment, the same second pressure-sensitive adhesive layer as in Example 1 was used.
<膠粘劑層的製作><Production of Adhesive Layer>
將環氧樹脂(日本化藥有限公司製造,商品名:EPPN501HY)200重量份、酚醛樹脂(明和化成有限公司製造,商品名:MEH7800)200重量份、丙烯酸類共聚物(NOGAWA化學有限公司製造,商品名:Ravital AR31,重量平均分子量70萬,玻璃化轉變温度-15℃)100重量份和作為填料的球形二氧化矽(ADMATECHS有限公司製造,商品名:SO-25R,平均粒径0.5μm)200重量份溶解於甲乙酮中,得到濃度23.6重量%的膠粘劑組合物溶液。200 parts by weight of an epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EPPN501HY), 200 parts by weight of a phenol resin (manufactured by Megumi Kasei Co., Ltd., trade name: MEH7800), and an acrylic copolymer (manufactured by NOGAWA Chemical Co., Ltd.) Trade name: Ravital AR31, weight average molecular weight 700,000, glass transition temperature -15 ° C) 100 parts by weight and spherical cerium oxide as a filler (manufactured by ADMATECHS Co., Ltd., trade name: SO-25R, average particle diameter 0.5 μm) 200 parts by weight was dissolved in methyl ethyl ketone to obtain a solution of the adhesive composition having a concentration of 23.6% by weight.
將該膠粘劑組合物溶液塗布到經聚矽氧烷脫膜處理後的厚度50μm的聚對苯二甲酸乙二醇酯薄膜構成的脫模處理薄膜(剝離襯墊)上,然後在130℃乾燥2分鐘。由此,製作厚度25μm的膠粘劑層。The adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm after the polysiloxane treatment, and then dried at 130 ° C. minute. Thus, an adhesive layer having a thickness of 25 μm was produced.
<半導體裝置製造用薄膜的製作><Production of Thin Film for Semiconductor Device Manufacturing>
作為在基材層上層疊有第一粘合劑層的載帶,使用與實施例1同樣的載帶。在該載帶的第一粘合劑層上,在常溫下粘貼切出為315mmΦ的第二粘合劑層。之後,以切出為330mmΦ的膠粘劑層完全覆蓋第二粘合劑層的方式在40℃進行粘貼,製作本實施例的半導體裝置製造用薄膜。As the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer, the same carrier tape as in Example 1 was used. On the first adhesive layer of the carrier tape, a second adhesive layer cut at 315 mmφ was attached at a normal temperature. Thereafter, the adhesive layer having a thickness of 330 mmφ was cut so as to completely cover the second pressure-sensitive adhesive layer, and the film was bonded at 40° C. to produce a film for producing a semiconductor device of the present example.
(實施例11)(Example 11)
<第二粘合劑層的製作><Production of Second Adhesive Layer>
關於本實施例的第二粘合劑層,使用與實施例8同樣的第二粘合劑層。Regarding the second pressure-sensitive adhesive layer of the present embodiment, the same second pressure-sensitive adhesive layer as in Example 8 was used.
<膠粘劑層的製作><Production of Adhesive Layer>
關於本實施例的膠粘劑層,使用與實施例10同樣的膠粘劑層。Regarding the adhesive layer of the present embodiment, the same adhesive layer as in Example 10 was used.
<半導體裝置製造用薄膜的製作><Production of Thin Film for Semiconductor Device Manufacturing>
作為在基材層上層疊有第一粘合劑層的載帶,使用與實施例1同樣的載帶。在該載帶的第一粘合劑層上,在常溫下粘貼切出為315mmΦ的第二粘合劑層。之後,以切出為330mmΦ的膠粘劑層完全覆蓋第二粘合劑層的方式在40℃進行粘貼,製作本實施例的半導體裝置製造用薄膜。As the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer, the same carrier tape as in Example 1 was used. On the first adhesive layer of the carrier tape, a second adhesive layer cut at 315 mmφ was attached at a normal temperature. Thereafter, the adhesive layer having a thickness of 330 mmφ was cut so as to completely cover the second pressure-sensitive adhesive layer, and the film was bonded at 40° C. to produce a film for producing a semiconductor device of the present example.
(實施例12)(Embodiment 12)
<第二粘合劑層前驅物的製作><Preparation of second adhesive layer precursor>
關於本實施例的第二粘合劑層前驅物,使用與實施例8同樣的第二粘合劑層前驅物。Regarding the second pressure-sensitive adhesive layer precursor of the present embodiment, the same second pressure-sensitive adhesive layer precursor as in Example 8 was used.
<膠粘劑層的製作><Production of Adhesive Layer>
關於本實施例的膠粘劑層,使用與實施例10同樣的膠粘劑層。Regarding the adhesive layer of the present embodiment, the same adhesive layer as in Example 10 was used.
<半導體裝置製造用薄膜的製作><Production of Thin Film for Semiconductor Device Manufacturing>
作為在基材層上層疊有第一粘合劑層的載帶,使用與實施例1同樣的載帶。在該載帶的第一粘合劑層上,在常溫下粘貼切出為315mmΦ的第二粘合劑層。之後,以切出為330mmΦ的膠粘劑層完全覆蓋第二粘合劑層前驅物的方式在40℃進行粘貼,然後,使用紫外線(UV)照射裝置(商品名“UM-810”,日東精機有限公司製造),從基材層一側以紫外線照射累積光量:300mJ/cm2 對第二粘合劑層前驅物照射紫外線,形成第二粘合劑層。由此,製作本實施例的半導體裝置製造用薄膜。As the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer, the same carrier tape as in Example 1 was used. On the first adhesive layer of the carrier tape, a second adhesive layer cut at 315 mmφ was attached at a normal temperature. Thereafter, the adhesive layer having a thickness of 330 mmφ was completely covered to cover the second adhesive layer precursor at 40 ° C, and then an ultraviolet (UV) irradiation device (trade name "UM-810", Nitto Seiki Co., Ltd.) was used. Manufactured, the second adhesive layer precursor was irradiated with ultraviolet light by irradiating ultraviolet light with a cumulative amount of light from the side of the substrate layer: 300 mJ/cm 2 to form a second pressure-sensitive adhesive layer. Thus, a film for semiconductor device production of the present example was produced.
(實施例13)(Example 13)
<第二粘合劑層前驅物的製作><Preparation of second adhesive layer precursor>
關於本實施例的第二粘合劑層前驅物,使用與實施例9同樣的第二粘合劑層前驅物。Regarding the second pressure-sensitive adhesive layer precursor of the present embodiment, the same second pressure-sensitive adhesive layer precursor as in Example 9 was used.
<膠粘劑層的製作><Production of Adhesive Layer>
關於本實施例的膠粘劑層,使用與實施例1同樣的膠粘劑層。Regarding the adhesive layer of the present embodiment, the same adhesive layer as in Example 1 was used.
<半導體裝置製造用薄膜的製作><Production of Thin Film for Semiconductor Device Manufacturing>
作為在基材層上層疊有第一粘合劑層的載帶,使用與實施例1同樣的載帶。在該載帶的第一粘合劑層上,在常溫下粘貼切出為315mmΦ的第二粘合劑層前驅物。之後,以切出為330mmΦ的膠粘劑層完全覆蓋第二粘合劑層前驅物的方式在40℃進行粘貼,然後,使用紫外線(UV)照射裝置(商品名“UM-810”,日東精機有限公司製造),從基材層一側以紫外線照射累積光量:300mJ/cm2 對第二粘合劑層前驅物照射紫外線,形成第二粘合劑層。由此,製作本實施例的半導體裝置製造用薄膜。As the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer, the same carrier tape as in Example 1 was used. On the first adhesive layer of the carrier tape, a second adhesive layer precursor cut out at 315 mmφ was attached at a normal temperature. Thereafter, the adhesive layer having a thickness of 330 mmφ was completely covered to cover the second adhesive layer precursor at 40 ° C, and then an ultraviolet (UV) irradiation device (trade name "UM-810", Nitto Seiki Co., Ltd.) was used. Manufactured, the second adhesive layer precursor was irradiated with ultraviolet light by irradiating ultraviolet light with a cumulative amount of light from the side of the substrate layer: 300 mJ/cm 2 to form a second pressure-sensitive adhesive layer. Thus, a film for semiconductor device production of the present example was produced.
(實施例14)(Example 14)
<第二粘合劑層前驅物的製作><Preparation of second adhesive layer precursor>
在具有冷凝管、氮氣導入管、溫度計和攪拌裝置的反應容器中,加入丙烯酸-2-乙基己酯(2EHA):80重量份、丙烯酸-2-羥基乙酯(HEA):20重量份和甲苯:65重量份,在氮氣流中在61℃進行6小時的聚合處理,得到丙烯酸類聚合物X。In a reaction vessel having a condenser tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 2-ethylhexyl acrylate (2EHA) was added: 80 parts by weight, 2-hydroxyethyl acrylate (HEA): 20 parts by weight, and Toluene: 65 parts by weight, and polymerization treatment was carried out at 61 ° C for 6 hours in a nitrogen stream to obtain an acrylic polymer X.
在該丙烯酸類聚合物X:100重量份中,加入2-甲基丙烯醯氧乙基異氰酸酯(MOI):24.1重量份(相對於HEA為90莫耳%),在空氣氣流中在50℃進行48小時加成反應處理,得到丙烯酸類聚合物Y。In the acrylic polymer X: 100 parts by weight, 2-methylpropenyloxyethyl isocyanate (MOI) was added: 24.1 parts by weight (90 mol% relative to HEA), and carried out in an air stream at 50 ° C The 48-hour addition reaction treatment gave an acrylic polymer Y.
然後,在丙烯酸類聚合物Y:100重量份中,加入多異氰酸酯化合物(商品名“coronate L”,日本聚氨酯工業有限公司製造):8重量份以及光聚合引發劑(商品名“Irgacure 651”,汽巴精化有限公司製造)5重量份,製備粘合劑溶液。Then, a polyisocyanate compound (trade name "coronate L", manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to 100 parts by weight of the acrylic polymer Y: 8 parts by weight and a photopolymerization initiator (trade name "Irgacure 651", A binder solution was prepared in an amount of 5 parts by weight manufactured by Ciba Specialty Chemicals Co., Ltd.
將所述中製備的粘合劑溶液塗布到厚度50μm PET薄膜的經聚矽氧烷處理的面上,在80℃下加熱交聯3分鐘,形成厚度30μm的輻射線固化型的第二粘合劑層前驅物。The binder solution prepared in the above was applied to a polysiloxane-treated surface of a PET film having a thickness of 50 μm, and cross-linked by heating at 80 ° C for 3 minutes to form a radiation-curable second bond having a thickness of 30 μm. Agent layer precursor.
<膠粘劑層的製作><Production of Adhesive Layer>
關於本實施例的膠粘劑層,使用與實施例1同樣的膠粘劑層。Regarding the adhesive layer of the present embodiment, the same adhesive layer as in Example 1 was used.
<半導體裝置製造用薄膜的製作><Production of Thin Film for Semiconductor Device Manufacturing>
作為在基材層上層疊有第一粘合劑層的載帶,使用日東電工有限公司製造的商品名S-400X。在該載帶的第一粘合劑層上,在常溫下粘貼切出為315mmΦ的第二粘合劑層前驅物。之後,使用紫外線(UV)照射裝置(商品名“UM-810”,日東精機有限公司製造),從基材層一側以紫外線照射累積光量:300mJ/cm2 對第二粘合劑層前驅物照射紫外線,形成第二粘合劑層。之後,以切出為330mmΦ的膠粘劑層完全覆蓋第二粘合劑層的方式在40℃進行粘貼,製作本實施例的半導體裝置製造用薄膜。As a carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer, a trade name of S-400X manufactured by Nitto Denko Corporation was used. On the first adhesive layer of the carrier tape, a second adhesive layer precursor cut out at 315 mmφ was attached at a normal temperature. Thereafter, an ultraviolet (UV) irradiation device (trade name "UM-810", manufactured by Nitto Seiki Co., Ltd.) was used, and the cumulative amount of light was irradiated with ultraviolet rays from the side of the substrate layer: 300 mJ/cm 2 to the second adhesive layer precursor. The ultraviolet rays are irradiated to form a second adhesive layer. Thereafter, the adhesive layer having a thickness of 330 mmφ was cut so as to completely cover the second pressure-sensitive adhesive layer, and the film was bonded at 40° C. to produce a film for producing a semiconductor device of the present example.
(比較例1)(Comparative Example 1)
在本比較例中,使用OPP薄膜(雙軸拉伸的聚丙烯薄膜,FUTAMURA化學有限公司製造,商品名:FBS-6)代替第二粘合劑層,除此以外與實施例1同樣操作,製作本比較例的半導體裝置製造用薄膜。In the comparative example, the same operation as in Example 1 was carried out except that an OPP film (a biaxially oriented polypropylene film, manufactured by FUTAMURA Chemical Co., Ltd., trade name: FBS-6) was used instead of the second pressure-sensitive adhesive layer. A film for semiconductor device production of this comparative example was produced.
(比較例2)(Comparative Example 2)
在本比較例中,使用表面經聚矽氧烷處理後的PE薄膜(聚乙烯薄膜,王子特殊紙有限公司製造,商品名:40RL-02)代替第二粘合劑層,除此以外與實施例1同樣操作,製作本比較例的半導體裝置製造用薄膜。另外,所述PE薄膜中的與膠粘劑層粘貼的粘貼面為經聚矽氧烷處理後的面。In this comparative example, a PE film (polyethylene film, manufactured by Oji Paper Co., Ltd., trade name: 40RL-02) treated with polysiloxane was used instead of the second pressure-sensitive adhesive layer, and other methods were implemented. In the same manner as in Example 1, a film for producing a semiconductor device of the comparative example was produced. Further, the adhesive surface adhered to the adhesive layer in the PE film is a surface treated with polyoxymethane.
(比較例3)(Comparative Example 3)
本比較例中,所述實施例1的半導體裝置製造用薄膜為不具有第二粘合劑層的結構,除此以外,與該實施例同樣操作,製作本比較例的半導體裝置製造用薄膜。即,在載帶的第一粘合劑層上不粘貼第二粘合劑層,而是在40℃下僅粘貼切出為330mmΦ的膠粘劑層,製作半導體裝置製造用薄膜。In the comparative example, the thin film for semiconductor device manufacturing of this comparative example was produced in the same manner as in the above except that the film for semiconductor device manufacturing of the first embodiment was not provided with the second pressure-sensitive adhesive layer. In other words, the second pressure-sensitive adhesive layer was not attached to the first pressure-sensitive adhesive layer of the carrier tape, and only an adhesive layer cut at 330 mmφ was adhered at 40° C. to produce a film for semiconductor device production.
(比較例4)(Comparative Example 4)
<第二粘合劑層的製作><Production of Second Adhesive Layer>
在具有冷凝管、氮氣導入管、溫度計和攪拌裝置的反應容器中,加入丙烯酸-2-乙基己酯(2EHA):80重量份、丙烯酸-2-羥基乙酯(HEA):20重量份和甲苯:65重量份,在氮氣流中在61℃進行6小時的聚合處理,得到丙烯酸類聚合物X。In a reaction vessel having a condenser tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 2-ethylhexyl acrylate (2EHA) was added: 80 parts by weight, 2-hydroxyethyl acrylate (HEA): 20 parts by weight, and Toluene: 65 parts by weight, and polymerization treatment was carried out at 61 ° C for 6 hours in a nitrogen stream to obtain an acrylic polymer X.
在該丙烯酸類聚合物X:100重量份中,加入2-甲基丙烯醯氧乙基異氰酸酯(MOI):24.1重量份(相對於HEA為90莫耳%),在空氣氣流中在50℃進行48小時加成反應處理,得到丙烯酸類聚合物Y。In the acrylic polymer X: 100 parts by weight, 2-methylpropenyloxyethyl isocyanate (MOI) was added: 24.1 parts by weight (90 mol% relative to HEA), and carried out in an air stream at 50 ° C The 48-hour addition reaction treatment gave an acrylic polymer Y.
然後,在丙烯酸類聚合物Y:100重量份中,加入多異氰酸酯化合物(商品名“coronate L”,日本聚氨酯工業有限公司製造):5重量份以及光聚合引發劑(商品名“Irgacure 651”,汽巴精化有限公司製造)5重量份,製備粘合劑溶液。Then, a polyisocyanate compound (trade name "coronate L", manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to 100 parts by weight of the acrylic polymer Y: 5 parts by weight and a photopolymerization initiator (trade name "Irgacure 651", A binder solution was prepared in an amount of 5 parts by weight manufactured by Ciba Specialty Chemicals Co., Ltd.
將所述中製備的粘合劑溶液塗布到厚度50μm PET薄膜的經聚矽氧烷處理的面上,在80℃下加熱交聯3分鐘,形成厚度30μm的輻射線固化型的第二粘合劑層。The binder solution prepared in the above was applied to a polysiloxane-treated surface of a PET film having a thickness of 50 μm, and cross-linked by heating at 80 ° C for 3 minutes to form a radiation-curable second bond having a thickness of 30 μm. Agent layer.
<膠粘劑層的製作><Production of Adhesive Layer>
關於本比較例的膠粘劑層,使用與實施例9同樣的膠粘劑層。The adhesive layer similar to that of Example 9 was used for the adhesive layer of this comparative example.
<半導體裝置製造用薄膜的製作><Production of Thin Film for Semiconductor Device Manufacturing>
作為在基材層上層疊有第一粘合劑層的載帶,使用與實施例1同樣的載帶。在該載帶的第一粘合劑層上,在常溫下粘貼切出為315mmΦ的第二粘合劑層前驅物。之後,以切出為330mmΦ的膠粘劑層完全覆蓋第二粘合劑層的方式在40℃進行粘貼,由此,製作本比較例的半導體裝置製造用薄膜。As the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer, the same carrier tape as in Example 1 was used. On the first adhesive layer of the carrier tape, a second adhesive layer precursor cut out at 315 mmφ was attached at a normal temperature. Thereafter, the adhesive layer having a thickness of 330 mmφ was cut so as to completely cover the second pressure-sensitive adhesive layer, and the film was bonded at 40° C., whereby the film for semiconductor device production of the comparative example was produced.
(比較例5)(Comparative Example 5)
在本比較例中,作為在基材層上層疊有第一粘合劑層的載帶,使用日東電工有限公司製造的商品名GE-300,除此以外,與比較例4同樣操作,製作本比較例的半導體裝置製造用薄膜。In the present comparative example, the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer was produced in the same manner as in Comparative Example 4 except that the product name GE-300 manufactured by Nitto Denko Corporation was used. A film for semiconductor device production of a comparative example.
(比較例6)(Comparative Example 6)
在本比較例中,作為在基材層上層疊有第一粘合劑層的載帶,使用日東電工有限公司製造的商品名BT-315S,除此以外,與比較例4同樣操作,製作本比較例的半導體裝置製造用薄膜。In the present comparative example, the carrier tape in which the first pressure-sensitive adhesive layer was laminated on the base material layer was produced in the same manner as in Comparative Example 4 except that the product name BT-315S manufactured by Nitto Denko Corporation was used. A film for semiconductor device production of a comparative example.
(第二粘合劑層與膠粘劑層之間的剝離強度)(peel strength between the second adhesive layer and the adhesive layer)
由各實施例和比較例製作的半導體裝置製造用薄膜切出長100mm×寬20mm的試樣。然後,在常溫下在膠粘劑層的表面粘貼帶(日東電工有限公司製造,商品名:BT-315),對膠粘劑層進行增強。另外,將第二粘合劑層與膠粘劑層夾緊,使用拉伸試驗機(有限公司島津製作所製造,商品名:AGS-J)測定兩者間的剝離強度。在剝離速度300mm/分鐘、溫度25℃、相對濕度50%Rh的剝離條件下進行。A sample having a length of 100 mm and a width of 20 mm was cut out from the film for manufacturing a semiconductor device produced in each of Examples and Comparative Examples. Then, a tape (manufactured by Nitto Denko Co., Ltd., trade name: BT-315) was attached to the surface of the adhesive layer at a normal temperature to reinforce the adhesive layer. In addition, the second pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer were clamped, and the peel strength between the two was measured using a tensile tester (manufactured by Shimadzu Corporation, trade name: AGS-J). This was carried out under the peeling conditions of a peeling speed of 300 mm/min, a temperature of 25 ° C, and a relative humidity of 50% Rh.
(第一粘合劑層與第二粘合劑層之間的剝離力)(peeling force between the first adhesive layer and the second adhesive layer)
從各實施例和比較例製作的半導體裝置製造用薄膜上將膠粘劑層剝離。接著,由膠粘劑層剝離後的各半導體裝置製造用薄膜切出長100mm×寬20mm的試樣。然後,在常溫下在第二粘合劑層的表面粘貼膠帶(日東電工有限公司製造,商品名:BT-315),對第二粘合劑層進行增強。另外,將第二粘合劑層與第一粘合劑層夾緊,使用拉伸試驗機(有限公司島津製作所制,商品名:AGS-J)測定兩者間的剝離強度。在剝離速度300mm/分鐘、溫度25℃、相對濕度50%Rh的剝離條件下進行。The adhesive layer was peeled off from the film for semiconductor device production produced in each of the examples and the comparative examples. Next, a sample having a length of 100 mm and a width of 20 mm was cut out from each of the films for manufacturing a semiconductor device after the adhesive layer was peeled off. Then, a tape (manufactured by Nitto Denko Co., Ltd., trade name: BT-315) was attached to the surface of the second pressure-sensitive adhesive layer at room temperature to enhance the second pressure-sensitive adhesive layer. In addition, the second pressure-sensitive adhesive layer was clamped to the first pressure-sensitive adhesive layer, and the peel strength between the two was measured using a tensile tester (manufactured by Shimadzu Corporation, trade name: AGS-J). This was carried out under the peeling conditions of a peeling speed of 300 mm/min, a temperature of 25 ° C, and a relative humidity of 50% Rh.
(第一粘合劑層與SUS間的剝離力)(peeling force between the first adhesive layer and SUS)
從各實施例和比較例製作的半導體裝置製造用薄膜上將膠粘劑層和第二粘合劑層剝離。接著,由膠粘劑層和第二粘合劑層剝離後的各半導體裝置製造用薄膜切出長100mm×寬20mm的試樣。然後,使用2kg的輥在第一粘合劑層的表面粘貼SUS-304BA板。之後,將第一粘合劑層與SUS304-BA板夾緊,使用拉伸試驗機(有限公司島津製作所制,商品名:AGS-J)測定兩者間的剝離強度。在剝離速度300mm/分鐘、溫度25℃、相對濕度50%Rh的剝離條件下進行。The adhesive layer and the second pressure-sensitive adhesive layer were peeled off from the film for semiconductor device production produced in each of the examples and the comparative examples. Next, a sample having a length of 100 mm and a width of 20 mm was cut out from each of the films for manufacturing a semiconductor device after the adhesive layer and the second pressure-sensitive adhesive layer were peeled off. Then, a SUS-304BA plate was stuck on the surface of the first adhesive layer using a 2 kg roller. Thereafter, the first pressure-sensitive adhesive layer was clamped to a SUS304-BA plate, and the peel strength between the two was measured using a tensile tester (manufactured by Shimadzu Corporation, trade name: AGS-J). This was carried out under the peeling conditions of a peeling speed of 300 mm/min, a temperature of 25 ° C, and a relative humidity of 50% Rh.
(環粘貼性)(ring adhesion)
使用各實施例和比較例各自的半導體裝置製造用薄膜,通過以下的要點對切割環粘貼性進行評價。The film for semiconductor device production of each of the examples and the comparative examples was used, and the adhesiveness of the dicing ring was evaluated by the following points.
從半導體裝置製造用薄膜上將隔片剝離後,在25℃下在其第一粘合劑層上輥壓接切割環而進行粘貼。此時,將可以在不產生皺褶的情況下進行粘貼的情況評價為○、將產生皺褶的情況評價為×,對環粘貼性進行評價。結果如表1~表3所示。After the separator was peeled off from the film for semiconductor device production, the dicing ring was pressure-bonded to the first pressure-sensitive adhesive layer at 25 ° C to bond it. In this case, the case where the sticking was performed without wrinkles was evaluated as ○, and the wrinkle was evaluated as ×, and the loop adhesiveness was evaluated. The results are shown in Tables 1 to 3.
(再加工(rework)性)(rework)
使用各實施例和比較例各自的半導體裝置製造用薄膜,通過以下的要點對再加工性進行評價。The film for semiconductor device production of each of the examples and the comparative examples was used, and the reworkability was evaluated by the following points.
從半導體裝置製造用薄膜上將隔片剝離後,在25℃下在其第一粘合劑層上輥壓接切割環而進行粘貼。由粘貼有半導體裝置製造用薄膜的環上將半導體裝置製造用薄膜剝離,將環上未確認有第一粘合劑層殘渣(膠糊殘留)的情況評價為○、將確認有該殘渣的情況評價為×,對再加工性進行評價。結果如表1~表3所示。After the separator was peeled off from the film for semiconductor device production, the dicing ring was pressure-bonded to the first pressure-sensitive adhesive layer at 25 ° C to bond it. The film for semiconductor device production was peeled off from the ring to which the film for semiconductor device production was bonded, and the case where the first adhesive layer residue (residual residue) was not confirmed on the ring was evaluated as ○, and the residue was confirmed. For X, the reworkability was evaluated. The results are shown in Tables 1 to 3.
(玻璃化轉變溫度(Tg)的測定)(Measurement of glass transition temperature (Tg))
各實施例和比較例中使用的丙烯酸類共聚物的玻璃化轉變溫度,使用粘彈性測定裝置(Rheometic Scientific公司制ARES),以10℃/分鐘的升溫速度由頻率1Hz下的Tan(G”(損耗彈性模量)/G’(儲能彈性模量))進行測定。The glass transition temperature of the acrylic copolymer used in each of the examples and the comparative examples was determined by a viscoelasticity measuring apparatus (ARES manufactured by Rheometic Scientific Co., Ltd.) at a temperature increase rate of 10 ° C/min from Tan (G" at a frequency of 1 Hz ( The loss elastic modulus) / G' (storage elastic modulus) was measured.
(晶片粘貼性、晶片飛散、晶片污染性及拾取性)( wafer stickiness, wafer scattering, wafer contamination, and pick-up)
使用各實施例和比較例的各自的半導體裝置製造用薄膜,通過以下的要點實際進行從半導體晶片的背面磨削製程至拾取製程對晶片粘貼性、晶片飛散、晶片污染性及拾取性進行評價。Using the film for semiconductor device manufacturing of each of the examples and the comparative examples, the wafer sticking property, the wafer scattering, the wafer contamination property, and the pick-up property were evaluated from the back surface grinding process of the semiconductor wafer to the pick-up process by the following points.
對半導體晶片(直徑12英寸、厚度0.6mm)進行背面研磨處理,使用厚度0.05mm的鏡面晶片作為工件。從半導體裝置製造用薄膜上將隔片剝離後,在40℃下將鏡面晶片輥壓接在其膠粘劑層上進行粘貼。此時,將可以無皺褶粘貼的情況評價為○、將產生皺褶的情況評價為×,對晶片粘貼性進行評價。結果如表1~表3所示。另外,進行切割,形成20個半導體晶片。切割中,進行全切割以得到10mm見方的晶片尺寸。另外,切割中,在達到半導體晶片的一半厚度為止使用下述的切割刀片Z1。另外,在達到第二粘合劑層的一半厚度為止使用下述的切割刀片Z2。另外,根據切割刀片Z1和Z2的種類,可以將切割條件進行以下變更。切割時產生半導體晶片的晶片飛散的情況評價為○、不產生晶片飛散的情況評價為×,對晶片飛散進行評價。結果如表1~表3所示。A semiconductor wafer (12 inches in diameter and 0.6 mm in thickness) was subjected to back grinding treatment using a mirror wafer having a thickness of 0.05 mm as a workpiece. After the separator was peeled off from the film for semiconductor device production, the mirror wafer roll was pressure-bonded to the adhesive layer at 40 ° C to be pasted. At this time, the case where the wrinkles were not affixed was evaluated as ○, and the case where wrinkles were generated was evaluated as ×, and the wafer adhesiveness was evaluated. The results are shown in Tables 1 to 3. Further, cutting was performed to form 20 semiconductor wafers. In the cutting, full cutting was performed to obtain a wafer size of 10 mm square. Further, in the dicing, the following dicing blade Z1 was used up to half the thickness of the semiconductor wafer. Further, the following cutting blade Z2 was used until the thickness of the second adhesive layer was half. Further, depending on the type of the cutting blades Z1 and Z2, the cutting conditions can be changed as follows. The case where the wafer of the semiconductor wafer was scattered during the dicing was evaluated as ○, and the case where the wafer was not scattered was evaluated as ×, and the wafer scattering was evaluated. The results are shown in Tables 1 to 3.
<晶片磨削條件><Wafer grinding conditions>
磨削装置:DISCO公司製造,DFG-8560Grinding device: manufactured by DISCO, DFG-8560
半導體晶片:12英寸直徑(從厚度0.6mm背面磨削至0.05mm)Semiconductor wafer: 12" diameter (from 0.6mm back thickness to 0.05mm)
<晶片粘貼條件>< wafer paste condition>
粘貼裝置:日東精機製造,MA-3000IIPasting device: Nitto Seiki Manufacturing, MA-3000II
粘貼速度計:10mm/分鐘Paste speed meter: 10mm/min
粘貼壓力:0.15MPaPasting pressure: 0.15MPa
粘貼時的平臺溫度:40℃Platform temperature when pasting: 40 ° C
<切割條件><Cutting conditions>
切割装置:DISCO公司製造,DFD-6361Cutting device: manufactured by DISCO, DFD-6361
切割環:2-12-1(DISCO公司製造)Cutting ring: 2-12-1 (manufactured by DISCO)
切割速度:30mm/秒Cutting speed: 30mm / sec
切割刀片:Cutting blade:
Z1:DISCO公司製造的NBC-ZH2030-SE27HCDDZ1: NBC-ZH2030-SE27HCDD manufactured by DISCO
切割刀片轉速:40,000rpmCutting blade speed: 40,000 rpm
刀片高度:半導體晶片厚度的一半Blade height: half the thickness of the semiconductor wafer
Z2:DISCO公司製造的NBC-ZH1030-SE27HCBBZ2: NBC-ZH1030-SE27HCBB manufactured by DISCO
切割刀片轉速:45,000rpmCutting blade speed: 45,000 rpm
刀片高度:第二粘合劑層的厚度的一半Blade height: half the thickness of the second adhesive layer
切割方式:A模式/階梯式切割Cutting method: A mode / step cutting
晶片晶片尺寸:10.0mm見方Wafer chip size: 10.0mm square
然後,將半導體裝置製造用薄膜進行牽引,進行使各晶片間為規定間隔的擴展(expanded)製程。另外,以從各半導體裝置製造用薄膜的基材層一側用針上推的方式拾取半導體晶片,對拾取性進行評價。具體而言,連續地拾取20個半導體晶片,併用顯微鏡觀察各半導體晶片。拾取條件如下所述。觀察的結果,在半導體晶片的側面附著的毛刺或細須的數量為0的情況評價為○、為1~10個的情況評價為△、為11個以上的情況評價為×,對晶片污染性進行評價。另外,在拾取高度為0μm~600μm範圍內進行半導體晶片的拾取,全部拾取的情況評價為○、一個也不能拾取的情況評價為×,對拾取性進行評價。結果如表1~表3所示。Then, the film for semiconductor device manufacturing is pulled, and an expanded process for setting a predetermined interval between the wafers is performed. In addition, the semiconductor wafer was picked up by the push-up from the side of the base material layer of each thin film for semiconductor device manufacturing, and the pick-up property was evaluated. Specifically, 20 semiconductor wafers were continuously picked up, and each semiconductor wafer was observed with a microscope. The pickup conditions are as follows. As a result of the observation, the case where the number of burrs or whiskers attached to the side surface of the semiconductor wafer was 0 was evaluated as ○, when it was 1 to 10, it was evaluated as Δ, and when it was 11 or more, it was evaluated as ×, and the wafer was contaminated. Conduct an evaluation. In addition, the semiconductor wafer was picked up in the range of the pickup height of 0 μm to 600 μm, and the case where all the pickups were evaluated as ○ and the case where the pickup could not be picked up was evaluated as ×, and the pickup property was evaluated. The results are shown in Tables 1 to 3.
<拾取條件><Picking conditions>
拾取裝置:SPA-300(新川有限公司製造)Pickup device: SPA-300 (made by Shinkawa Co., Ltd.)
針數:5根Number of stitches: 5
針種類:直徑0.7mm、銳角度數15°、長度10mm、前端R350μmNeedle type: diameter 0.7mm, sharp angle 15°, length 10mm, front end R350μm
拾取時間:1000毫秒Pick up time: 1000 milliseconds
拾取速度:5mm/秒Picking speed: 5mm / sec
拾取高度:如前所述Pick height: as mentioned
(彎曲剛性的測定)(Measurement of bending rigidity)
測定將基材層、第一粘合劑層和第二粘合劑層依次粘貼得到的薄膜(切割薄膜)的厚度。之後,切割為10mm寬度,使用動態粘彈性測定裝置(RSA-III,Rheometrics Scientific公司製造)以5℃/分鐘的升溫速度來測定拉伸儲能彈性模量,並記錄25℃時的拉伸儲能彈性模量的值(E[單位Pa])。而且,求出由E×I計算的彎曲剛性。在此,I為以b×T3 /12表示的截面二次矩,b為切割薄膜的試驗片的寬度10(mm),T為切割薄膜的厚度(mm),E為切割薄膜的25℃下的拉伸儲能彈性模量(Pa)。結果如表1~表3所示。The thickness of the film (cut film) obtained by sequentially bonding the base material layer, the first pressure-sensitive adhesive layer, and the second pressure-sensitive adhesive layer was measured. Thereafter, the film was cut to a width of 10 mm, and the tensile storage elastic modulus was measured at a temperature elevation rate of 5 ° C / minute using a dynamic viscoelasticity measuring device (RSA-III, manufactured by Rheometrics Scientific Co., Ltd.), and the tensile storage at 25 ° C was recorded. The value of the elastic modulus (E [unit Pa]). Further, the bending rigidity calculated by E × I was obtained. Here, I is the second moment of the section indicated by b×T 3 /12, b is the width (mm) of the test piece of the cut film, T is the thickness (mm) of the cut film, and E is 25 ° C of the cut film. The tensile energy storage elastic modulus (Pa). The results are shown in Tables 1 to 3.
(綜合判定)(Comprehensive judgment)
環粘貼性、晶片粘貼性、晶片污染性、晶片飛散、拾取性、再加工性的評價結果中,即使存在一個×的情況也評價為×,全部評價結果為○的情況評價為○。結果如表1~表3所示。In the evaluation results of the ring adhesiveness, the wafer adhesiveness, the wafer contamination, the wafer scattering, the pick-up property, and the reworkability, even if there is one ×, it is evaluated as ×, and when all the evaluation results are ○, it is evaluated as ○. The results are shown in Tables 1 to 3.
(結果)(result)
從所述表1和表2可以看出,實施例1~14的半導體裝置製造用薄膜通過形成為在基材層上依次設置有第一粘合劑層和第二粘合劑層的結構,從而在切割時,可以防止薄型且大面積的半導體晶片的晶片飛散。另外,在半導體晶片的側面不附著毛刺或細須,也可以防止半導體晶片的污染。另外,半導體晶片的拾取時,全部半導體晶片都可以良好地拾取,並且可以確認剝離性也優良。As can be seen from Tables 1 and 2, the films for manufacturing a semiconductor device of Examples 1 to 14 are formed by sequentially providing a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer on a substrate layer. Thereby, it is possible to prevent the wafer of the thin and large-area semiconductor wafer from scattering during the dicing. In addition, burrs or whiskers are not attached to the side surface of the semiconductor wafer, and contamination of the semiconductor wafer can be prevented. Further, at the time of picking up the semiconductor wafer, all of the semiconductor wafers can be picked up satisfactorily, and it is confirmed that the peeling property is also excellent.
另一方面,如比較例1的半導體裝置製造用薄膜那樣使用OPP薄膜代替第二粘合劑層的情況下,由於切割時切割刀片切割到OPP薄膜的一部分,因此可以確認到起因於OPP薄膜的切削屑以毛刺或細須的形態附著在半導體晶片的側面等。另外,與膠粘劑層的剝離性差,因此也產生半導體晶片的拾取不良。另外,如比較例2的半導體裝置製造用薄膜那樣使用經聚矽氧烷處理後的PE薄膜代替第二粘合劑層的情況下,由於切割時切割刀片切割到PE薄膜的一部分,因此可以確認到起因於PE薄膜的切削屑以毛刺或細須的形態附著在半導體晶片的側面等。另外,如比較例4的半導體裝置製造用薄膜那樣未對第二粘合劑層照射紫外線的情況下,第二粘合劑層未固化,與膠粘劑層的剝離性顯著減少,產生半導體晶片的拾取不良。另外,如比較例5的半導體裝置製造用薄膜那樣彎曲剛性小的情況下,晶片粘貼時產生皺褶,因此不好。另外,如比較例6的半導體裝置製造用薄膜那樣彎曲剛性大的情況下,拾取時薄膜不彎曲,不產生膠粘劑層與第二粘合劑層的剝離起點,因此不良。On the other hand, when the OPP film was used instead of the second adhesive layer as in the film for semiconductor device manufacturing of Comparative Example 1, since the dicing blade was cut into a part of the OPP film at the time of cutting, it was confirmed that the OPP film was caused. The chips are attached to the side surface of the semiconductor wafer or the like in the form of burrs or whiskers. Further, since the peeling property with the adhesive layer is inferior, pickup defects of the semiconductor wafer are also caused. Further, when a PE film treated with polysiloxane is used in place of the second pressure-sensitive adhesive layer as in the film for semiconductor device production of Comparative Example 2, since the dicing blade is cut into a part of the PE film at the time of cutting, it can be confirmed. The chips resulting from the PE film are attached to the side surface of the semiconductor wafer in the form of burrs or whiskers. Further, when the second pressure-sensitive adhesive layer is not irradiated with ultraviolet rays as in the film for semiconductor device production of Comparative Example 4, the second pressure-sensitive adhesive layer is not cured, and the peeling property with the pressure-sensitive adhesive layer is remarkably reduced to cause pick-up of the semiconductor wafer. bad. In addition, when the bending rigidity is small as in the film for manufacturing a semiconductor device of Comparative Example 5, wrinkles are generated during wafer bonding, which is not preferable. Further, when the bending rigidity is large as in the film for manufacturing a semiconductor device of Comparative Example 6, the film is not bent at the time of picking up, and the peeling starting point of the adhesive layer and the second pressure-sensitive adhesive layer does not occur, which is disadvantageous.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,故本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
1...半導體裝置製造用薄膜1. . . Semiconductor device manufacturing film
11...基材層11. . . Substrate layer
12...第一粘合劑層12. . . First adhesive layer
13...第二粘合劑層13. . . Second adhesive layer
14...膠粘劑層14. . . Adhesive layer
14a...周邊部14a. . . Peripheral part
15...隔片15. . . bead
18...切割環的粘貼部分18. . . Pasting part of the cutting ring
21...半導體晶片twenty one. . . Semiconductor wafer
22...半導體晶片twenty two. . . Semiconductor wafer
23...切割環twenty three. . . Cutting ring
24...切割刀片twenty four. . . Cutting blade
圖1是表示本發明的一個實施方式的半導體裝置製造用薄膜的剖面示意圖。1 is a schematic cross-sectional view showing a film for manufacturing a semiconductor device according to an embodiment of the present invention.
圖2是從隔片一側觀看所述半導體裝置製造用薄膜時的俯視圖。FIG. 2 is a plan view of the semiconductor device manufacturing film viewed from the side of the spacer.
圖3是使用所述半導體裝置製造用薄膜的半導體裝置的製造方法的說明圖,圖3(a)表示在半導體裝置製造用薄膜上粘貼半導體晶片的製程,圖3(b)表示切割所述半導體晶片的製程,圖3(c)表示拾取半導體晶片的製程。3 is an explanatory view showing a method of manufacturing a semiconductor device using the thin film for manufacturing a semiconductor device, wherein FIG. 3(a) shows a process of attaching a semiconductor wafer to a thin film for manufacturing a semiconductor device, and FIG. 3(b) shows cutting the semiconductor. The process of the wafer, FIG. 3(c) shows the process of picking up the semiconductor wafer.
1...半導體裝置製造用薄膜1. . . Semiconductor device manufacturing film
11...基材層11. . . Substrate layer
12...第一粘合劑層12. . . First adhesive layer
13...第二粘合劑層13. . . Second adhesive layer
14...膠粘劑層14. . . Adhesive layer
15...隔片15. . . bead
Claims (16)
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI688633B (en) * | 2014-09-22 | 2020-03-21 | 日商琳得科股份有限公司 | Work fixing sheet having resin layer |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6170290B2 (en) * | 2012-10-11 | 2017-07-26 | 日東電工株式会社 | Laminate |
US20160297180A1 (en) * | 2013-11-22 | 2016-10-13 | Lintec Corporation | Base film for dicing sheet and method of manufacturing base film |
JPWO2015076126A1 (en) * | 2013-11-22 | 2017-03-16 | リンテック株式会社 | Dicing sheet base film, dicing sheet provided with the base film, and method for manufacturing the base film |
CN106104759B (en) * | 2014-03-17 | 2019-05-17 | 琳得科株式会社 | Cutting sheet and the manufacturing method of chip for using the cutting sheet |
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SG11201808212XA (en) * | 2016-03-30 | 2018-10-30 | Lintec Corp | Film adhesive, semiconductor processing sheet, and method for manufacturing semiconductor apparatus |
JP6721398B2 (en) * | 2016-04-22 | 2020-07-15 | 日東電工株式会社 | Dicing die bonding film, dicing die bonding tape, and method for manufacturing semiconductor device |
WO2018181767A1 (en) * | 2017-03-31 | 2018-10-04 | リンテック株式会社 | Semiconductor device production method and adhesive sheet |
CN107760221A (en) * | 2017-10-25 | 2018-03-06 | 上海固柯胶带科技有限公司 | A kind of UV adhesive tapes and preparation method thereof |
CN110144175A (en) * | 2018-02-13 | 2019-08-20 | 日东电工株式会社 | Bonding sheet and bonding laminate |
JP7304143B2 (en) * | 2018-02-13 | 2023-07-06 | 日東電工株式会社 | Adhesive sheet and adhesive sheet laminate |
KR102642969B1 (en) * | 2018-03-27 | 2024-03-04 | 에스케이온 주식회사 | Bettery cell and fabricating method of the same |
CN111048461B (en) * | 2018-10-12 | 2022-06-03 | 瀚宇彩晶股份有限公司 | Release front structure of electronic device and manufacturing method of electronic device |
JP7446773B2 (en) * | 2019-11-07 | 2024-03-11 | 日東電工株式会社 | Dicing tape and dicing die bond film |
KR102172003B1 (en) * | 2019-11-28 | 2020-11-02 | (주)매그나텍 | Method for manufacturing substitute substrate for adhesive |
CN114364761B (en) * | 2020-07-30 | 2024-02-02 | 古河电气工业株式会社 | Adhesive tape for semiconductor processing |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI307545B (en) * | 2002-10-15 | 2009-03-11 | Nitto Denko Corp | Dicing/die-bonding film, method of fixing chipped work and semiconductor device |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4536367B2 (en) * | 2003-12-24 | 2010-09-01 | 東レ・ダウコーニング株式会社 | Sheet for dicing die bonding and manufacturing method thereof |
JP4776189B2 (en) * | 2004-08-03 | 2011-09-21 | 古河電気工業株式会社 | Wafer processing tape |
JP5286084B2 (en) * | 2006-07-19 | 2013-09-11 | 積水化学工業株式会社 | Dicing die bonding tape and semiconductor chip manufacturing method |
KR100816881B1 (en) | 2006-08-31 | 2008-03-26 | 한국화학연구원 | The composition of a film-typed adhesive used in both dicing of wafer and bonding of the diced chips |
JP2009246216A (en) | 2008-03-31 | 2009-10-22 | Sumitomo Bakelite Co Ltd | Semiconductor processing adhesive tape |
-
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Publication number | Priority date | Publication date | Assignee | Title |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI688633B (en) * | 2014-09-22 | 2020-03-21 | 日商琳得科股份有限公司 | Work fixing sheet having resin layer |
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