TW201812878A - Method of manufacturing semiconductor chip having protective film and method of manufacturing semiconductor device - Google Patents
Method of manufacturing semiconductor chip having protective film and method of manufacturing semiconductor device Download PDFInfo
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- TW201812878A TW201812878A TW106113978A TW106113978A TW201812878A TW 201812878 A TW201812878 A TW 201812878A TW 106113978 A TW106113978 A TW 106113978A TW 106113978 A TW106113978 A TW 106113978A TW 201812878 A TW201812878 A TW 201812878A
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- Prior art keywords
- protective film
- forming
- film
- meth
- acrylate
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- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- 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
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67092—Apparatus for mechanical treatment
-
- 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
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Dicing (AREA)
- High Energy & Nuclear Physics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本發明係關於一種附有保護膜的半導體晶片的製造方法以及半導體裝置的製造方法。 The present invention relates to a method for manufacturing a semiconductor wafer with a protective film and a method for manufacturing a semiconductor device.
本申請案主張基於2016年4月28日在日本提出申請之日本特願2016-92010號的優先權，並將該申請案的內容引用至本文中。 This application claims priority based on Japanese Patent Application No. 2016-92010 filed in Japan on April 28, 2016, and the contents of this application are incorporated herein by reference.
近年來，業界使用稱為所謂倒裝(face down)方式之安裝方法製造半導體裝置。倒裝方式中，使用於電路面上具有凸塊(bump)等電極之半導體晶片，將前述電極與基板接合。因此，會有半導體晶片中的與電路面為相反側的背面裸露之情形。 In recent years, the industry has been manufacturing semiconductor devices using a so-called face-down mounting method. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. Therefore, there may be cases where the back surface of the semiconductor wafer opposite to the circuit surface is exposed.
會有於該裸露之半導體晶片的背面形成含有有機材料之樹脂膜作為保護膜，從而以附有保護膜的半導體晶片 之形式組入至半導體裝置之情形。 There may be a case where a resin film containing an organic material is formed as a protective film on the back surface of the bare semiconductor wafer, and it is incorporated into a semiconductor device in the form of a semiconductor wafer with a protective film.
保護膜係用以防止在切割步驟或封裝之後半導體晶片產生龜裂。 The protective film is used to prevent cracking of the semiconductor wafer after the dicing step or packaging.
為了形成此種保護膜，例如使用於支持片上具備用以形成保護膜之保護膜形成用膜而成之保護膜形成用複合片。保護膜形成用複合片中，可使保護膜形成用膜藉由硬化而形成保護膜，進而可利用支持片作為切割片(dicing sheet)，從而可製成保護膜形成用膜與切割片形成為一體之保護膜形成用複合片。 In order to form such a protective film, for example, a composite sheet for forming a protective film, which is formed on a supporting sheet and includes a film for forming a protective film for forming a protective film, is used. In the protective film forming composite sheet, the protective film forming film can be hardened to form a protective film, and further, a supporting sheet can be used as a dicing sheet, so that the protective film forming film and the dicing sheet can be formed into Integrated protective film forming composite sheet.
作為此種保護膜形成用複合片，例如至今主要利用具備熱硬化性之保護膜形成用膜而成之保護膜形成用複合片，前述熱硬化性之保護膜形成用膜係藉由加熱而硬化，藉此形成保護膜。該情形時，例如於半導體晶圓的背面(與電極形成面為相反側的面)藉由熱硬化性之保護膜形成用膜貼附保護膜形成用複合片後，藉由加熱使保護膜形成用膜硬化而成為保護膜，藉由切割將半導體晶圓連同保護膜一起分割而製成半導體晶片。然後，將半導體晶片在保持貼附有該保護膜之狀態下直接自支持片拉離而進行拾取。再者，亦存在保護膜形成用膜之硬化及切割以與此相反之順序進行之情形。 As such a composite sheet for forming a protective film, for example, a composite sheet for forming a protective film has been mainly formed by a film having a thermosetting protective film, and the film for forming a protective film forming a thermosetting film is hardened by heating. , Thereby forming a protective film. In this case, for example, a protective film forming composite sheet is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface) with a thermosetting film, and then the protective film is formed by heating. The film is hardened to form a protective film, and the semiconductor wafer and the protective film are divided by dicing to produce a semiconductor wafer. Then, the semiconductor wafer is directly picked up from the support sheet while the protective film is attached, and picked up. Further, the curing and cutting of the protective film-forming film may be performed in the reverse order.
但是，熱硬化性之保護膜形成用膜之加熱硬化通常需 要數小時左右之長時間，因此期望縮短硬化時間。針對上述情形，業界正研究將可藉由照射紫外線等能量線而硬化之保護膜形成用膜用於形成保護膜。例如揭示有：形成於剝離膜上之能量線硬化型保護膜(參照專利文獻1)；可形成高硬度且對半導體晶片之密接性優異之保護膜之能量線硬化型晶片保護用膜(參照專利文獻2)。 However, heat curing of a film for forming a thermosetting protective film usually requires several hours, and therefore it is desirable to shorten the curing time. In view of the above circumstances, the industry is studying the use of a protective film-forming film that can be cured by irradiating energy rays such as ultraviolet rays, to form a protective film. For example, it is disclosed that an energy ray-curable protective film formed on a release film (see Patent Document 1); an energy ray-curable wafer protective film that can form a protective film with high hardness and excellent adhesion to a semiconductor wafer (see Patent) Reference 2).
[先前技術文獻] [Prior technical literature]
[專利文獻] [Patent Literature]
專利文獻1：日本特許第5144433號公報。 Patent Document 1: Japanese Patent No. 5144433.
專利文獻2：日本特開2010-031183號公報。 Patent Document 2: Japanese Patent Application Laid-Open No. 2010-031183.
但是，使用專利文獻1及專利文獻2中所揭示之能量線硬化型晶片保護用膜製造半導體晶片、半導體裝置之過程中，切割半導體晶圓時，存在刀片堵塞之問題，或者於保護層產生小缺損，亦即碎片之虞。 However, in the process of manufacturing semiconductor wafers and semiconductor devices using the energy-ray-curable wafer protection films disclosed in Patent Documents 1 and 2, there is a problem that the blade is clogged when the semiconductor wafer is cut, or a small amount of the protective layer is generated. Defects, that is, the risk of debris.
另外，對於拾取後的附有保護膜的半導體晶片，為了於下一步驟中使用，會有包裝於如圖8所示之壓紋載帶(emboss carrier tape)102，且該壓紋載帶102以捲繞於捲盤(reel)之狀態進行保管、搬送、或商業交易之情形。收納於前述壓紋載帶102時，通常對於拾取後的附有保護膜的半導體晶片101係使半導體晶片的電路面側朝向壓紋載 帶102的口袋(pocket)102a的底部，使保護膜側朝向前述口袋102a的開口部進行收納。貼附構成壓紋載帶102的蓋部之蓋帶103，藉此將前述開口部封閉而進行包裝。將附有保護膜的半導體晶片101於下一步驟中使用時，例如，將包裝有附有保護膜的半導體晶片101之壓紋載帶102連同捲盤一起設置於貼片機(mounter)，對基板安裝附有保護膜的半導體晶片101。此時，剝離前述蓋帶103，自壓紋載帶102的口袋102a取出附有保護膜的半導體晶片101，但會有附有保護膜的半導體晶片101藉由保護膜附著於蓋帶103而成為對基板安裝附有保護膜的半導體晶片101之安裝步驟之障礙之情形。 In addition, the picked-up semiconductor wafer with a protective film is packaged in an emboss carrier tape 102 as shown in FIG. 8 for use in the next step, and the embossed carrier tape 102 When it is wound on a reel for storage, transportation, or commercial transactions. When stored in the embossed carrier tape 102, the semiconductor wafer 101 with a protective film after picking up is usually directed toward the bottom of the pocket 102a of the embossed carrier tape 102 with the circuit surface side of the semiconductor wafer and the protective film It is accommodated toward the opening part of the said pocket 102a. A cover tape 103 constituting a cover portion of the embossed carrier tape 102 is attached, and the aforementioned opening portion is closed to be packed. When the protective wafer-attached semiconductor wafer 101 is used in the next step, for example, the embossed carrier tape 102 containing the protective wafer-attached semiconductor wafer 101 is set in a mounter together with a reel, and A semiconductor wafer 101 with a protective film is mounted on the substrate. At this time, the cover tape 103 is peeled off, and the semiconductor wafer 101 with the protective film is taken out from the pocket 102a of the embossed carrier tape 102. However, the semiconductor wafer 101 with the protective film is attached to the cover tape 103 by the protective film and becomes In the case where the mounting step of the semiconductor wafer 101 with a protective film mounted on the substrate is troublesome.
因此，本發明之目的在於提供一種附有保護膜的半導體晶片的製造方法以及半導體裝置的製造方法，前述附有保護膜的半導體晶片的製造方法具有以下特性：切割半導體晶圓時，不易產生刀片堵塞或碎片，將附有保護膜的半導體晶片收納於壓紋載帶的口袋時，可抑制附有保護膜的半導體晶片附著於蓋帶。 Therefore, an object of the present invention is to provide a method for manufacturing a semiconductor wafer with a protective film and a method for manufacturing a semiconductor device. The aforementioned method for manufacturing a semiconductor wafer with a protective film has the following characteristics: when a semiconductor wafer is cut, it is difficult to produce a blade When the semiconductor wafer with the protective film is clogged or chipped, the semiconductor wafer with the protective film is prevented from adhering to the cover tape when the semiconductor wafer with the protective film is stored in the pocket of the embossed carrier tape.
為了解決上述課題，本發明之附有保護膜的半導體晶片的製造方法係於半導體晶圓貼附能量線硬化性之保護膜形成用膜後，對前述保護膜形成用膜照射能量線而使前述保護膜形成用膜硬化，接著對前述半導體晶圓進行切 割；且對前述保護膜形成用膜照射能量線而成為保護膜時，前述保護膜的拉伸彈性率為500MPa以上。 In order to solve the above-mentioned problem, a method for manufacturing a semiconductor wafer with a protective film according to the present invention is to attach an energy ray-curable protective film-forming film to a semiconductor wafer, and then irradiate the protective film-forming film with energy rays to cause the aforementioned When the film for forming a protective film is cured, and then the semiconductor wafer is diced; and when the film for forming the protective film is irradiated with energy rays to become a protective film, the tensile elastic modulus of the protective film is 500 MPa or more.
本發明之附有保護膜的半導體晶片的製造方法中，可對前述保護膜形成用膜照射能量線而成為保護膜後，將前述保護膜貼附於支持片，接著對前述半導體晶圓進行切割。 In the method for manufacturing a semiconductor wafer with a protective film according to the present invention, after the protective film forming film is irradiated with energy rays to form a protective film, the protective film is attached to a support sheet, and then the semiconductor wafer is diced. .
本發明之附有保護膜的半導體晶片的製造方法中，可將於支持片上具備前述保護膜形成用膜而成之保護膜形成用複合片的前述保護膜形成用膜側貼附於前述半導體晶圓。 In the method for manufacturing a semiconductor wafer with a protective film of the present invention, the protective film forming film side of the protective film forming composite sheet including the protective film forming film on a supporting sheet may be attached to the semiconductor crystal. circle.
本發明之半導體裝置的製造方法係拾取藉由上述中任一項所記載之製造方法所獲得之附有保護膜的半導體晶片，將前述半導體晶片連接於基板。 A method of manufacturing a semiconductor device according to the present invention is to pick up a semiconductor wafer with a protective film obtained by the manufacturing method described in any one of the above, and connect the semiconductor wafer to a substrate.
根據本發明，提供一種附有保護膜的半導體晶片的製造方法以及半導體裝置的製造方法，前述附有保護膜的半導體晶片的製造方法中，切割半導體晶圓時不易產生刀片堵塞或碎片，將附有保護膜的半導體晶片收納於壓紋載帶的口袋時可抑制附有保護膜的半導體晶片附著於蓋帶。 According to the present invention, there are provided a method for manufacturing a semiconductor wafer with a protective film and a method for manufacturing a semiconductor device. In the aforementioned method for manufacturing a semiconductor wafer with a protective film, blade clogging or chipping is unlikely to occur when cutting a semiconductor wafer. When the semiconductor wafer with a protective film is stored in the pocket of the embossed carrier tape, the semiconductor wafer with the protective film can be prevented from adhering to the cover tape.
1A、1B、1C、1D、1E‧‧‧保護膜形成用複合片 1A, 1B, 1C, 1D, 1E‧‧‧ composite film for protective film formation
2F‧‧‧保護膜形成用片 2F‧‧‧Protective film forming sheet
10‧‧‧支持片 10‧‧‧ Support
10a‧‧‧(支持片的)表面 10a‧‧‧ surface
11‧‧‧基材 11‧‧‧ Substrate
11a‧‧‧(基材的)表面 11a‧‧‧ surface (of the substrate)
12‧‧‧黏著劑層 12‧‧‧ Adhesive layer
12a‧‧‧(黏著劑層的)表面 12a‧‧‧ (adhesive layer) surface
13、23‧‧‧保護膜形成用膜 13, 23‧‧‧ film for protective film formation
13'‧‧‧保護膜 13'‧‧‧ protective film
13a、23a‧‧‧(保護膜形成用膜的一方的)表面 13a, 23a ‧‧‧ (one side of the film for protective film formation)
13b‧‧‧(保護膜形成用膜的另一方的)表面 13b‧‧‧ (the other side of the film for forming a protective film)
15‧‧‧剝離膜 15‧‧‧ peeling film
15'‧‧‧第1剝離膜 15'‧‧‧The first release film
15"‧‧‧第2剝離膜 15 "‧‧‧Second Release Film
16‧‧‧治具用接著劑層 16‧‧‧ Adhesive layer for fixture
16a‧‧‧(治具用接著劑層的)表面 16a‧‧‧ (the surface of the adhesive layer for the fixture)
17‧‧‧環狀框 17‧‧‧ ring frame
18‧‧‧半導體晶圓 18‧‧‧Semiconductor wafer
19‧‧‧半導體晶片 19‧‧‧Semiconductor wafer
20‧‧‧切割刀片 20‧‧‧ cutting blade
21‧‧‧能量線照射裝置 21‧‧‧Energy ray irradiation device
101‧‧‧附有保護膜的半導體晶片 101‧‧‧ semiconductor wafer with protective film
102‧‧‧壓紋載帶 102‧‧‧ Embossed Carrier Tape
102a‧‧‧(壓紋載帶的)口袋 102a‧‧‧ (embossed carrier tape) pocket
103‧‧‧蓋帶 103‧‧‧ Cover tape
圖1係顯示本發明之附有保護膜的半導體晶片的製造方法之概略圖。 FIG. 1 is a schematic view showing a method for manufacturing a semiconductor wafer with a protective film according to the present invention.
圖2係以示意方式顯示可用於本發明之保護膜形成用複合片的一實施形態之剖視圖。 2 is a cross-sectional view schematically showing an embodiment of a composite sheet for forming a protective film that can be used in the present invention.
圖3係以示意方式顯示可用於本發明之保護膜形成用複合片的另一實施形態之剖視圖。 3 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.
圖4係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 FIG. 4 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.
圖5係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 5 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.
圖6係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 6 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.
圖7係以示意方式顯示可用於本發明之保護膜形成用片的實施形態之剖視圖。 7 is a cross-sectional view schematically showing an embodiment of a sheet for forming a protective film that can be used in the present invention.
圖8係以示意方式顯示將附有保護膜的半導體晶片收納於壓紋載帶的口袋，並貼附蓋帶而封蓋的狀態，以及剝離前述蓋帶後的狀態之剖視圖。 8 is a cross-sectional view schematically showing a state in which a semiconductor wafer with a protective film is stored in a pocket of an embossed carrier tape, a cover tape is attached and sealed, and a state after the cover tape is peeled off.
◇附有保護膜的半導體晶片以及半導體裝置的製造方法 ◇ Semiconductor wafer with protective film and manufacturing method of semiconductor device
圖1係顯示本發明之附有保護膜的半導體晶片的製造方法之概略圖。 FIG. 1 is a schematic view showing a method for manufacturing a semiconductor wafer with a protective film according to the present invention.
本發明之附有保護膜的半導體晶片19的製造方法係於半導體晶圓18貼附能量線硬化性之保護膜形成用膜13後，對保護膜形成用膜13照射能量線而使保護膜形成用 膜13硬化，接著對半導體晶圓18進行切割。 The method for manufacturing a semiconductor wafer 19 with a protective film according to the present invention is to attach an energy ray-curable protective film-forming film 13 to the semiconductor wafer 18, and then irradiate the protective film-forming film 13 with energy rays to form a protective film. The film 13 is hardened, and then the semiconductor wafer 18 is diced.
對保護膜形成用膜13照射能量線而使保護膜形成用膜13硬化後進行切割，藉此切割時之保護膜13'較硬，因此切割半導體晶圓18時不易產生刀片堵塞或碎片。另外，由於保護膜13'的拉伸彈性率較硬為500MPa以上，故而可抑制附有保護膜的半導體晶片附著於蓋帶。 The protective film-forming film 13 is irradiated with energy rays to harden the protective film-forming film 13 and then cut. As a result, the protective film 13 ′ at the time of dicing is hard. Therefore, it is difficult to generate a blade clogging or chipping when cutting the semiconductor wafer 18. In addition, since the tensile elastic modulus of the protective film 13 'is harder than 500 MPa or more, the semiconductor wafer with the protective film can be prevented from adhering to the cover tape.
本發明之附有保護膜的半導體晶片的製造方法中，可對前述保護膜形成用膜照射能量線而成為保護膜後，將前述保護膜貼附於支持片，接著對前述半導體晶圓進行切割。此時，可分別適宜選擇適於半導體晶圓之製品、製造之保護膜形成用膜及支持片而使用。 In the method for manufacturing a semiconductor wafer with a protective film according to the present invention, after the protective film forming film is irradiated with energy rays to form a protective film, the protective film is attached to a support sheet, and then the semiconductor wafer is diced. . In this case, a product suitable for a semiconductor wafer, a film for forming a protective film, and a support sheet suitable for manufacturing can be appropriately selected and used.
該情形之本發明之附有保護膜的半導體晶片的製造方法如下：於半導體晶圓的背面(與電極形成面為相反側的面)貼附能量線硬化性之保護膜形成用膜後，對前述保護膜形成用膜照射能量線而使前述保護膜形成用膜硬化，成為保護膜後，將前述保護膜貼附於支持片，接著對前述半導體晶圓進行切割。 In this case, the method for manufacturing a semiconductor wafer with a protective film according to the present invention is as follows: After attaching a film for forming a protective film of energy ray hardening on the back surface (surface opposite to the electrode formation surface) of the semiconductor wafer, The protective film-forming film is irradiated with energy rays to harden the protective film-forming film, and after the protective film is formed into a protective film, the protective film is attached to a support sheet, and then the semiconductor wafer is diced.
本發明之附有保護膜的半導體晶片的製造方法中，可將於支持片上具備前述保護膜形成用膜而成之保護膜形成用複合片的前述保護膜形成用膜側貼附於前述半導體晶圓，藉此可將貼附步驟簡化。 In the method for manufacturing a semiconductor wafer with a protective film of the present invention, the protective film forming film side of the protective film forming composite sheet including the protective film forming film on a supporting sheet may be attached to the semiconductor crystal. Circle, which simplifies the attaching step.
該情形之本發明之附有保護膜的半導體晶片的製造方法可示於以下。 The manufacturing method of the semiconductor wafer with a protective film of this invention in this case can be shown below.
本發明之附有保護膜的半導體晶片的製造方法如下：將於支持片上具備前述保護膜形成用膜而成之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜貼附於半導體晶圓的背面(與電極形成面為相反側的面)。接著，對前述保護膜形成用膜照射能量線而使前述保護膜形成用膜硬化，接著對前述半導體晶圓進行切割。 A method for manufacturing a semiconductor wafer with a protective film according to the present invention is as follows: a protective film-forming composite sheet comprising the above-mentioned protective film-forming film on a support sheet, and the protective film formation of the protective film-forming composite sheet The film is attached to the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer. Next, the protective film forming film is irradiated with energy rays to harden the protective film forming film, and then the semiconductor wafer is diced.
以下，利用與先前法相同的方法，將附有保護膜的半導體晶片在保持貼附有該保護膜之狀態下直接自支持片拉離而進行拾取，將所獲得之附有保護膜的半導體晶片的半導體晶片倒裝晶片連接於基板的電路面後，製成半導體封裝。然後，使用該半導體封裝，製作目標半導體裝置即可。 Hereinafter, using the same method as in the previous method, the semiconductor wafer with a protective film is pulled out from the support sheet to pick up the semiconductor wafer with the protective film, and the obtained semiconductor wafer with the protective film is picked up. After the semiconductor wafer is flip-chip connected to the circuit surface of the substrate, a semiconductor package is fabricated. Then, using the semiconductor package, a target semiconductor device may be manufactured.
◇保護膜形成用複合片 ◇ Composite sheet for protective film formation
可用於本發明之保護膜形成用複合片於支持片上具備能量線硬化性之保護膜形成用膜。 The protective film-forming composite sheet which can be used in the present invention has a protective film-forming film having energy ray curability on a supporting sheet.
本說明書中，所謂「保護膜形成用膜」意指硬化前之保護膜形成用膜，所謂「保護膜」意指保護膜形成用膜硬化後之膜。 In the present specification, the "film for forming a protective film" means a film for forming a protective film before curing, and the "protective film" means a film after curing the film for forming a protective film.
本發明中，所謂「能量線」意指具有能量量子的電磁波或帶電粒子束，作為前述能量線的示例，可列舉紫外線、放射線、電子束等。 In the present invention, the "energy ray" means an electromagnetic wave or a charged particle beam having an energy quantum. Examples of the energy ray include ultraviolet rays, radiation, and electron beams.
紫外線例如可藉由使用高壓水銀燈、融合(Fusion)H型燈、氙氣燈、黑光燈或LED(Light-Emitting Diode；發光二極體)燈等作為紫外線源進行照射。電子束可照射藉由電子束加速器等所產生之電子束。 The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a Fusion H-type lamp, a xenon lamp, a black light lamp, or an LED (Light-Emitting Diode) lamp as the ultraviolet light source. The electron beam may irradiate an electron beam generated by an electron beam accelerator or the like.
本發明中，所謂「能量線硬化性」意指藉由照射能量線而硬化之性質，所謂「非能量線硬化性」意指即便照射能量線亦不硬化之性質。 In the present invention, "energy ray hardenability" means a property that is hardened by irradiating energy rays, and "non-energy ray hardenability" means a property that does not harden even when energy rays are irradiated.
本說明書中，將依序具備有支持片、能量線硬化性之保護膜形成用膜及半導體晶圓之切割對象稱為「積層體」。 In this specification, a dicing object including a support sheet, a protective film for energy ray hardening, and a semiconductor wafer in this order is referred to as a "laminate".
前述積層體中的支持片與前述保護膜形成用膜之間的黏著力並無特別限定，例如可為80mN/25mm以上，較佳為100mN/25mm以上，更佳為150mN/25mm以上，尤佳為200mN/25mm以上。另外，上限值並無特別限定，例如可為10000mN/25mm以下，可為8000mN/25mm以下，亦可為7000mN/25mm以下。藉由調整為前述下限值以上，切割時保護膜形成用膜與支持片之剝離得到抑制，例如切割時矽晶片之飛散得到抑制。另外，藉由調整為前述上限值以下，隨後藉由照射能量線使之硬化而成為保護膜時，可容易地適當調整前述保護膜與前述支持片之間的黏著力。 The adhesive force between the support sheet in the laminated body and the protective film-forming film is not particularly limited, and may be, for example, 80 mN / 25 mm or more, preferably 100 mN / 25 mm or more, more preferably 150 mN / 25 mm or more, and particularly preferably 200mN / 25mm or more. The upper limit value is not particularly limited, and may be, for example, 10,000 mN / 25 mm or less, 8000 mN / 25 mm or less, or 7000 mN / 25 mm or less. By adjusting it to be more than the aforementioned lower limit value, peeling of the protective film-forming film and the support sheet during dicing is suppressed, and for example, scattering of the silicon wafer during dicing is suppressed. In addition, when the protective film is adjusted to be equal to or lower than the upper limit value and then cured by irradiating energy rays, the adhesive force between the protective film and the support sheet can be easily adjusted appropriately.
本說明書中，前述支持片與前述保護膜形成用膜之間的黏著力可藉由後述之測定方法進行測定。 In this specification, the adhesive force between the said support sheet and the said film for protective film formation can be measured with the measuring method mentioned later.
前述保護膜形成用膜藉由照射能量線而硬化，成為保護膜。該保護膜保護半導體晶圓或半導體晶片的背面(與電極形成面為相反側的面)。保護膜形成用膜為軟質，可容易地貼附於貼附對象物。對前述保護膜形成用膜照射能量線而成為保護膜時，前述保護膜與前述支持片之間的黏著力較佳為50mN/25mm至1500mN/25mm，更佳為52mN/25mm至1450mN/25mm，尤佳為53mN/25mm至1430mN/25mm。 The film for forming a protective film is hardened by irradiating energy rays to become a protective film. This protective film protects the semiconductor wafer or the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface). The film for forming a protective film is soft and can be easily attached to an object to be attached. When the protective film forming film is irradiated with energy rays to become a protective film, the adhesive force between the protective film and the support sheet is preferably 50mN / 25mm to 1500mN / 25mm, more preferably 52mN / 25mm to 1450mN / 25mm, Especially preferred is 53mN / 25mm to 1430mN / 25mm.
藉由前述黏著力為前述下限值以上，拾取附有保護膜的半導體晶片時，目標外的附有保護膜的半導體晶片之拾取得到抑制，從而可高選擇性地拾取目標之附有保護膜的半導體晶片。藉由前述黏著力為前述上限值以下，拾取附有保護膜的半導體晶片時，半導體晶片之破裂及缺損得到抑制。如此，藉由前述黏著力為特定範圍內，保護膜形成用複合片具有良好的拾取適性。 When the adhesive force is equal to or greater than the aforementioned lower limit value, when picking up a semiconductor wafer with a protective film, picking up a semiconductor wafer with a protective film outside the target is suppressed, so that the target with a protective film can be picked up with high selectivity. Semiconductor wafer. When the adhesive force is equal to or lower than the upper limit value, when a semiconductor wafer with a protective film is picked up, cracks and defects of the semiconductor wafer are suppressed. In this way, with the aforementioned adhesive force being within a specific range, the composite sheet for forming a protective film has good pickup suitability.
本說明書中，前述保護膜與前述支持片之間的黏著力可藉由後述之測定方法進行測定。 In this specification, the adhesive force between the said protective film and the said support sheet can be measured by the measuring method mentioned later.
作為本發明之一態樣，前述保護膜的拉伸彈性率較佳為500MPa至10000MPa，更佳為600MPa至8000MPa，尤佳為700MPa至5000MPa。 As one aspect of the present invention, the tensile elastic modulus of the protective film is preferably 500 MPa to 10,000 MPa, more preferably 600 MPa to 8000 MPa, and even more preferably 700 MPa to 5000 MPa.
藉由前述拉伸彈性率為此種範圍，對使用前述保護膜之半導體晶圓進行切割時，不易產生刀片堵塞或碎片，將附有保護膜的半導體晶片收納於壓紋載帶的口袋時，可抑制附有保護膜的半導體晶片附著於蓋帶。 With the aforementioned tensile elasticity ratio in this range, when dicing a semiconductor wafer using the protective film, blade clogging or chipping is unlikely to occur, and when the semiconductor wafer with the protective film is stored in a pocket of an embossed carrier tape, It is possible to prevent the semiconductor wafer with the protective film from being attached to the cover tape.
本說明書中，前述拉伸彈性率可藉由後述之實施例中所記載之測定方法進行測定。 In this specification, the said tensile elasticity can be measured by the measuring method as described in the Example mentioned later.
可用於本發明之保護膜形成用複合片中，前述保護膜形成用膜為能量線硬化性，藉此相較於具備熱硬化性之保護膜形成用膜之以往之保護膜形成用複合片之情形而言，可藉由短時間內之硬化而形成保護膜。 In the composite sheet for forming a protective film according to the present invention, the film for forming a protective film is energy ray-curable, thereby being compared with the conventional composite sheet for forming a protective film having a film for forming a protective film having thermosetting properties. In some cases, a protective film can be formed by curing in a short time.
本發明中，可不使用保護膜形成用複合片，而於半導體晶圓的背面貼附保護膜形成用膜後，於前述保護膜形成用膜貼附支持片，此時的保護膜形成用膜及支持片可適宜使用上述之保護膜形成用複合片之說明中所說明之保護膜形成用膜及支持片。 In the present invention, the protective film forming film may be attached to the back surface of the semiconductor wafer without using the protective film forming composite sheet, and then a support sheet may be attached to the protective film forming film. In this case, the protective film forming film and As the supporting sheet, the protective film-forming film and the supporting sheet described in the description of the protective film-forming composite sheet described above can be suitably used.
本發明中，作為保護膜形成用複合片之使用對象之半導體晶圓或半導體晶片的厚度並無特別限定，就獲得更顯著的本發明之功效而言，較佳為30μm至1000μm，更佳為100μm至300μm。 In the present invention, the thickness of the semiconductor wafer or semiconductor wafer used as a target for forming a protective film-forming composite sheet is not particularly limited. In order to obtain a more significant effect of the present invention, it is preferably 30 μm to 1000 μm, and more preferably 100 μm to 300 μm.
以下，對本發明之構成進行詳細的說明。 Hereinafter, the configuration of the present invention will be described in detail.
◎支持片 ◎ Support
前述支持片可由1層(單層)構成，亦可由2層以上之複數層構成。於支持片由複數層構成之情形時，這些複數層的構成材料及厚度相互可相同亦可不同，只要無損本發明之功效，則這些複數層之組合並無特別限定。 The support sheet may be composed of one layer (single layer), or may be composed of a plurality of layers. In the case where the support sheet is composed of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, as long as the effect of the present invention is not impaired, the combination of the plurality of layers is not particularly limited.
本說明書中，並不限於支持片之情形，所謂「複數層相互可相同亦可不同」意指「可全部層相同，亦可全部層皆不同，還可僅一部分層相同」，進而所謂「複數層相互不同」意指「各層的構成材料及厚度的至少一者相互不同」。 In this specification, it is not limited to the case of supporting films. The so-called "multiple layers may be the same or different from each other" means "all layers may be the same, all layers may be different, and only a part of the layers may be the same." The “layers are different from each other” means “at least one of the constituent materials and thicknesses of the layers are different from each other”.
作為較佳的支持片，例如可列舉：於基材上以直接接觸之方式積層黏著劑層而成之支持片、於基材上經由中間層積層黏著劑層而成之支持片、僅由基材構成之支持片等。 As a preferred support sheet, for example, a support sheet in which an adhesive layer is laminated on a substrate in a direct contact manner, a support sheet in which an adhesive layer is laminated on an intermediate substrate, and only a base Supporting film made of wood, etc.
以下，參照圖式並按照上述支持片之每個種類說明可用於本發明之保護膜形成用複合片的示例。對於以下之說明中所使用之圖，為了易於理解本發明之特徵，方便起見，會有將成為主要部分之部分放大顯示之情形，而並不限於各構成要素的尺寸比率等與實際相同。 Hereinafter, examples of the composite sheet for forming a protective film that can be used in the present invention will be described with reference to the drawings and for each type of the above-mentioned support sheet. As for the drawings used in the following description, in order to easily understand the features of the present invention, for convenience, there may be a case where the main part is enlarged and displayed, and the size ratio of each component is not limited to the same as the actual one.
圖2係以示意方式顯示可用於本發明之保護膜形成用複合片的一實施形態之剖視圖。 2 is a cross-sectional view schematically showing an embodiment of a composite sheet for forming a protective film that can be used in the present invention.
此處所示之保護膜形成用複合片1A係於基材11上具備黏著劑層12並於黏著劑層12上具備保護膜形成用膜13而成。支持片10為基材11及黏著劑層12之積層體，換言之，保護膜形成用複合片1A具有於支持片10的一方的表面10a上積層有保護膜形成用膜13之構成。保護膜 形成用複合片1A進一步於保護膜形成用膜13上具備剝離膜15。 The protective film-forming composite sheet 1A shown here is formed by including an adhesive layer 12 on a substrate 11 and a protective film-forming film 13 on the adhesive layer 12. The support sheet 10 is a laminated body of the base material 11 and the adhesive layer 12. In other words, the protective film-forming composite sheet 1A has a structure in which a protective film-forming film 13 is laminated on one surface 10 a of the support sheet 10. The protective film-forming composite sheet 1A further includes a release film 15 on the protective film-forming film 13.
保護膜形成用複合片1A中，於基材11的一方的表面11a積層有黏著劑層12，於黏著劑層12的表面12a的整個面積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的一部分亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的表面13a中未積層治具用接著劑層16之面及治具用接著劑層16的表面16a(上表面及側面)積層有剝離膜15。 In the protective film-forming composite sheet 1A, an adhesive layer 12 is laminated on one surface 11a of the substrate 11, and a protective film-forming film 13 is layered on the entire area of the surface 12a of the adhesive layer 12, and is used for protective film formation. A part of the surface 13 a of the film 13, that is, a region near the peripheral edge portion, is laminated with a fixture adhesive layer 16. The surface of the protective film forming film 13 a is not laminated with the fixture adhesive layer 16 and the fixture surface. A release film 15 is laminated on the surface 16 a (upper surface and side surface) of the adhesive layer 16.
保護膜形成用複合片1A中，硬化後之保護膜形成用膜13(亦即保護膜13')與支持片10之間的黏著力，換言之保護膜13'與黏著劑層12之間的黏著力較佳為50mN/25mm至1500mN/25mm。 In the protective film-forming composite sheet 1A, the adhesive force between the cured protective film-forming film 13 (that is, the protective film 13 ') and the support sheet 10, in other words, the adhesion between the protective film 13' and the adhesive layer 12 The force is preferably 50mN / 25mm to 1500mN / 25mm.
治具用接著劑層16例如可為含有接著劑成分之單層結構，亦可為於成為芯材之片的雙面積層有含有接著劑成分之層之複數層結構。 The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a multiple-layer structure including a layer containing an adhesive component in a double-area layer of a core material sheet.
圖2所示之保護膜形成用複合片1A係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a貼附半導體晶圓(省略圖示)的背面，並進一步將治具用接著劑層16的表面16a中的上表面貼附於環狀框 等治具。 The protective film forming composite sheet 1A shown in FIG. 2 is used in a state in which the back surface of a semiconductor wafer (not shown) is attached to the surface 13 a of the protective film forming film 13 with the release film 15 removed. Further, the upper surface of the surface 16a of the adhesive layer 16 for a jig is further attached to a jig such as a ring frame.
圖3係以示意方式顯示可用於本發明之保護膜形成用複合片的另一實施形態之剖視圖。再者，圖3以後之圖中，對於既已說明之圖所示相同的構成要素，標附與該已說明之圖之情形相同的符號，並省略該符號的詳細說明。 3 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention. In the drawings subsequent to FIG. 3, the same constituent elements shown in the already-explained drawings are marked with the same symbols as in the case of the already-explained drawings, and detailed explanations of the symbols are omitted.
關於此處所示之保護膜形成用複合片1B，除了不具備治具用接著劑層16之方面以外，與圖2所示之保護膜形成用複合片1A相同。亦即，保護膜形成用複合片1B中，於基材11的一方的表面11a積層有黏著劑層12，於黏著劑層12的表面12a的整個面積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的整個面積層有剝離膜15。 The protective film forming composite sheet 1B shown here is the same as the protective film forming composite sheet 1A shown in FIG. 2 except that it does not include a jig adhesive layer 16. That is, in the composite sheet 1B for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the substrate 11, and a protective film forming film 13 is layered on the entire area of the surface 12a of the adhesive layer 12 for protection. A release film 15 is layered over the entire area of the surface 13 a of the film-forming film 13.
圖3所示之保護膜形成用複合片1B係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a中的中央側的一部分區域貼附半導體晶圓(省略圖示)的背面，並進一步將保護膜形成用膜13的周緣部附近的區域貼附於環狀框等治具。 The protective film forming composite sheet 1B shown in FIG. 3 is used in a state where a semiconductor wafer is attached to a part of the center side of the surface 13 a of the protective film forming film 13 with the release film 15 removed. On the back surface (not shown), a region near the peripheral edge portion of the protective film-forming film 13 is further attached to a jig such as a ring frame.
圖4係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 FIG. 4 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.
關於此處所示之保護膜形成用複合片1C，除了不具 備黏著劑層12之方面以外，與圖2所示之保護膜形成用複合片1A相同。亦即，保護膜形成用複合片1C中，支持片10僅由基材11構成。於基材11的一方的表面11a(支持片10的一方的表面10a)積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的一部分亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的表面13a中未積層治具用接著劑層16之面及治具用接著劑層16的表面16a(上表面及側面)積層剝離膜15。 The protective film-forming composite sheet 1C shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 2 except that the adhesive layer 12 is not provided. That is, in the composite sheet 1C for forming a protective film, the support sheet 10 is composed of only the base material 11. A protective film-forming film 13 is laminated on one surface 11a of the base material 11 (one surface 10a of the support sheet 10), and a part of the surface 13a of the protective film-forming film 13, that is, a region near the peripheral portion is laminated. The adhesive layer 16 for the protective film is not laminated on the surface 13 a of the protective film forming film 13, and the release film 15 is laminated on the surface of the adhesive layer 16 for the jig and the surface 16 a (upper surface and side surface) of the adhesive layer 16 for the jig. .
保護膜形成用複合片1C中，硬化後之保護膜形成用膜13(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與基材11之間的黏著力較佳為50mN/25mm至1500mN/25mm。 In the protective sheet forming composite sheet 1C, the adhesive force between the cured protective film forming film 13 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the substrate 11 is preferably 50 mN. / 25mm to 1500mN / 25mm.
圖4所示之保護膜形成用複合片1C係以下述方式使用：與圖2所示之保護膜形成用複合片1A同樣地，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a貼附半導體晶圓(省略圖示)的背面，並進一步將治具用接著劑層16的表面16a中的上表面貼附於環狀框等治具。 The protective film forming composite sheet 1C shown in FIG. 4 is used in the same manner as the protective film forming composite sheet 1A shown in FIG. 2 with the release film 15 removed from the protective film forming film. A surface 13a of 13 is attached to a back surface of a semiconductor wafer (not shown), and an upper surface of the surface 16a of the adhesive layer 16 for a jig is further attached to a jig such as a ring frame.
圖5係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 5 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.
關於此處所示之保護膜形成用複合片1D，除了不具備治具用接著劑層16之方面以外，與圖4所示之保護膜 形成用複合片1C相同。亦即，保護膜形成用複合片1D中，於基材11的一方的表面11a積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的整個面積層有剝離膜15。 The protective film-forming composite sheet 1D shown here is the same as the protective film-forming composite sheet 1C shown in FIG. 4 except that it does not include a jig adhesive layer 16. That is, in the protective film-forming composite sheet 1D, a protective film-forming film 13 is laminated on one surface 11 a of the substrate 11, and a release film 15 is layered on the entire area of the surface 13 a of the protective film-forming film 13.
圖5所示之保護膜形成用複合片1D係以下述方式使用：與圖3所示之保護膜形成用複合片1B同樣地，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a中的中央側的一部分區域貼附半導體晶圓(省略圖示)的背面，並進一步將保護膜形成用膜13的周緣部附近的區域貼附於環狀框等治具。 The protective film-forming composite sheet 1D shown in FIG. 5 is used in the same manner as the protective film-forming composite sheet 1B shown in FIG. 3 with the protective film-forming film in a state where the release film 15 is removed. A part of the central portion of the front surface 13a of 13 is attached to the back surface of a semiconductor wafer (not shown), and an area near the peripheral edge portion of the protective film forming film 13 is further attached to a jig such as a ring frame.
圖6係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 6 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.
關於此處所示之保護膜形成用複合片1E，除了保護膜形成用膜之形狀不同之方面以外，與圖3所示之保護膜形成用複合片1B相同。亦即，保護膜形成用複合片1E係於基材11上具備黏著劑層12並於黏著劑層12上具備保護膜形成用膜23而成。支持片10為基材11及黏著劑層12之積層體，換言之，保護膜形成用複合片1E具有於支持片10的一方的表面10a上積層有保護膜形成用膜23之構成。保護膜形成用複合片1E中，進一步於保護膜形成用膜23上具備剝離膜15。 The protective film-forming composite sheet 1E shown here is the same as the protective film-forming composite sheet 1B shown in FIG. 3 except that the shape of the protective film-forming film is different. That is, the protective film-forming composite sheet 1E is formed by including the adhesive layer 12 on the base material 11 and the protective film-forming film 23 on the adhesive layer 12. The support sheet 10 is a laminated body of the substrate 11 and the adhesive layer 12. In other words, the protective film-forming composite sheet 1E has a structure in which a protective film-forming film 23 is laminated on one surface 10 a of the support sheet 10. In the protective film forming composite sheet 1E, a release film 15 is further provided on the protective film forming film 23.
保護膜形成用複合片1E中，於基材11的一方的表面11a積層有黏著劑層12，於黏著劑層12的表面12a的一部分亦即中央側的區域積層有保護膜形成用膜23。於黏著劑層12的表面12a中未積層保護膜形成用膜23之面及保護膜形成用膜23的表面23a(上表面及側面)上積層有剝離膜15。 In the protective film-forming composite sheet 1E, an adhesive layer 12 is laminated on one surface 11 a of the base material 11, and a protective film-forming film 23 is laminated on a part of the surface 12 a of the adhesive layer 12, that is, a central region. A release film 15 is laminated on the surface 12a (upper surface and side surface) of the protective film formation film 23 and the surface 23a (upper surface and side surface) of the protective film formation film 23 on the surface 12a of the adhesive layer 12.
自上方往下俯視保護膜形成用複合片1E時，保護膜形成用膜23的表面積小於黏著劑層12，並例如具有圓形狀等形狀。 When the protective film forming composite sheet 1E is viewed from above, the protective film forming film 23 has a smaller surface area than the adhesive layer 12 and has a shape such as a circular shape.
保護膜形成用複合片1E中，硬化後之保護膜形成用膜23(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與黏著劑層12之間的黏著力較佳為50mN/25mm至1500mN/25mm。 In the protective film-forming composite sheet 1E, the adhesive force between the cured protective film-forming film 23 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is preferably 50mN / 25mm to 1500mN / 25mm.
圖6所示之保護膜形成用複合片1E係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成用膜23的表面23a貼附半導體晶圓(省略圖示)的背面，並進一步將黏著劑層12的表面12a中未積層保護膜形成用膜23之面貼附於環狀框等治具。 The protective film-forming composite sheet 1E shown in FIG. 6 is used in a state in which the back surface of a semiconductor wafer (not shown) is attached to the surface 23 a of the protective film-forming film 23 with the release film 15 removed. Then, the surface of the surface 12a of the adhesive layer 12 on which the protective film-forming film 23 is not laminated is attached to a jig such as a ring frame.
圖6所示之保護膜形成用複合片1E中，亦可於黏著劑層12的表面12a中未積層保護膜形成用膜23之面，與 圖2及圖4所示之保護膜形成用複合片同樣地，積層治具用接著劑層(省略圖示)。具備此種治具用接著劑層之保護膜形成用複合片1E係與圖2及圖4所示之保護膜形成用複合片同樣地，將治具用接著劑層的表面貼附於環狀框等治具而使用。 In the protective film-forming composite sheet 1E shown in FIG. 6, a surface on which the protective film-forming film 23 is not laminated on the surface 12 a of the adhesive layer 12 may be laminated with the protective film-forming film shown in FIGS. 2 and 4. In the same manner, an adhesive layer (not shown) for a laminated jig is laminated. The protective film-forming composite sheet 1E having such an adhesive layer for a jig is similar to the protective film-forming composite sheet shown in FIGS. 2 and 4, and the surface of the adhesive layer for a jig is attached to a ring shape. And other fixtures.
如此，可用於本發明之保護膜形成用複合片中，無論支持片及保護膜形成用膜為何種形態，均可具備治具用接著劑層。但是，通常如圖2及圖4所示，作為具備治具用接著劑層之保護膜形成用複合片，較佳為於保護膜形成用膜上具備治具用接著劑層。 As described above, the composite sheet for forming a protective film that can be used in the present invention can be provided with an adhesive layer for a fixture regardless of the form of the support sheet and the film for forming a protective film. However, as shown in FIG. 2 and FIG. 4, as a composite film for forming a protective film having an adhesive layer for a jig, it is preferable to include an adhesive layer for a jig on the protective film-forming film.
可用於本發明之保護膜形成用複合片並不限定於圖2至圖6所示之保護膜形成用複合片，在無損本發明之功效之範圍內，亦可變更或刪除圖2至圖6所示之保護膜形成用複合片的一部分構成，或者對前文所說明之保護膜形成用複合片進而追加其他構成。 The composite sheet for forming a protective film that can be used in the present invention is not limited to the composite sheet for forming a protective film shown in FIG. 2 to FIG. 6. As long as the effect of the present invention is not impaired, FIG. 2 to FIG. A part of the protective film-forming composite sheet is shown as a structure, or another structure is added to the protective film-forming composite sheet described above.
例如，圖4及圖5所示之保護膜形成用複合片中，亦可於基材11與保護膜形成用膜13之間設置中間層。作為中間層，可根據目的選擇任意中間層。 For example, in the protective film-forming composite sheet shown in FIGS. 4 and 5, an intermediate layer may be provided between the substrate 11 and the protective film-forming film 13. As the intermediate layer, any intermediate layer can be selected according to the purpose.
圖2、圖3及圖6所示之保護膜形成用複合片中，亦可於基材11與黏著劑層12之間設置中間層。亦即，可用於本發明之保護膜形成用複合片中，支持片亦可由基材、 中間層及黏著劑層依序積層而成。此處，所謂中間層係與圖4及圖5所示之保護膜形成用複合片中可設置之中間層相同。 In the composite sheet for forming a protective film shown in FIGS. 2, 3, and 6, an intermediate layer may be provided between the substrate 11 and the adhesive layer 12. That is, the protective sheet can be used in the composite sheet for forming a protective film of the present invention, and the support sheet may be formed by sequentially stacking a base material, an intermediate layer, and an adhesive layer. Here, the intermediate layer is the same as the intermediate layer that can be provided in the protective film-forming composite sheet shown in FIGS. 4 and 5.
圖2至圖6所示之保護膜形成用複合片中，可將前述中間層以外之層設置於任意部位。 In the composite sheet for forming a protective film shown in FIGS. 2 to 6, a layer other than the intermediate layer may be provided at an arbitrary position.
可用於本發明之保護膜形成用複合片中，亦可於剝離膜與和該剝離膜直接接觸之層之間產生一部分間隙。 It can be used in the composite sheet for forming a protective film of the present invention, and a gap may be partially formed between the release film and a layer in direct contact with the release film.
可用於本發明之保護膜形成用複合片中，各層的大小或形狀可根據目的任意調節。 The size or shape of each layer that can be used in the composite sheet for forming a protective film of the present invention can be arbitrarily adjusted according to the purpose.
可用於本發明之保護膜形成用複合片中，如後述般，較佳為黏著劑層等支持片中的與保護膜形成用膜直接接觸之層為非能量線硬化性。藉由使用此種保護膜形成用複合片，可更容易地拾取背面具備保護膜之半導體晶片。 The composite sheet for forming a protective film that can be used in the present invention, as described later, is preferably non-energy ray hardenable in a layer in a support sheet such as an adhesive layer that is in direct contact with the film for forming a protective film. By using such a composite sheet for forming a protective film, it is possible to more easily pick up a semiconductor wafer having a protective film on the back surface.
支持片可為透明、不透明、或者根據目的而著色。 The support sheet may be transparent, opaque, or colored according to purpose.
其中，保護膜形成用膜具有能量線硬化性之本發明中，支持片較佳為使能量線透過之支持片。 Among them, in the present invention in which the film for forming a protective film has energy ray-curability, the support sheet is preferably a support sheet that transmits energy rays.
例如，支持片中，波長375nm之光之透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜照射能量線(紫外線)時，保護膜形成用膜之硬化度進一步提高。 For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and even more preferably 70% or more. When the light transmittance is in such a range, when the protective film-forming film is irradiated with energy rays (ultraviolet rays) through the support sheet, the hardening degree of the protective film-forming film is further improved.
另一方面，支持片中，波長375nm之光之透過率的上限值並無特別限定，例如可設為95%。 On the other hand, in the supporting sheet, the upper limit of the transmittance of light having a wavelength of 375 nm is not particularly limited, and may be set to 95%, for example.
支持片中，波長532nm之光之透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。 In the supporting sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and even more preferably 70% or more.
藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜或保護膜照射雷射光而於這些進行印字時，可更清晰地進行印字。 When the light transmittance is within this range, the protective film-forming film or the protective film is irradiated with laser light through the support sheet, and printing can be performed more clearly when these are printed.
另一方面，支持片中，波長532nm之光之透過率的上限值並無特別限定，例如可設為95%。 On the other hand, the upper limit of the transmittance of light having a wavelength of 532 nm in the support sheet is not particularly limited, and may be set to 95%, for example.
支持片中，波長1064nm之光之透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜或保護膜照射雷射光而於這些進行印字時，可更清晰地進行印字。 In the supporting sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and even more preferably 70% or more. When the light transmittance is within this range, the protective film-forming film or the protective film is irradiated with laser light through the support sheet, and printing can be performed more clearly when these are printed.
另一方面，支持片中，波長1064nm之光之透過率的上限值並無特別限定，例如可設為95%。 On the other hand, the upper limit of the transmittance of light having a wavelength of 1064 nm in the supporting sheet is not particularly limited, and may be set to 95%, for example.
其次，對構成支持片之各層進行更詳細的說明。 Next, the layers constituting the support sheet will be described in more detail.
○基材 ○ Substrate
前述基材為片狀或膜狀，作為前述基材的構成材料，例如可列舉各種樹脂。 The substrate is in the form of a sheet or a film, and examples of the constituent material of the substrate include various resins.
作為前述樹脂，例如可列舉：低密度聚乙烯(LDPE；low density polyethylene)、直鏈低密度聚乙烯(LLDPE； linear low density polyethylene)、高密度聚乙烯(HDPE；high density polyethylene)等聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、降冰片烯樹脂等聚乙烯以外之聚烯烴；乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-降冰片烯共聚物等乙烯系共聚物(使用乙烯作為單體而獲得之共聚物)；聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂(使用氯乙烯作為單體而獲得之樹脂)；聚苯乙烯；聚環烯烴；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚萘二甲酸乙二酯、聚間苯二甲酸乙二酯、聚2,6-萘二羧酸乙二酯、全部結構單元具有芳香族環式基之全芳香族聚酯等聚酯；2種以上之前述聚酯之共聚物；聚(甲基)丙烯酸酯；聚胺基甲酸酯；聚丙烯酸胺基甲酸酯；聚醯亞胺；聚醯胺；聚碳酸酯；氟樹脂；聚縮醛；改質聚苯醚；聚苯硫醚；聚碸；聚醚酮等。 Examples of the resin include polyethylene such as low density polyethylene (LDPE; low density polyethylene), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (Meth) acrylic acid ester copolymers, ethylene-norbornene copolymers and other ethylene-based copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine Resin obtained from ethylene as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate, polyethylene naphthalate, polyethylene naphthalate, polyethylene isophthalate Polyesters such as esters, polyethylene 2,6-naphthalene dicarboxylate, wholly aromatic polyesters having an aromatic cyclic group in all structural units; copolymers of two or more of the aforementioned polyesters; poly (methyl) Acrylate; polyurethane; polyacrylic acid Allophanate; polyimide; polyamides; polycarbonates; fluorine resin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyether ketone.
作為前述樹脂，例如亦可列舉前述聚酯與前述聚酯以外的樹脂之混合物等聚合物合金。前述聚酯與前述聚酯以外的樹脂之聚合物合金較佳為聚酯以外的樹脂之量為相對較少量。 Examples of the resin include a polymer alloy such as a mixture of the polyester and a resin other than the polyester. The polymer alloy of the aforementioned polyester and a resin other than the aforementioned polyester is preferably a relatively small amount of a resin other than the polyester.
作為前述樹脂，例如亦可列舉：前文所例示之前述樹脂之1種或2種以上交聯而成之交聯樹脂；使用前文所例示之前述樹脂之1種或2種以上之離子聚合物等改質樹脂。 Examples of the resin include crosslinked resins obtained by crosslinking one or more of the resins exemplified above; use of one or more ionic polymers of the resins exemplified above; Modified resin.
本說明書中，「(甲基)丙烯酸」的概念係包含有「丙 烯酸」及「甲基丙烯酸」兩者。關於與(甲基)丙烯酸類似之用語亦相同。 In this specification, the concept of "(meth) acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth) acrylic acid.
構成基材之樹脂可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The resin constituting the substrate may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
基材可由1層(單層)構成，亦可由2層以上之複數層構成；於由複數層構成之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The substrate may be composed of one layer (single layer), or may be composed of two or more layers. When the substrate is composed of plural layers, these plural layers may be the same as or different from each other. The combination of the plural layers is not particularly limited.
基材的厚度較佳為50μm至300μm，更佳為60μm至100μm。藉由基材的厚度為此種範圍，前述保護膜形成用複合片的可撓性、及對半導體晶圓或半導體晶片之貼附性進一步提高。 The thickness of the substrate is preferably 50 μm to 300 μm, and more preferably 60 μm to 100 μm. When the thickness of the base material is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer are further improved.
此處，所謂「基材的厚度」意指基材整體的厚度，例如，所謂由複數層構成之基材的厚度意指構成基材之全部層的合計厚度。 Here, the "thickness of the base material" means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material.
本說明書中，所謂「厚度」係指利用接觸式厚度計，測定對象物之任意5個部位，以所測得之厚度之平均顯示之值。 In the present specification, the "thickness" refers to a value displayed as an average of the measured thicknesses at any five locations of the measurement target using a contact thickness gauge.
基材較佳為厚度精度高，亦即任何部位的厚度不均均得到抑制。上述之構成材料中，作為可用於構成此種厚度精度高的基材之材料，例如可列舉：聚乙烯、聚乙烯以外 的聚烯烴、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物等。 The thickness of the substrate is preferably high, that is, thickness unevenness at any part is suppressed. Among the above-mentioned constituent materials, examples of materials that can be used to form such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymerization. Things.
基材中，除了前述樹脂等主要構成材料以外，亦可含有填充材料、著色劑、抗靜電劑、抗氧化劑、有機潤滑劑、觸媒、軟化劑(塑化劑)等公知的各種添加劑。 The substrate may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the resin.
基材的光學特性滿足前文所說明之支持片的光學特性即可。亦即，基材可為透明、不透明、根據目的而著色，或者蒸鍍其他層。 The optical characteristics of the substrate need only satisfy the optical characteristics of the support sheet described above. That is, the substrate may be transparent, opaque, colored according to the purpose, or other layers may be vapor-deposited.
保護膜形成用膜具有能量線硬化性之本發明中，基材較佳為使能量線透過之基材。 In the present invention in which the film for forming a protective film has energy ray curability, the substrate is preferably a substrate that transmits energy rays.
基材的表面亦可經實施以下處理以提高與設置於該基材上之黏著劑層等其他層之密接性：利用噴砂處理、溶劑處理等之凹凸化處理；或者電暈放電處理、電子束照射處理、電漿處理、臭氧/紫外線照射處理、火焰處理、鉻酸處理、熱風處理等氧化處理等。 The surface of the substrate may also be subjected to the following treatments to improve the adhesion with other layers such as an adhesive layer provided on the substrate: a roughening treatment using a sandblasting treatment, a solvent treatment, or the like; or a corona discharge treatment, an electron beam Oxidation treatment such as irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc.
基材的表面亦可經實施底塗(primer)處理。 The surface of the substrate may be subjected to a primer treatment.
基材亦可具有抗靜電塗層或以下用途之層等：將保護膜形成用複合片重疊保存時，防止基材接著於其他片或基材接著於吸附台。 The substrate may have an antistatic coating or a layer for the following purposes: When the composite sheet for forming a protective film is stacked and stored, the substrate is prevented from adhering to another sheet or the substrate to an adsorption table.
這些之中，就抑制因切割時刀片摩擦而導致基材產生斷片之方面而言，基材尤佳為表面經實施電子束照射處 理。 Among these, in terms of suppressing chipping of the base material due to blade friction during cutting, it is particularly preferable that the base material is subjected to an electron beam irradiation treatment on the surface.
基材可利用公知的方法進行製造。例如，含有樹脂之基材可藉由使含有前述樹脂之樹脂組成物成形而進行製造。 The substrate can be produced by a known method. For example, a resin-containing substrate can be produced by molding a resin composition containing the resin.
○黏著劑層 ○ Adhesive layer
前述黏著劑層為片狀或膜狀，含有黏著劑。 The adhesive layer is sheet-like or film-like and contains an adhesive.
作為前述黏著劑，例如可列舉：丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等黏著性樹脂，較佳為丙烯酸系樹脂。 Examples of the adhesive include acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin. The resin is preferably an acrylic resin.
本發明中，「黏著性樹脂」的概念係包含有具有黏著性之樹脂及具有接著性之樹脂兩者，例如不僅包含本身具有黏著性之樹脂，亦包含藉由與添加劑等其他成分併用而顯示黏著性之樹脂、或者藉由存在熱或水等觸發劑而顯示接著性之樹脂等。 In the present invention, the concept of "adhesive resin" includes both resins having adhesive properties and resins having adhesive properties. For example, not only resins having adhesive properties but also other components such as additives are used. Adhesive resin, or resin exhibiting adhesiveness by the presence of a trigger such as heat or water.
黏著劑層可由1層(單層)構成，亦可由2層以上之複數層構成；於由複數層構成之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The adhesive layer may be composed of one layer (single layer) or plural layers of two or more layers. In the case of plural layers, the plural layers may be the same as or different from each other. The combination of the plural layers is not particularly limited. .
黏著劑層的厚度較佳為1μm至100μm，更佳為1μm 至60μm，尤佳為1μm至30μm。 The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and even more preferably 1 μm to 30 μm.
此處，所謂「黏著劑層的厚度」意指黏著劑層整體的厚度，例如，所謂由複數層構成之黏著劑層的厚度意指構成黏著劑層之全部層的合計厚度。 Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer, and for example, the thickness of the adhesive layer composed of plural layers means the total thickness of all the layers constituting the adhesive layer.
黏著劑層的光學特性滿足前文所說明之支持片的光學特性即可。亦即，黏著劑層可為透明、不透明、或者根據目的而著色。 The optical characteristics of the adhesive layer may satisfy the optical characteristics of the support sheet described above. That is, the adhesive layer may be transparent, opaque, or colored according to the purpose.
保護膜形成用膜具有能量線硬化性之本發明中，黏著劑層較佳為使能量線透過之黏著劑層。 In the present invention in which the film for forming a protective film has energy ray hardening property, the adhesive layer is preferably an adhesive layer that allows energy rays to pass through.
黏著劑層可使用能量線硬化性黏著劑而形成，亦可使用非能量線硬化性黏著劑而形成。使用能量線硬化性之黏著劑所形成之黏著劑層可容易地調節硬化前及硬化後的物性。 The adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. The adhesive layer formed using an energy ray-curable adhesive can easily adjust physical properties before and after curing.
<<黏著劑組成物>> << Adhesive composition >>
黏著劑層可使用含有黏著劑之黏著劑組成物而形成。例如，於黏著劑層之形成對象面塗敷黏著劑組成物，視需要使黏著劑組成物乾燥，藉此可於目標部位形成黏著劑層。關於黏著劑層的更具體的形成方法，與其他層的形成方法一起，隨後詳細地進行說明。黏著劑組成物中的常溫下不會氣化的成分彼此的含量比率，通常與黏著劑層中的前述成分彼此的含量比率相同。本說明書中，所謂「常 溫」意指不特別冷或特別熱的溫度，亦即平常的溫度，例如可列舉15℃至25℃之溫度等。 The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive composition is coated on the formation target surface of the adhesive layer, and if necessary, the adhesive composition is dried to form an adhesive layer at a target portion. A more specific method of forming the adhesive layer will be described in detail later along with the method of forming other layers. The content ratio of the components that do not vaporize at normal temperature in the adhesive composition is usually the same as the content ratio of the components in the adhesive layer. In this specification, "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, and for example, a temperature of 15 ° C to 25 ° C can be mentioned.
利用公知的方法塗敷黏著劑組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、繞線棒(Meyer bar)式塗佈機、刮棒式塗佈機(rod coater)、接觸式塗佈機等。 The adhesive composition may be applied by a known method, and examples thereof include a method using various applicators: an air knife applicator, a blade applicator, a bar coater, a gravure coater, and a roll coater. Cloth machine, roll knife coater, curtain coater, mold coater, knife coater, screen coater, Meyer bar coater, doctor bar coater Rod coater, contact coater, etc.
黏著劑組成物的乾燥條件並無特別限定，於黏著劑組成物含有後述溶劑之情形時，較佳為進行加熱乾燥，該情形時，較佳為於例如70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the adhesive composition are not particularly limited. In the case where the adhesive composition contains a solvent to be described later, it is preferable to perform drying by heating. In this case, it is preferably 70 ° C to 130 ° C and 10 seconds to 5 Dry under minutes.
於黏著劑層為能量線硬化性之情形時，作為含有能量線硬化性黏著劑之黏著劑組成物，亦即能量線硬化性之黏著劑組成物，例如可列舉以下黏著劑組成物等：黏著劑組成物(I-1)，含有非能量線硬化性之黏著性樹脂(I-1a)(以下，有時簡記為「黏著性樹脂(I-1a)」)、及能量線硬化性化合物；黏著劑組成物(I-2)，含有能量線硬化性之黏著性樹脂(I-2a)(以下，有時簡記為「黏著性樹脂(I-2a)」)，該黏著性樹脂(I-2a)於非能量線硬化性之黏著性樹脂(I-1a)的側鏈導入有不飽和基；黏著劑組成物(I-3)，含有前述黏著 性樹脂(I-2a)、及能量線硬化性化合物。 In the case where the adhesive layer is energy ray-curable, as the adhesive composition containing the energy-ray-curable adhesive, that is, the energy-ray-curable adhesive composition, for example, the following adhesive compositions are listed: Adhesion The agent composition (I-1) contains a non-energy-ray-curable adhesive resin (I-1a) (hereinafter, sometimes simply referred to as "adhesive resin (I-1a)") and an energy-ray-curable compound; The adhesive composition (I-2) contains an energy ray-curable adhesive resin (I-2a) (hereinafter, sometimes simply referred to as "adhesive resin (I-2a)"), and this adhesive resin (I- 2a) An unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a); the adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a), and an energy ray Hardening compound.
<黏著劑組成物(I-1)> <Adhesive composition (I-1)>
如上所述，前述黏著劑組成物(I-1)含有非能量線硬化性之黏著性樹脂(I-1a)、及能量線硬化性化合物。 As described above, the adhesive composition (I-1) contains a non-energy-ray-curable adhesive resin (I-1a) and an energy-ray-curable compound.
[黏著性樹脂(I-1a)] [Adhesive resin (I-1a)]
前述黏著性樹脂(I-1a)較佳為丙烯酸系樹脂。 The adhesive resin (I-1a) is preferably an acrylic resin.
作為前述丙烯酸系樹脂，例如可列舉：至少具有源自(甲基)丙烯酸烷基酯之結構單元之丙烯酸系聚合物。 Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate.
前述丙烯酸系樹脂所具有之結構單元可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The acrylic resin may have only one structural unit or two or more structural units. When there are two or more structural units, these combinations and ratios may be arbitrarily selected.
作為前述(甲基)丙烯酸烷基酯，例如可列舉構成烷基酯之烷基的碳數為1至20之(甲基)丙烯酸烷基酯，前述烷基較佳為直鏈狀或支鏈狀。 Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester. The alkyl group is preferably linear or branched. shape.
作為(甲基)丙烯酸烷基酯，更具體而言，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基) 丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯(亦稱為(甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯(亦稱為(甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯(亦稱為(甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯(亦稱為(甲基)丙烯酸硬脂酯)、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等。 Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Ester, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, (formyl) (Hexyl) hexyl acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n- (meth) acrylate Nonyl ester, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (also known as (meth) acrylic acid Lauryl), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also known as myristyl (meth) acrylate), pentadecyl (meth) acrylate, Hexadecyl (meth) acrylate (also known as palmityl (meth) acrylate), Heptadecyl (meth) acrylate, Stearyl (meth) acrylate (also known as (methyl) Base) stearyl acrylate), (meth) acrylic acid Undecyl ester, eicosyl (meth) acrylate, and the like.
就黏著劑層的黏著力提高之方面而言，前述丙烯酸系聚合物較佳為具有源自前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯之結構單元。就黏著劑層的黏著力進一步提高之方面而言，前述烷基的碳數較佳為4至12，更佳為4至8。前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯較佳為丙烯酸烷基酯。 In terms of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit having an alkyl (meth) acrylate having a carbon number of 4 or more derived from the alkyl group. In terms of further improving the adhesion of the adhesive layer, the carbon number of the alkyl group is preferably 4 to 12, and more preferably 4 to 8. The alkyl (meth) acrylate having a carbon number of 4 or more of the alkyl group is preferably an alkyl acrylate.
前述丙烯酸系聚合物較佳為除了源自(甲基)丙烯酸烷基酯之結構單元以外，進一步具有源自含官能基之單體之結構單元。 The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
作為前述含官能基之單體，例如可列舉以下單體：可藉由前述官能基與後述之交聯劑反應而成為交聯的起點，或者可藉由前述官能基與後述之含不飽和基之化合物中的不飽和基反應，而於丙烯酸系聚合物的側鏈導入不飽和基。 As the functional group-containing monomer, for example, the following monomers may be mentioned: the functional group may be reacted with a cross-linking agent described later to become a starting point of cross-linking, or the functional group may be unsaturated-containing group described later The unsaturated group in the compound reacts, and an unsaturated group is introduced into the side chain of the acrylic polymer.
作為含官能基之單體中的前述官能基，例如可列舉：羥基、羧基、胺基、環氧基等。 Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amine group, and an epoxy group.
亦即，作為含官能基之單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含環氧基之單體等。 That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and an epoxy group-containing monomer.
作為前述含羥基之單體，例如可列舉：(甲基)丙烯酸羥基甲酯、(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3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。 Examples of the hydroxyl-containing monomer include: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Hydroxyalkyl (meth) acrylates such as hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; vinyl alcohol, Non- (meth) acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols having no (meth) acrylfluorenyl skeleton) and the like.
作為前述含羧基之單體，例如可列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；反丁烯二酸、衣康酸、順丁烯二酸、檸康酸等乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧酸)；前述乙烯性不飽和二羧酸之酐；甲基丙烯酸2-羧基乙酯等(甲基)丙烯酸羧基烷基酯等。 Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth) acrylic acid and butene acid; fumaric acid and itaconic acid. Acid, maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate (Meth) acrylic acid alkyl esters and the like.
含官能基之單體較佳為含羥基之單體、含羧基之單體，更佳為含羥基之單體。 The functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.
構成前述丙烯酸系聚合物之含官能基之單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The functional group-containing monomer constituting the acrylic polymer may be only one type, or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
前述丙烯酸系聚合物中，源自含官能基之單體之結構單元的含量相對於結構單元的總質量，較佳為1質量%至35質量%，更佳為2質量%至32質量%，尤佳為3質量%至30質量%。 The content of the structural unit derived from the functional group-containing monomer in the acrylic polymer is preferably 1% to 35% by mass, and more preferably 2% to 32% by mass. It is particularly preferably 3 to 30% by mass.
前述丙烯酸系聚合物中，除了源自(甲基)丙烯酸烷基酯之結構單元及源自含官能基之單體之結構單元以外，亦可進一步具有源自其他單體之結構單元。 The acrylic polymer may further include a structural unit derived from another monomer in addition to a structural unit derived from an alkyl (meth) acrylate and a structural unit derived from a functional group-containing monomer.
前述其他單體只要能夠與(甲基)丙烯酸烷基酯等共聚合，則並無特別限定。 The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth) acrylate or the like.
作為前述其他單體，例如可列舉：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲酸乙烯酯、乙酸乙烯酯、丙烯腈、丙烯醯胺等。 Examples of the other monomer include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.
構成前述丙烯酸系聚合物之前述其他單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The aforementioned other monomers constituting the acrylic polymer may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be arbitrarily selected.
前述丙烯酸系聚合物可用作上述之非能量線硬化性之黏著性樹脂(I-1a)。 The acrylic polymer can be used as the non-energy-ray-curable adhesive resin (I-1a).
另一方面，使前述丙烯酸系聚合物中的官能基，與具有能量線聚合性不飽和基(能量線聚合性基)之含不飽和基之化合物反應而成之化合物可用作上述之能量線硬化性之黏著性樹脂(I-2a)。 On the other hand, a compound obtained by reacting a functional group in the acrylic polymer with an unsaturated ray-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the energy ray. Hardening adhesive resin (I-2a).
黏著劑組成物(I-1)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type, or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-1)中，黏著性樹脂(I-1a)的含量相對於前述黏著劑組成物(I-1)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 The content of the adhesive resin (I-1a) in the adhesive composition (I-1) is preferably 5% to 99% by mass relative to the total mass of the adhesive composition (I-1), and more preferably It is 10% by mass to 95% by mass, and particularly preferably 15% by mass to 90% by mass.
[能量線硬化性化合物] [Energy ray hardening compound]
作為黏著劑組成物(I-1)所含有之前述能量線硬化性化合物，可列舉：具有能量線聚合性不飽和基，且可藉由照射能量線而硬化之單體或低聚物。 Examples of the energy ray-curable compound contained in the adhesive composition (I-1) include monomers or oligomers which have an energy ray polymerizable unsaturated group and can be hardened by irradiating energy rays.
能量線硬化性化合物中，作為單體，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、季戊四醇四(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、1,6-己二醇(甲基)丙烯酸酯等多元(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯；聚酯(甲基)丙烯酸酯；聚醚(甲基)丙烯酸酯；環氧(甲 基)丙烯酸酯等。 Examples of the energy ray curable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (methyl) Poly) (meth) acrylates such as acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol (meth) acrylate; poly (meth) acrylates Esters; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates and the like.
能量線硬化性化合物中，作為低聚物，例如可列舉上述所例示之單體進行聚合而成之低聚物等。 Among the energy ray curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above.
就分子量相對較大，不易使黏著劑層的儲存彈性率降低之方面而言，能量線硬化性化合物較佳為(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯酸胺基甲酸酯低聚物。 From the viewpoint that the molecular weight is relatively large and the storage elastic modulus of the adhesive layer is not easily reduced, the energy ray hardening compound is preferably a (meth) acrylic acid urethane or (meth) acrylic acid urethane. Oligomer.
黏著劑組成物(I-1)所含有之前述能量線硬化性化合物可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The aforementioned energy ray-curable compound contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
前述黏著劑組成物(I-1)中，前述能量線硬化性化合物的含量相對於前述黏著劑組成物(I-1)的總質量，較佳為1質量%至95質量%，更佳為5質量%至90質量%，尤佳為10質量%至85質量%。 The content of the energy ray-curable compound in the adhesive composition (I-1) is preferably 1% by mass to 95% by mass, and more preferably, based on the total mass of the adhesive composition (I-1). 5 mass% to 90 mass%, particularly preferably 10 mass% to 85 mass%.
[交聯劑] [Crosslinking agent]
於使用除了源自(甲基)丙烯酸烷基酯之結構單元以外，進一步具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-1a)之情形時，黏著劑組成物(I-1)較佳為進一步含有交聯劑。 When the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), The adhesive composition (I-1) preferably further contains a crosslinking agent.
前述交聯劑例如與前述官能基反應，使黏著性樹脂(I-1a)彼此交聯。 The crosslinking agent reacts, for example, with the functional group to crosslink the adhesive resin (I-1a) with each other.
作為交聯劑，例如可列舉：甲苯二異氰酸酯、六亞甲基二異氰酸酯、苯二甲基二異氰酸酯、這些二異氰酸酯之加合物等異氰酸酯系交聯劑(具有異氰酸酯基之交聯劑)；乙二醇縮水甘油基醚等環氧系交聯劑(具有縮水甘油基之交聯劑)；六[1-(2-甲基)-氮丙啶基]三膦三嗪等氮丙啶系交聯劑(具有氮丙啶基之交聯劑)；鋁螯合物等金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)；異氰脲酸酯系交聯劑(具有異氰脲酸骨架之交聯劑)等。 Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (cross-linking agents with glycidyl groups); aziridine-based systems such as hexa [1- (2-methyl) -aziridinyl] triphosphine triazine Crosslinking agent (crosslinking agent with aziridinyl); metal chelate-based crosslinkers such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanurate-based crosslinker (Crosslinking agent having an isocyanuric acid skeleton) and the like.
就提高黏著劑的凝聚力而提高黏著劑層的黏著力之方面、及容易獲取等方面而言，交聯劑較佳為異氰酸酯系交聯劑。 In terms of improving the cohesive force of the adhesive and improving the adhesive force of the adhesive layer, and in terms of easy availability, the crosslinking agent is preferably an isocyanate-based crosslinking agent.
黏著劑組成物(I-1)所含有之交聯劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-1) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
前述黏著劑組成物(I-1)中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the said adhesive composition (I-1), content of a crosslinking agent with respect to content of the adhesive resin (I-1a) is 100 mass parts, Preferably it is 0.01 mass part-50 mass parts, More preferably, it is 0.1 mass parts 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.
[光聚合起始劑] [Photopolymerization initiator]
黏著劑組成物(I-1)亦可進一步含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-1)，即便照射紫外 線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a hardening reaction even when a relatively low energy energy beam such as ultraviolet rays is irradiated.
作為前述光聚合起始劑，例如可列舉：安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫化物、一硫化四甲基秋蘭姆等硫化物化合物；1-羥基環己基苯基酮等α-酮醇化合物；偶氮雙異丁腈等偶氮化合物；二茂鈦等二茂鈦化合物；噻噸酮等噻噸酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯；二苯偶醯；二苯甲酮；2,4-二乙基噻噸酮；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。 Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, and other phenethyl Ketone compounds; fluorenyl phosphine oxide compounds such as bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide; benzyl Sulfide compounds such as phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanium Titanocene compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diketones such as diethylfluorene; benzophenone; benzophenazine; benzophenone; ; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone; 2-chloroanthraquinone and the like.
作為前述光聚合起始劑，例如亦可使用1-氯蒽醌等醌化合物；胺等光增感劑等。 Examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; and photosensitizers such as amines.
黏著劑組成物(I-1)所含有之光聚合起始劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-1) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-1)中，光聚合起始劑的含量相對於前述能量線硬化性化合物的含量100質量份，較佳為0.01 質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 The content of the photopolymerization initiator in the adhesive composition (I-1) is 100 parts by mass, preferably 0.01 to 20 parts by mass, and more preferably 0.03 parts by mass to the content of the energy ray-curable compound. 10 parts by mass, particularly preferably 0.05 to 5 parts by mass.
[其他添加劑] [Other additives]
黏著劑組成物(I-1)中，在無損本發明之功效之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-1) may contain other additives which do not belong to any of the above components, as long as the effect of the present invention is not impaired.
作為前述其他添加劑，例如可列舉：抗靜電劑、抗氧化劑、軟化劑(塑化劑)、填充材料(填料)、防鏽劑、著色劑(顏料、染料)、增感劑、黏著賦予劑、反應延遲劑、交聯促進劑(觸媒)等公知的添加劑。 Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion-imparting agents, Well-known additives such as a reaction retarder and a cross-linking accelerator (catalyst).
所謂反應延遲劑，例如，抑制因混入至黏著劑組成物(I-1)中之觸媒之作用，導致保存中之黏著劑組成物(I-1)中，進行目標外的交聯反應。作為反應延遲劑，例如可列舉藉由針對觸媒之螯合物形成螯合物錯合物之化合物，更具體而言，可列舉1分子中具有2個以上之羰基(-C(=O)-)之化合物。 The so-called reaction delaying agent suppresses, for example, a cross-linking reaction out of the target adhesive composition (I-1) during storage due to the action of a catalyst mixed into the adhesive composition (I-1). Examples of the reaction delaying agent include compounds that form a chelate complex by a chelate of a catalyst, and more specifically, a compound having two or more carbonyl groups (-C (= O) in one molecule) -) Compounds.
黏著劑組成物(I-1)所含有之其他添加劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-1) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-1)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 The content of the other additives in the adhesive composition (I-1) is not particularly limited, and may be appropriately selected according to the type of the other additives.
[溶劑] [Solvent]
黏著劑組成物(I-1)亦可含有溶劑。黏著劑組成物(I-1)藉由含有溶劑，對塗敷對象面之塗敷適性提高。 The adhesive composition (I-1) may contain a solvent. When the adhesive composition (I-1) contains a solvent, the applicability to the surface to be coated is improved.
前述溶劑較佳為有機溶劑，作為前述有機溶劑，例如可列舉：甲基乙基酮、丙酮等酮；乙酸乙酯等酯(羧酸酯)；四氫呋喃、二噁烷(dioxane)等醚；環己烷、正己烷等脂肪族烴；甲苯、二甲苯等芳香族烴；1-丙醇、2-丙醇等醇等。 The solvent is preferably an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as hexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.
作為前述溶劑，例如，可將製造黏著性樹脂(I-1a)時所使用之溶劑不自黏著性樹脂(I-1a)中去除而直接於黏著劑組成物(I-1)中使用，亦可於製造黏著劑組成物(I-1)時另行添加與製造黏著性樹脂(I-1a)時所使用之溶劑相同種類或不同種類之溶劑。 As the aforementioned solvent, for example, the solvent used in producing the adhesive resin (I-1a) can be used directly in the adhesive composition (I-1) without removing it from the adhesive resin (I-1a). When manufacturing the adhesive composition (I-1), a solvent of the same type or a different type from that used when manufacturing the adhesive resin (I-1a) may be separately added.
黏著劑組成物(I-1)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-1) may be only one type, or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-1)中，溶劑的含量並無特別限定，適宜調節即可。 The content of the solvent in the adhesive composition (I-1) is not particularly limited, and may be appropriately adjusted.
<黏著劑組成物(I-2)> <Adhesive composition (I-2)>
如上所述，前述黏著劑組成物(I-2)含有能量線硬化性 之黏著性樹脂(I-2a)，該黏著性樹脂(I-2a)於非能量線硬化性之黏著性樹脂(I-1a)的側鏈導入有不飽和基。 As described above, the adhesive composition (I-2) contains an energy-ray-curable adhesive resin (I-2a), and the adhesive resin (I-2a) is non-energy-ray-curable adhesive resin (I-2a). -1a) introduces an unsaturated group into the side chain.
[黏著性樹脂(I-2a)] [Adhesive resin (I-2a)]
前述黏著性樹脂(I-2a)例如藉由使黏著性樹脂(I-1a)中的官能基與具有能量線聚合性不飽和基之含不飽和基之化合物反應而獲得。 The adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.
前述含不飽和基之化合物除具有前述能量線聚合性不飽和基以外，進一步具有以下基：該基藉由與黏著性樹脂(I-1a)中的官能基反應，而可與黏著性樹脂(I-1a)鍵結。 The unsaturated group-containing compound, in addition to the energy ray polymerizable unsaturated group, further has a group which can react with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) ( I-1a) bonding.
作為前述能量線聚合性不飽和基，例如可列舉：(甲基)丙烯醯基、乙烯基(亦稱為次乙基)、烯丙基(亦稱為2-丙烯基)等，較佳為(甲基)丙烯醯基。 Examples of the energy ray polymerizable unsaturated group include a (meth) acrylfluorenyl group, a vinyl group (also referred to as a hypoethyl group), and an allyl group (also referred to as a 2-propenyl group). (Meth) acrylfluorenyl.
作為可與黏著性樹脂(I-1a)中的官能基鍵結之基，例如可列舉：可與羥基或胺基鍵結之異氰酸酯基及縮水甘油基、以及可與羧基或環氧基鍵結之羥基及胺基等。 Examples of the group which can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group which can be bonded to a hydroxyl group or an amino group, and a carboxyl group or an epoxy group to be bonded. Hydroxyl and amine groups.
作為前述含不飽和基之化合物，例如可列舉：異氰酸(甲基)丙烯醯氧基乙酯、(甲基)丙烯醯基異氰酸酯、(甲基)丙烯酸縮水甘油酯等。 Examples of the unsaturated group-containing compound include (meth) acrylfluorenyl ethyl isocyanate, (meth) acrylfluorenyl isocyanate, and glycidyl (meth) acrylate.
黏著劑組成物(I-2)所含有之黏著性樹脂(I-2a)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組 合及比率可任意選擇。 The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-2)中，黏著性樹脂(I-2a)的含量相對於前述黏著劑組成物(I-2)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為10質量%至90質量%。 The content of the adhesive resin (I-2a) in the adhesive composition (I-2) is preferably 5% to 99% by mass relative to the total mass of the adhesive composition (I-2), and more preferably It is 10% by mass to 95% by mass, and particularly preferably 10% by mass to 90% by mass.
[交聯劑] [Crosslinking agent]
於使用例如與黏著性樹脂(I-1a)中相同的具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-2a)之情形時，黏著劑組成物(I-2)亦可進一步含有交聯劑。 When using, for example, the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer as the adhesive resin (I-2a) as the adhesive resin (I-1a), the adhesive composition (I-2) may further contain a crosslinking agent.
作為黏著劑組成物(I-2)中的前述交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 Examples of the crosslinking agent in the adhesive composition (I-2) include the same compounds as the crosslinking agent in the adhesive composition (I-1).
黏著劑組成物(I-2)所含有之交聯劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-2) may be only one type, or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
前述黏著劑組成物(I-2)中，交聯劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the said adhesive composition (I-2), content of a crosslinking agent with respect to content of the adhesive resin (I-2a) is 100 mass parts, Preferably it is 0.01 mass part-50 mass parts, More preferably, it is 0.1 mass parts 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.
[光聚合起始劑] [Photopolymerization initiator]
黏著劑組成物(I-2)亦可進一步含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-2)，即便照射紫外線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when a relatively low energy energy ray such as ultraviolet rays is irradiated.
作為黏著劑組成物(I-2)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).
黏著劑組成物(I-2)所含有之光聚合起始劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-2) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-2)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 The content of the photopolymerization initiator in the adhesive composition (I-2) is 100 parts by mass with respect to the content of the adhesive resin (I-2a), preferably 0.01 to 20 parts by mass, and more preferably 0.03 by mass Parts to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass.
[其他添加劑] [Other additives]
黏著劑組成物(I-2)中，在無損本發明之功效之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-2) may contain other additives which do not belong to any of the above components, as long as the effect of the present invention is not impaired.
作為黏著劑組成物(I-2)中的前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的化合物。 Examples of the other additives in the adhesive composition (I-2) include the same compounds as the other additives in the adhesive composition (I-1).
黏著劑組成物(I-2)所含有之其他添加劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-2) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-2)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 The content of the other additives in the adhesive composition (I-2) is not particularly limited, and may be appropriately selected according to the type of the other additives.
[溶劑] [Solvent]
以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-2)亦可含有溶劑。 For the same purpose as in the case of the adhesive composition (I-1), the adhesive composition (I-2) may contain a solvent.
作為黏著劑組成物(I-2)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 Examples of the solvent in the adhesive composition (I-2) include the same solvents as those in the adhesive composition (I-1).
黏著劑組成物(I-2)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-2) may be only one type, or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-2)中，溶劑的含量並無特別限定，適宜調節即可。 The content of the solvent in the adhesive composition (I-2) is not particularly limited, and may be appropriately adjusted.
<黏著劑組成物(I-3)> <Adhesive composition (I-3)>
如上所述，前述黏著劑組成物(I-3)含有前述黏著性樹脂(I-2a)、及能量線硬化性化合物。 As described above, the adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray-curable compound.
黏著劑組成物(I-3)中，黏著性樹脂(I-2a)的含量相對於前述黏著劑組成物(I-3)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 The content of the adhesive resin (I-2a) in the adhesive composition (I-3) is preferably 5% to 99% by mass relative to the total mass of the adhesive composition (I-3), and more preferably It is 10% by mass to 95% by mass, and particularly preferably 15% by mass to 90% by mass.
[能量線硬化性化合物] [Energy ray hardening compound]
作為黏著劑組成物(I-3)所含有之前述能量線硬化性化合物，可列舉具有能量線聚合性不飽和基，且可藉由照射能量線而硬化之單體及低聚物，可列舉與黏著劑組成物(I-1)所含有之能量線硬化性化合物相同的化合物。 Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers which have an energy ray polymerizable unsaturated group and can be hardened by irradiating energy rays, and examples thereof include: The same compound as the energy ray-curable compound contained in the adhesive composition (I-1).
黏著劑組成物(I-3)所含有之前述能量線硬化性化合物可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The aforementioned energy ray-curable compound contained in the adhesive composition (I-3) may be only one kind, or two or more kinds; in the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
前述黏著劑組成物(I-3)中，前述能量線硬化性化合物的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至300質量份，更佳為0.03質量份至200質量份，尤佳為0.05質量份至100質量份。 In the adhesive composition (I-3), the content of the energy ray-curable compound is 100 parts by mass with respect to the content of the adhesive resin (I-2a), preferably 0.01 to 300 parts by mass, and more preferably 0.03 parts by mass to 200 parts by mass, particularly preferably 0.05 to 100 parts by mass.
[光聚合起始劑] [Photopolymerization initiator]
黏著劑組成物(I-3)亦可進一步含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-3)，即便照射紫外線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a hardening reaction even when a relatively low energy energy ray such as ultraviolet rays is irradiated.
作為黏著劑組成物(I-3)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).
黏著劑組成物(I-3)所含有之光聚合起始劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type, or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-3)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)及前述能量線硬化性化合物的總含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 The content of the photopolymerization initiator in the adhesive composition (I-3) is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray-curable compound. Mass parts, more preferably 0.03 parts by mass to 10 parts by mass, and even more preferably 0.05 parts by mass to 5 parts by mass.
[其他添加劑] [Other additives]
黏著劑組成物(I-3)中，在無損本發明之功效之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-3) may contain other additives which do not belong to any of the above components, as long as the effect of the present invention is not impaired.
作為前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的溶劑。 Examples of the other additives include the same solvents as the other additives in the adhesive composition (I-1).
黏著劑組成物(I-3)所含有之其他添加劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-3) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-3)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 The content of the other additives in the adhesive composition (I-3) is not particularly limited, and may be appropriately selected according to the type of the other additives.
[溶劑] [Solvent]
以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-3)亦可含有溶劑。 For the same purpose as in the case of the adhesive composition (I-1), the adhesive composition (I-3) may contain a solvent.
作為黏著劑組成物(I-3)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 Examples of the solvent in the adhesive composition (I-3) include the same solvents as those in the adhesive composition (I-1).
黏著劑組成物(I-3)所含有之溶劑可僅為1種，亦可為 2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-3) may be only one type, or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-3)中，溶劑的含量並無特別限定，適宜調節即可。 The content of the solvent in the adhesive composition (I-3) is not particularly limited, and may be appropriately adjusted.
<黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物> <Adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3)>
前文主要對黏著劑組成物(I-1)、黏著劑組成物(I-2)及黏著劑組成物(I-3)進行了說明，但對於這些3種黏著劑組成物以外之全部黏著劑組成物(本說明書中，稱為「黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物」)，亦可同樣地使用作為這些含有成分所說明之成分。 The foregoing has mainly described the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3). However, all adhesives other than these three adhesive compositions are described. The composition (referred to as "adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3)" in this specification) can also be used in the same manner as described for these contained components. ingredient.
作為黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物，除了能量線硬化性之黏著劑組成物以外，亦可列舉非能量線硬化性之黏著劑組成物。 As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy ray-curable adhesive composition, non-energy ray-curable adhesives can also be mentioned组合 物。 Composition.
作為非能量線硬化性之黏著劑組成物，例如可列舉：含有丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等非能量線硬化性之黏著性樹脂(I-1a)之黏著劑組成物(I-4)，較佳為含有丙烯酸系樹脂之黏著劑組成物。 Examples of non-energy-ray-curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, and polycarbonates. The adhesive composition (I-4) of the non-energy-ray-curable adhesive resin (I-1a), such as an ester or an ester-based resin, is preferably an adhesive composition containing an acrylic resin.
黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物較佳為含有1種或2種以上之交聯劑，該交聯劑 的含量可設為與上述之黏著劑組成物(I-1)等之情形相同。 The adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contains one or two or more kinds of cross-linking agents, and the content of the cross-linking agent can be set to be equal to The same applies to the above-mentioned adhesive composition (I-1) and the like.
<黏著劑組成物(I-4)> <Adhesive composition (I-4)>
作為較佳的黏著劑組成物(I-4)，例如可列舉：含有前述黏著性樹脂(I-1a)及交聯劑之黏著劑組成物。 As a preferable adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.
[黏著性樹脂(I-1a)] [Adhesive resin (I-1a)]
作為黏著劑組成物(I-4)中的黏著性樹脂(I-1a)，可列舉與黏著劑組成物(I-1)中的黏著性樹脂(I-1a)相同的樹脂。 Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same resins as the adhesive resin (I-1a) in the adhesive composition (I-1).
黏著劑組成物(I-4)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-4)中，黏著性樹脂(I-1a)的含量相對於前述黏著劑組成物(I-4)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 The content of the adhesive resin (I-1a) in the adhesive composition (I-4) is preferably 5% to 99% by mass relative to the total mass of the adhesive composition (I-4), and more preferably It is 10% by mass to 95% by mass, and particularly preferably 15% by mass to 90% by mass.
[交聯劑] [Crosslinking agent]
於使用除了源自(甲基)丙烯酸烷基酯之結構單元以外，進一步具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-1a)之情形時，黏著劑組成物(I-4)較佳為進一步含有交聯劑。 When the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), The adhesive composition (I-4) preferably further contains a crosslinking agent.
作為黏著劑組成物(I-4)中的交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 Examples of the crosslinking agent in the adhesive composition (I-4) include the same compounds as the crosslinking agent in the adhesive composition (I-1).
黏著劑組成物(I-4)所含有之交聯劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-4) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
前述黏著劑組成物(I-4)中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the said adhesive composition (I-4), content of a crosslinking agent with respect to content of the adhesive resin (I-1a) is 100 mass parts, Preferably it is 0.01 mass part-50 mass parts, More preferably, it is 0.1 mass parts 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.
[其他添加劑] [Other additives]
黏著劑組成物(I-4)中，在無損本發明之功效之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-4) may contain other additives which do not belong to any of the above components, as long as the effect of the present invention is not impaired.
作為前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的化合物。 Examples of the other additives include the same compounds as the other additives in the adhesive composition (I-1).
黏著劑組成物(I-4)所含有之其他添加劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-4) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-4)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 The content of the other additives in the adhesive composition (I-4) is not particularly limited, and may be appropriately selected according to the type of the other additives.
[溶劑] [Solvent]
以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-4)亦可含有溶劑。 For the same purpose as in the case of the adhesive composition (I-1), the adhesive composition (I-4) may contain a solvent.
作為黏著劑組成物(I-4)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 Examples of the solvent in the adhesive composition (I-4) include the same solvents as those in the adhesive composition (I-1).
黏著劑組成物(I-4)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-4) may be only one type, or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
黏著劑組成物(I-4)中，溶劑的含量並無特別限定，適宜調節即可。 The content of the solvent in the adhesive composition (I-4) is not particularly limited, and may be appropriately adjusted.
可用於本發明之保護膜形成用複合片中，黏著劑層較佳為非能量線硬化性。原因在於，若黏著劑層為能量線硬化性，則會有無法抑制於藉由照射能量線而使保護膜形成用膜硬化時黏著劑層亦同時硬化之情形。若黏著劑層與保護膜形成用膜同時硬化，則會有硬化後之保護膜形成用膜及黏著劑層於這些之界面黏附至無法剝離之程度之情形。該情形時，難以將背面具備硬化後之保護膜形成用膜，亦即保護膜之半導體晶片(本說明書中，有時稱為「附有保護膜的半導體晶片」)，自具備硬化後之黏著劑層之支持片剝離，無法正常地拾取附有保護膜的半導體晶片。藉由本發明中的支持片中的黏著劑層設為非能量線硬化性，可確實地避免此種不良情形，從而可更容易地拾取附有保護膜的半導體晶片。 The adhesive sheet that can be used in the protective film forming composite sheet of the present invention is preferably non-energy ray-curable. The reason is that if the adhesive layer is energy ray-curable, it may not be possible to prevent the adhesive layer from being simultaneously cured when the protective film-forming film is cured by irradiating the energy ray. If the adhesive layer and the protective film-forming film are cured at the same time, the cured protective film-forming film and the adhesive layer may adhere to such an interface that they cannot be peeled off. In this case, it is difficult to provide a hardened protective film forming film on the back surface, that is, a semiconductor wafer with a protective film (in this specification, sometimes referred to as a "semiconductor wafer with a protective film"). The support sheet of the agent layer is peeled off, and a semiconductor wafer with a protective film cannot be picked up normally. By making the adhesive layer in the support sheet of the present invention non-energy ray hardenable, such an undesirable situation can be reliably avoided, and a semiconductor wafer with a protective film can be more easily picked up.
本文對黏著劑層為非能量線硬化性之情形之功效進行了說明，但即便支持片中的與保護膜形成用膜直接接觸之層為黏著劑層以外之層，只要該層為非能量線硬化性，則亦發揮同樣的功效。 This article describes the effectiveness of the case where the adhesive layer is non-energy ray hardenable, but even if the layer in the support sheet that is in direct contact with the protective film-forming film is a layer other than the adhesive layer, as long as the layer is non-energy ray Sclerosis, it also plays the same role.
<<黏著劑組成物的製造方法>> << Manufacturing method of adhesive composition >>
黏著劑組成物(I-1)至黏著劑組成物(I-3)、或者黏著劑組成物(I-4)等黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物藉由下述方式而獲得：將前述黏著劑、及視需要之前述黏著劑以外的成分等用以構成黏著劑組成物之各成分加以調配。 Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-1) such as adhesive composition (I-4) to adhesive composition (I-3) The other adhesive composition is obtained by blending the components of the adhesive composition, such as the aforementioned adhesive, and optionally other components than the aforementioned adhesive, as necessary.
調配各成分時的添加順序並無特別限定，亦可同時添加2種以上之成分。 The order of adding the components is not particularly limited, and two or more components may be added simultaneously.
於使用溶劑之情形時，可藉由下述方式使用：將溶劑與溶劑以外的任一種調配成分混合而將該調配成分預先稀釋；亦可藉由下述方式使用：不將溶劑以外的任一種調配成分預先稀釋而將溶劑與這些調配成分混合。 When a solvent is used, it can be used by mixing the solvent with any formulation component other than the solvent and diluting the formulation component in advance; it can also be used by the following method: not using any solvent other than the solvent The preparation ingredients are diluted in advance, and the solvent is mixed with these preparation ingredients.
調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機而進行混合之方法；施加超音波而進行混合之方法等。 There is no particular limitation on the method of mixing the components during preparation, and it may be appropriately selected from the following known methods: a method in which a stirrer or a stirring blade is rotated to perform mixing; a method in which a mixer is used to perform mixing; Method of mixing and the like.
關於添加及混合各成分時的溫度及時間，只要不使各調配成分劣化，則並無特別限定，適宜調節即可，溫度較 佳為15℃至30℃。 The temperature and time when each component is added and mixed are not particularly limited as long as the prepared components are not deteriorated, and may be appropriately adjusted. The temperature is preferably 15 ° C to 30 ° C.
◎保護膜形成用片 ◎ Protective film forming sheet
本發明中，保護膜形成用膜除了以上述之保護膜形成用複合片之形式使用以外，亦可以於剝離膜上設置有保護膜形成用膜而成之保護膜形成用片之形式，貼附於前述半導體晶圓的背面後，貼附支持片而使用。 In the present invention, the protective film-forming film may be used in the form of a composite sheet for forming a protective film, as described above, or may be attached to a release film as a sheet for forming a protective film. After the back surface of the semiconductor wafer, a support sheet is attached and used.
此處可使用之保護膜形成用膜如上述之保護膜形成用複合片之項中所說明。 The protective film forming film which can be used here is as described in the item of the composite sheet for protective film formation mentioned above.
圖7係以示意方式顯示可用於本發明之保護膜形成用片2F的一實施形態之剖視圖。 FIG. 7 is a cross-sectional view schematically showing an embodiment of a sheet 2F for forming a protective film that can be used in the present invention.
此處所示之保護膜形成用片2F係於第1剝離膜15'上具備保護膜形成用膜13並於保護膜形成用膜13上具備第2剝離膜15"而成。 The protective film-forming sheet 2F shown here is formed by including a protective film-forming film 13 on the first release film 15 ′ and a second release film 15 ″ on the protective film-forming film 13.
圖7所示之保護膜形成用片2F係以下述方式使用：在移除輕剝離側的第2剝離膜15"之狀態下，於保護膜形成用膜13的表面13a中央側的一部分區域貼附半導體晶圓(省略圖示)的背面，並進一步在移除重剝離側的第1剝離膜15'之狀態下，於保護膜形成用膜13中的與表面13a為相反側的另一方的表面13b上貼附支持片。並且，如例如圖4般，將保護膜形成用膜13的周緣部附近的區域，經由治具用接著劑層16貼附於環狀框等治具，或者，如例如圖6般，將保護膜形成用片2F切成圓形而積層於支持片，藉由支持片中的黏著劑部保持於環狀框等治具。 The protective film forming sheet 2F shown in FIG. 7 is used in a state where the second release film 15 "on the light release side is removed, and a part of the area on the center side of the surface 13a of the protective film forming film 13 is applied. Attach the back surface of the semiconductor wafer (not shown) and further remove the first release film 15 'on the heavy release side. The protective film formation film 13 is on the other side opposite to the surface 13a. A support sheet is affixed to the surface 13b, and a region near the peripheral edge portion of the protective film-forming film 13 is attached to a jig such as a ring frame via the jig adhesive layer 16 as shown in FIG. 4, or, As shown in FIG. 6, for example, the protective film forming sheet 2F is cut into a circle and laminated on a support sheet, and the adhesive part in the support sheet is held on a jig such as a ring frame.
此處，將剝離力小的剝離膜稱為輕剝離側的剝離膜，將剝離力大的剝離膜稱為重剝離側的剝離膜。若使剝離力存在差異，則可防止在僅剝離輕剝離側的剝離膜時，保護膜形成用膜自重剝離側的剝離膜隆起之虞，或者保護膜形成用膜欲追隨於兩剝離膜而拉伸變形之情形。 Here, a peeling film with a small peeling force is called a peeling film with a light peeling side, and a peeling film with a high peeling force is called a peeling film with a heavy peeling side. If there is a difference in the peeling force, it is possible to prevent the peeling film on the peeling side of the protective film from bulging when the peeling film on the light peeling side is peeled only, or the protective film forming film is drawn to follow both peeling films Extension deformation.
本發明中，保護膜形成用膜硬化而獲得之保護膜與支持片之間的黏著力較佳為50mN/25mm至1500mN/25mm，更佳為52mN/25mm至1450mN/25mm，尤佳為53mN/25mm至1430mN/25mm。藉由前述黏著力為前述下限值以上，拾取附有保護膜的半導體晶片時，目標外的附有保護膜的半導體晶片之拾取得到抑制，從而可高選擇性地拾取目標之附有保護膜的半導體晶片。藉由前述黏著力為前述上限值以下，拾取附有保護膜的半導體晶片時，半導體晶片之破裂及缺損得到抑制。如此，藉由前述黏著力為特定範圍內，保護膜形成用複合片具有良好的拾取適性。 In the present invention, the adhesive force between the protective film and the support sheet obtained by curing the protective film forming film is preferably 50mN / 25mm to 1500mN / 25mm, more preferably 52mN / 25mm to 1450mN / 25mm, and even more preferably 53mN / 25mm to 1430mN / 25mm. When the adhesive force is equal to or greater than the aforementioned lower limit value, when picking up a semiconductor wafer with a protective film, picking up a semiconductor wafer with a protective film outside the target is suppressed, so that the target with a protective film can be picked up with high selectivity. Semiconductor wafer. When the adhesive force is equal to or lower than the upper limit value, when a semiconductor wafer with a protective film is picked up, cracks and defects of the semiconductor wafer are suppressed. In this way, with the aforementioned adhesive force being within a specific range, the composite sheet for forming a protective film has good pickup suitability.
本發明中，即便為保護膜形成用膜硬化後，只要維持支持片及保護膜形成用膜之硬化物(換言之，支持片及保護膜)之積層結構，則亦將該積層結構體稱為「保護膜形成用複合片」。 In the present invention, even after the protective film forming film is cured, as long as the laminated structure of the support sheet and the protective film forming film (in other words, the supporting sheet and the protective film) is maintained, the laminated structure is referred to as " Composite sheet for protective film formation ".
保護膜與支持片之間的黏著力可利用以下方法進行測定。 The adhesive force between a protective film and a support sheet can be measured by the following method.
亦即，將寬度為25mm且長度為任意之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜，貼附於被接著體。 That is, a protective film-forming composite sheet having a width of 25 mm and an arbitrary length is attached to the adherend through the protective film-forming film of the protective film-forming composite sheet.
接著，照射能量線使保護膜形成用膜硬化而形成保護膜後，自貼附於被接著體之該保護膜，將支持片以剝離速度300mm/min剝離。此時的剝離係設為以下所謂之180°剝離：以保護膜及支持片相互接觸之面彼此成為180°之角度之方式，將支持片沿該支持片的長度方向(保護膜形成用複合片的長度方向)剝離。然後，測定該180°剝離時的荷重(剝離力)，將該荷重(剝離力)的測定值設為前述黏著力(mN/25mm)。 Next, the protective film is cured by irradiating energy rays to form a protective film, and then the protective film is self-adhered to the adherend, and the support sheet is peeled at a peeling speed of 300 mm / min. The peeling at this time is a so-called 180 ° peeling in which the support film and the supporting sheet contact each other at an angle of 180 °, and the supporting sheet is formed along the longitudinal direction of the supporting sheet (the protective film-forming composite sheet). Length direction). Then, the load (peeling force) at the time of the 180 ° peeling was measured, and the measured value of the load (peeling force) was the aforementioned adhesive force (mN / 25mm).
供於測定之保護膜形成用複合片的長度只要為可穩定地檢測出黏著力之範圍，則並無特別限定，較佳為100mm至300mm。測定時，較佳為使保護膜形成用複合片成為貼附於被接著體之狀態，從而使保護膜形成用複合片之貼附狀態穩定化。 The length of the protective film-forming composite sheet for measurement is not particularly limited as long as it is a range in which the adhesive force can be stably detected, and is preferably 100 mm to 300 mm. At the time of measurement, it is preferred that the composite sheet for forming a protective film is in a state of being adhered to an adherend, thereby stabilizing the attached state of the composite sheet for forming a protective film.
本發明中，保護膜形成用膜與前述支持片之間的黏著力並無特別限定，例如可為80mN/25mm以上等，較佳為100mN/25mm以上，更佳為150mN/25mm以上，尤佳為200mN/25mm以上。藉由前述黏著力為100mN/25mm以上，切割時保護膜形成用膜與支持片之剝離得到抑制，例如，背面具備保護膜形成用膜之半導體晶片自支持片之飛 散得到抑制。 In the present invention, the adhesive force between the protective film-forming film and the support sheet is not particularly limited, and may be, for example, 80 mN / 25 mm or more, preferably 100 mN / 25 mm or more, more preferably 150 mN / 25 mm or more, and particularly preferably 200mN / 25mm or more. With the aforementioned adhesive force of 100 mN / 25 mm or more, peeling of the protective film-forming film from the supporting sheet during dicing is suppressed, and for example, scattering of a semiconductor wafer having a protective film-forming film on the back from the supporting sheet is suppressed.
另一方面，保護膜形成用膜與前述支持片之間的黏著力的上限值並無特別限定，例如可設為4000mN/25mm、3500mN/25mm、3000mN/25mm等之任一者。但是，這些為一例。 On the other hand, the upper limit of the adhesive force between the protective film-forming film and the support sheet is not particularly limited, and may be, for example, any of 4000 mN / 25 mm, 3500 mN / 25 mm, and 3000 mN / 25 mm. However, these are examples.
關於保護膜形成用膜與支持片之間的黏著力，除了不藉由照射能量線使供於測定之保護膜形成用膜硬化之方面以外，可利用與上述之保護膜與支持片之間的黏著力相同的方法進行測定。 Regarding the adhesive force between the protective film-forming film and the supporting sheet, in addition to the fact that the protective film-forming film for measurement is not hardened by irradiating energy rays, it is possible to use the adhesive force between the protective film and the supporting sheet described above. Adhesion was measured by the same method.
上述之保護膜與支持片之間的黏著力、及保護膜形成用膜與支持片之間的黏著力例如可藉由調節保護膜形成用膜的含有成分的種類及量、支持片中的設置保護膜形成用膜之層的構成材料、該層的表面狀態等而適宜調節。 The adhesive force between the protective film and the support sheet described above, and the adhesive force between the protective film-forming film and the support sheet can be adjusted by, for example, the type and amount of components contained in the protective film-forming film, and the setting in the support sheet. The material constituting the layer of the protective film-forming film, the surface state of the layer, and the like are appropriately adjusted.
例如，保護膜形成用膜的含有成分的種類及量可藉由後述之保護膜形成用組成物的含有成分的種類及量進行調節。並且，藉由調節保護膜形成用組成物的含有成分中，例如不具有能量線硬化性基之聚合物(b)的種類及含量、填充材料(d)的含量、或交聯劑(f)的含量，可更容易地調節保護膜或保護膜形成用膜與支持片之間的黏著力。 For example, the type and amount of the component contained in the film for forming a protective film can be adjusted by the type and amount of the component contained in the composition for forming a protective film described later. In addition, by adjusting the content of the protective film-forming composition, for example, the type and content of the polymer (b) having no energy ray-curable group, the content of the filler (d), or the crosslinking agent (f) Content, it is easier to adjust the adhesion between the protective film or the film for forming a protective film and the support sheet.
例如，於支持片中的設置保護膜形成用膜之層為黏著 劑層之情形時，該層的構成材料可藉由調節黏著劑層的含有成分的種類及量而適宜調節。並且，黏著劑層的含有成分的種類及量可藉由上述之黏著劑組成物的含有成分的種類及量而進行調節。 For example, in the case where the layer provided with the film for forming a protective film in the support sheet is an adhesive layer, the constituent material of the layer can be appropriately adjusted by adjusting the type and amount of the components contained in the adhesive layer. In addition, the type and amount of the component contained in the adhesive layer can be adjusted by the type and amount of the component contained in the adhesive composition described above.
另一方面，於支持片中的設置保護膜形成用膜之層為基材之情形時，保護膜或保護膜形成用膜與支持片之間的黏著力，除了基材的構成材料以外，亦可藉由基材的表面狀態進行調節。並且，基材的表面狀態例如可藉由實施前文作為提高基材與其他層之密接性之處理所列舉之表面處理而進行調節：利用噴砂處理、溶劑處理等之凹凸化處理；電暈放電處理、電子束照射處理、電漿處理、臭氧/紫外線照射處理、火焰處理、鉻酸處理、熱風處理等氧化處理；底塗處理等任一處理。 On the other hand, in the case where the layer provided with the film for forming a protective film in the support sheet is a base material, the adhesive force between the protective film or the film for forming a protective film and the support sheet is not only the constituent material of the base material, but also It can be adjusted by the surface state of the substrate. In addition, the surface state of the substrate can be adjusted, for example, by implementing the surface treatments listed above as the treatments for improving the adhesion between the substrate and other layers: roughening treatment using sandblasting treatment, solvent treatment, etc .; corona discharge treatment , Electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; any treatment such as primer coating treatment.
保護膜形成用膜可列舉：具有能量線硬化性，例如含有能量線硬化性成分(a)之膜。 Examples of the film for forming a protective film include energy ray curable films, for example, films containing an energy ray curable component (a).
能量線硬化性成分(a)較佳為未硬化，較佳為具有黏著性，更佳為未硬化且具有黏著性。 The energy ray-curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably is uncured and has adhesiveness.
保護膜形成用膜可僅為1層(單層)，亦可為2層以上之複數層；於為複數層之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The film for forming the protective film may be only one layer (single layer) or plural layers of two or more layers. In the case of plural layers, these plural layers may be the same as or different from each other. The combination of these plural layers is not Specially limited.
保護膜形成用膜的厚度較佳為1μm至100μm，更佳 為5μm至75μm，尤佳為5μm至50μm。藉由保護膜形成用膜的厚度為前述下限值以上，可形成保護能力更高的保護膜。藉由保護膜形成用膜的厚度為前述上限值以下，可抑制厚度過厚。 The thickness of the protective film-forming film is preferably 1 m to 100 m, more preferably 5 m to 75 m, and even more preferably 5 m to 50 m. When the thickness of the protective film-forming film is equal to or more than the aforementioned lower limit value, a protective film having a higher protective ability can be formed. When the thickness of the protective film-forming film is equal to or less than the above-mentioned upper limit, excessive thickness can be suppressed.
此處，所謂「保護膜形成用膜的厚度」意指保護膜形成用膜整體的厚度，例如，所謂由複數層構成之保護膜形成用膜的厚度意指構成保護膜形成用膜之全部層的合計厚度。 Here, the "thickness of the film for forming a protective film" means the thickness of the entire film for forming a protective film. For example, the thickness of the film for forming a protective film composed of a plurality of layers means all layers constituting the film for forming a protective film. Total thickness.
關於使保護膜形成用膜硬化而形成保護膜時的硬化條件，只要保護膜成為充分發揮該保護膜的功能之程度的硬化度，則並無特別限定，根據保護膜形成用膜的種類適宜選擇即可。 The hardening conditions when the protective film is cured to form the protective film are not particularly limited as long as the protective film has a degree of hardening sufficient to perform the function of the protective film, and is appropriately selected depending on the type of the protective film forming film. Just fine.
例如，保護膜形成用膜之硬化時，能量線之照度較佳為4mW/cm2至280mW/cm2。前述硬化時，能量線之光量較佳為3mJ/cm2至1000mJ/cm2。 For example, when curing the protective film-forming film, the illuminance of the energy ray is preferably 4 mW / cm 2 to 280 mW / cm 2 . In the aforementioned hardening, the light amount of the energy rays is preferably from 3 mJ / cm 2 to 1000 mJ / cm 2 .
<<保護膜形成用組成物>> << Composition for forming protective film >>
保護膜形成用膜可使用含有該保護膜形成用膜的構成材料之保護膜形成用組成物而形成。例如，於保護膜形成用膜之形成對象面塗敷保護膜形成用組成物，視需要使保護膜形成用組成物乾燥，藉此可於目標部位形成保護膜形成用膜。保護膜形成用組成物中的常溫下不會氣化的成分彼此的含量比率，通常與保護膜形成用膜中的前述成分 彼此的含量比率相同。此處，所謂「常溫」如前文所說明。 The film for protective film formation can be formed using the composition for protective film formation containing the constituent material of the film for protective film formation. For example, by applying the composition for forming a protective film on the formation target surface of the film for forming a protective film, and drying the composition for forming a protective film as necessary, a film for forming a protective film can be formed on a target portion. The content ratio of the components that do not vaporize at room temperature in the composition for forming a protective film is usually the same as the content ratio of the aforementioned components in the film for forming a protective film. Here, the so-called "normal temperature" is as described above.
利用公知的方法塗敷保護膜形成用組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、繞線棒式塗佈機、接觸式塗佈機等。 The composition for forming a protective film may be applied by a known method, and examples thereof include a method using various applicators: air knife applicators, doctor blade applicators, bar coaters, gravure coaters, and rollers. Type coater, roll knife coater, curtain coater, mold coater, knife coater, screen coater, wire rod coater, contact coater, etc.
保護膜形成用組成物的乾燥條件並無特別限定，於保護膜形成用組成物含有後述溶劑之情形時，較佳為進行加熱乾燥，該情形時，較佳為於例如70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the composition for forming a protective film are not particularly limited. When the composition for forming a protective film contains a solvent to be described later, it is preferable to perform drying by heating. In this case, it is preferably 70 ° C to 130 ° C and Dry for 10 seconds to 5 minutes.
<保護膜形成用組成物(IV-1)> <Protective film forming composition (IV-1)>
作為保護膜形成用組成物，例如可列舉含有前述能量線硬化性成分(a)之保護膜形成用組成物(IV-1)等。 Examples of the composition for forming a protective film include the composition (IV-1) for forming a protective film containing the energy ray-curable component (a).
[能量線硬化性成分(a)] [Energy ray hardening component (a)]
能量線硬化性成分(a)係藉由照射能量線而硬化之成分，該成分用以對保護膜形成用膜賦予造膜性或可撓性等。 The energy ray-curable component (a) is a component that is hardened by irradiating energy rays, and is used to impart film-forming properties, flexibility, and the like to a film for forming a protective film.
作為能量線硬化性成分(a)，例如可列舉：具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)、及具有能量線硬化性基且分子量為100至80000 之化合物(a2)。前述聚合物(a1)可至少一部分藉由後述之交聯劑(f)進行交聯，亦可不進行交聯。 Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray-curable group and a molecular weight of 100 to 80,000. (a2). The polymer (a1) may be crosslinked at least in part by a cross-linking agent (f) described later, or may not be cross-linked.
本說明書中，所謂重量平均分子量，只要無特別說明，則意指藉由凝膠滲透層析(GPC；Gel Permeation Chromatography)法所測定之聚苯乙烯換算值。 In this specification, the weight average molecular weight means a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
(具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)) (Polymer (a1) having an energy ray hardening group and a weight average molecular weight of 80,000 to 2,000,000)
作為具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)，例如可列舉丙烯酸系樹脂(a1-1)，該丙烯酸系樹脂(a1-1)係丙烯酸系聚合物(a11)與能量線硬化性化合物(a12)聚合而成，前述丙烯酸系聚合物(a11)具有可與其他化合物所具有之基反應之官能基，前述能量線硬化性化合物(a12)具有與前述官能基反應之基及能量線硬化性雙鍵等能量線硬化性基。 Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic resin (a1-1), and the acrylic resin (a1-1) acrylic polymer (a11) ) Is polymerized with an energy ray-curable compound (a12), the acrylic polymer (a11) has a functional group capable of reacting with a group of another compound, and the energy ray-curable compound (a12) has a functional group Reaction bases and energy ray hardenable groups such as energy ray hardenable double bonds.
作為可與其他化合物所具有之基反應之前述官能基，例如可列舉：羥基、羧基、胺基、取代胺基(胺基的1個或2個氫原子被氫原子以外的基取代而成之基)、環氧基等。但是，就防止半導體晶圓或半導體晶片等的電路腐蝕之方面而言，前述官能基較佳為羧基以外的基。 Examples of the functional group that can react with a group possessed by another compound include, for example, a hydroxyl group, a carboxyl group, an amine group, and a substituted amine group (where one or two hydrogen atoms of the amine group are substituted with a group other than a hydrogen atom Group), epoxy group, and the like. However, in terms of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor wafer, the functional group is preferably a group other than a carboxyl group.
這些之中，前述官能基較佳為羥基。 Among these, the functional group is preferably a hydroxyl group.
．具有官能基之丙烯酸系聚合物(a11) ． Acrylic polymer (a11) with functional group
前述具有官能基之丙烯酸系聚合物(a11)例如可列舉：使前述具有官能基之丙烯酸系單體與前述不具有官能基之丙烯酸系單體進行共聚合而成之聚合物，亦可為除這些單體以外，進一步使丙烯酸系單體以外的單體(非丙烯酸系單體)進行共聚合而成之聚合物。 Examples of the acrylic polymer (a11) having a functional group include a polymer obtained by copolymerizing the acrylic monomer having a functional group and the acrylic monomer having no functional group. In addition to these monomers, a polymer obtained by copolymerizing monomers (non-acrylic monomers) other than the acrylic monomer.
另外，前述丙烯酸系聚合物(a11)可為無規共聚物，亦可為嵌段共聚物。 The acrylic polymer (a11) may be a random copolymer or a block copolymer.
作為前述具有官能基之丙烯酸系單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含取代胺基之單體、含環氧基之單體等。 Examples of the acrylic monomer having a functional group include a hydroxyl-containing monomer, a carboxyl-containing monomer, an amine-containing monomer, a substituted amine-containing monomer, and an epoxy-containing monomer. .
作為前述含羥基之單體，例如可列舉：(甲基)丙烯酸羥基甲酯、(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3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。 Examples of the hydroxyl-containing monomer include: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Hydroxyalkyl (meth) acrylates such as hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; vinyl alcohol, Non- (meth) acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols having no (meth) acrylfluorenyl skeleton) and the like.
作為前述含羧基之單體，例如可列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；反丁烯二酸、衣康酸、順丁烯二酸、檸康酸等乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧 酸)；前述乙烯性不飽和二羧酸之酐；甲基丙烯酸2-羧基乙酯等(甲基)丙烯酸羧基烷基酯等。 Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth) acrylic acid and butene acid; fumaric acid and itaconic acid. Acid, maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate (Meth) acrylic acid alkyl esters and the like.
前述具有官能基之丙烯酸系單體較佳為含羥基之單體、含羧基之單體，更佳為含羥基之單體。 The acrylic monomer having a functional group is preferably a hydroxyl-containing monomer or a carboxyl-containing monomer, and more preferably a hydroxyl-containing monomer.
構成前述丙烯酸系聚合物(a11)之前述具有官能基之丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The acrylic monomer having a functional group constituting the acrylic polymer (a11) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
作為不具有前述官能基之丙烯酸系單體，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯(亦稱為(甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯(亦稱為(甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯(亦稱為(甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯(亦稱為(甲基)丙烯酸硬脂酯)等構成烷基酯之烷基的碳數 為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等。 Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate , Isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (also known as lauryl (meth) acrylate) ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also known as myristyl (meth) acrylate), pentadecyl (meth) acrylate, (formyl Cetyl acrylate (also known as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also known as (meth) Stearyl acrylate) and other constituent alkanes An ester of alkyl having a chain of 1 to 18 structures (meth) acrylate and the like.
另外，作為前述不具有官能基之丙烯酸系單體，例如亦可列舉：(甲基)丙烯酸甲氧基甲酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基甲酯、(甲基)丙烯酸乙氧基乙酯等含烷氧基烷基之(甲基)丙烯酸酯；包含(甲基)丙烯酸苯酯等(甲基)丙烯酸芳基酯等之具有芳香族基之(甲基)丙烯酸酯；非交聯性的(甲基)丙烯醯胺及其衍生物；(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丙酯等非交聯性的具有三級胺基之(甲基)丙烯酸酯等。 Examples of the acrylic monomer having no functional group include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, and ethoxymethyl (meth) acrylate. (Meth) acrylic acid esters containing alkoxyalkyl groups such as esters, ethoxyethyl (meth) acrylate, and aromatic groups containing aryl (meth) acrylates such as phenyl (meth) acrylate (Meth) acrylates; non-crosslinkable (meth) acrylamidonium and its derivatives; N, N-dimethylaminoethyl (meth) acrylate, N, N- (meth) acrylate Non-crosslinkable (meth) acrylates having tertiary amino groups, such as dimethylaminopropyl ester.
構成前述丙烯酸系聚合物(a11)之前述不具有官能基之丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The acrylic monomer (a11) constituting the acrylic polymer (a11) may have only one type of acrylic monomer or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
作為前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
構成前述丙烯酸系聚合物(a11)之前述非丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The non-acrylic monomers constituting the acrylic polymer (a11) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
前述丙烯酸系聚合物(a11)中，由具有前述官能基之丙烯酸系單體衍生之結構單元之量相對於構成該丙烯酸系聚合物(a11)之結構單元之總質量的比例(含量)較佳為0.1 質量%至50質量%，更佳為1質量%至40質量%，尤佳為3質量%至30質量%。藉由前述比例為此種範圍，可將由前述丙烯酸系聚合物(a11)與前述能量線硬化性化合物(a12)之共聚合所獲得之前述丙烯酸系樹脂(a1-1)中能量線硬化性基的含量容易地調節為使第1保護膜的硬化程度較佳之範圍。 In the aforementioned acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the aforementioned functional group to the total mass of the structural unit constituting the acrylic polymer (a11) is preferably It is 0.1 to 50% by mass, more preferably 1 to 40% by mass, and even more preferably 3 to 30% by mass. When the foregoing ratio is within this range, the energy ray-curable group in the acrylic resin (a1-1) obtained by copolymerizing the acrylic polymer (a11) and the energy ray-curable compound (a12) can be obtained. The content of is easily adjusted to a range in which the degree of hardening of the first protective film is better.
構成前述丙烯酸系樹脂(a1-1)之前述丙烯酸系聚合物(a11)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
保護膜形成用組成物(IV-1)中，丙烯酸系樹脂(a1-1)的含量相對於前述保護膜形成用組成物(IV-1)的總質量，較佳為1質量%至40質量%，更佳為2質量%至30質量%，尤佳為3質量%至20質量%。 The content of the acrylic resin (a1-1) in the protective film-forming composition (IV-1) is preferably 1% to 40% by mass based on the total mass of the protective film-forming composition (IV-1). %, More preferably 2% to 30% by mass, and even more preferably 3% to 20% by mass.
．能量線硬化性化合物(a12) ． Energy ray hardening compound (a12)
前述能量線硬化性化合物(a12)較佳為具有選自由異氰酸酯基、環氧基及羧基所組成之群組中的1種或2種以上作為可與前述丙烯酸系聚合物(a11)所具有之官能基反應之基，更佳為具有異氰酸酯基作為前述基。於前述能量線硬化性化合物(a12)例如具有異氰酸酯基作為前述基之情形時，該異氰酸酯基與前述具有羥基作為官能基之丙烯酸系聚合物(a11)的該羥基容易反應。 The energy ray-curable compound (a12) preferably has one or two or more kinds selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group, and has the same property as the acrylic polymer (a11). The functional group is preferably a group having an isocyanate group as the aforementioned group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as a functional group.
前述能量線硬化性化合物(a12)較佳為於1分子中具有1個至5個前述能量線硬化性基，更佳為具有1個至3個前述能量線硬化性基。 The energy ray-curable compound (a12) preferably has one to five energy ray-curable groups in one molecule, and more preferably has one to three energy ray-curable groups.
作為前述能量線硬化性化合物(a12)，例如可列舉：異氰酸2-甲基丙烯醯氧基乙酯、間-異丙烯基-α,α-二甲基苄基異氰酸酯、甲基丙烯醯基異氰酸酯、異氰酸烯丙酯、異氰酸1,1-(雙丙烯醯氧基甲基)乙酯；藉由二異氰酸酯化合物或多異氰酸酯化合物與(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物；藉由二異氰酸酯化合物或多異氰酸酯化合物、多元醇化合物及(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物等。 Examples of the energy ray-curable compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and methacrylium Isocyanate, allyl isocyanate, 1,1- (bispropenyloxymethyl) ethyl isocyanate; by reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate Acrylic fluorenyl monoisocyanate compounds obtained; propylene fluorenyl monoisocyanate compounds obtained by the reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate, and the like.
這些之中，前述能量線硬化性化合物(a12)較佳為異氰酸2-甲基丙烯醯氧基乙酯。 Among these, the energy ray-curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.
構成前述丙烯酸系樹脂(a1-1)之前述能量線硬化性化合物(a12)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one kind, or two or more kinds. In the case of two or more kinds, these combinations and ratios can be arbitrarily selected.
前述丙烯酸系樹脂(a1-1)中，源自前述能量線硬化性化合物(a12)之能量線硬化性基的含量相對於源自前述丙烯酸系聚合物(a11)之前述官能基的含量之比例較佳為20 莫耳%至120莫耳%，更佳為35莫耳%至100莫耳%，尤佳為50莫耳%至100莫耳%。藉由前述含量比例為此種範圍，由硬化所形成之保護膜的接著力變得更大。再者，於前述能量線硬化性化合物(a12)為一官能(於1分子中具有1個前述基)化合物之情形時，前述含量之比例的上限值成為100莫耳%，但於前述能量線硬化性化合物(a12)為多官能(於1分子中具有2個以上前述基)化合物之情形時，會有前述含量之比例的上限值超過100莫耳%之情形。 The ratio of the content of the energy-ray-curable group derived from the energy-ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) in the acrylic resin (a1-1). It is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%. When the aforementioned content ratio is in such a range, the adhesive force of the protective film formed by curing becomes larger. When the energy ray-curable compound (a12) is a monofunctional compound (having one of the aforementioned groups in one molecule), the upper limit of the content ratio is 100 mole%. When the linearly curable compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit value of the content ratio may exceed 100 mole%.
前述聚合物(a1)的重量平均分子量(Mw)較佳為100000至2000000，更佳為300000至1500000。 The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.
於前述聚合物(a1)的至少一部分藉由交聯劑(f)進行交聯之情形時，前述聚合物(a1)可使不屬於上述說明之構成前述丙烯酸系聚合物(a11)之任一單體且具有與交聯劑(f)反應之基之單體進行聚合，在前述與交聯劑(f)反應之基中進行交聯，亦可在源自前述能量線硬化性化合物(a12)之與前述官能基反應之基中進行交聯。 When at least a part of the polymer (a1) is cross-linked by a cross-linking agent (f), the polymer (a1) may not belong to any of the acrylic polymers (a11) constituting the acrylic polymer (a11) described above. A monomer having a monomer that reacts with a crosslinking agent (f) is polymerized, and the monomer is crosslinked in the aforementioned group that reacts with the crosslinking agent (f), or may be derived from the energy ray-curable compound (a12) ) Is crosslinked in the group which reacts with the aforementioned functional group.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之前述聚合物(a1)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition (IV-1) for forming a protective film and the polymer (a1) contained in the film for forming a protective film may be only one kind, or two or more kinds; in the case of two or more kinds, these combinations And the ratio can be arbitrarily selected.
(具有能量線硬化性基且分子量為100至80000之化 合物(a2)) (Compound (a2) having an energy ray hardening group and a molecular weight of 100 to 80,000)
作為具有能量線硬化性基且分子量為100至80000之化合物(a2)所具有之能量線硬化性基，可列舉包含能量線硬化性雙鍵之基，作為較佳的該基，可列舉(甲基)丙烯醯基、乙烯基等。 Examples of the energy ray-curable group possessed by the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond. As the preferable group, (A Group) acrylfluorenyl, vinyl and the like.
若前述化合物(a2)滿足上述條件，則並無特別限定，可列舉：具有能量線硬化性基之低分子量化合物、具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂等。 The compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include low-molecular-weight compounds having an energy-ray-curable group, epoxy resins having an energy-ray-curable group, and phenol resins having an energy-ray-curable group. Wait.
前述化合物(a2)中，作為具有能量線硬化性基之低分子量化合物，例如可列舉多官能之單體或低聚物等，較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。 Among the aforementioned compounds (a2), examples of the low-molecular-weight compound having an energy ray-curable group include polyfunctional monomers and oligomers, and an acrylate-based compound having a (meth) acrylfluorenyl group is preferred.
作為前述丙烯酸酯系化合物，例如可列舉：甲基丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、聚乙二醇二(甲基)丙烯酸酯、丙氧基化乙氧基化雙酚A二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基聚乙氧基)苯基]丙烷、乙氧基化雙酚A二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基二乙氧基)苯基]丙烷、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀、2,2-雙[4-((甲基)丙烯醯氧基聚丙氧基)苯基]丙烷、三環癸烷二甲醇二(甲基)丙烯酸酯(三環癸烷二羥甲基二(甲基)丙烯酸酯)、1,10-癸二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、二 丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基乙氧基)苯基]丙烷、新戊二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯、2-羥基-1,3-二(甲基)丙烯醯氧基丙烷等2官能(甲基)丙烯酸酯；異氰脲酸三(2-(甲基)丙烯醯氧基乙基)酯、ε-己內酯改性異氰脲酸三-(2-(甲基)丙烯醯氧基乙基)酯、乙氧基化甘油三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇聚(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯低聚物等多官能(甲基)丙烯酸酯低聚物等。 Examples of the acrylate-based compound include 2-hydroxy-3- (meth) acryloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, and propoxylated ethoxy group. Bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acrylic fluorenyloxy polyethoxy) phenyl] propane, ethoxylated bisphenol A bis (methyl) ) Acrylate, 2,2-bis [4-((meth) propenyloxy diethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) propenyloxy Ethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane, tricyclodecane dimethanol di (meth) acrylate (tri Cyclodecane dimethylol di (meth) acrylate), 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2,2-bis [4-((methyl ) Propylene ethoxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-bis (methyl) Group) bifunctional (meth) acrylates such as propylene alkoxypropane; tris (2- (meth) acryl ethoxyethyl) isocyanurate, ε-caprolactone modified isocyanurate tri -(2- (Meth) acryloxyethyl), ethoxylated glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Ester, di-trimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, di Polyfunctional (meth) acrylates such as pentaerythritol hexa (meth) acrylate; polyfunctional (meth) acrylate oligomers such as (meth) acrylate urethane oligomers and the like.
前述化合物(a2)中，作為具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂，例如可使用「日本特開2013-194102號公報」中的段落0043等中所記載之樹脂。此種樹脂亦符合構成後述之熱硬化性成分(h)之樹脂，但本發明中視作前述化合物(a2)。 Among the compounds (a2), as the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group, for example, it can be described in paragraph 0043 and the like of Japanese Patent Application Laid-Open No. 2013-194102. The resin. Such a resin also corresponds to a resin constituting a thermosetting component (h) described later, but is regarded as the aforementioned compound (a2) in the present invention.
前述化合物(a2)的重量平均分子量較佳為100至30000，更佳為300至10000。 The weight average molecular weight of the aforementioned compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之前述化合物(a2)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition (IV-1) for forming a protective film and the compound (a2) contained in the film for forming a protective film may be only one kind, or two or more kinds; in the case of two or more kinds, these combinations and The ratio can be arbitrarily selected.
[不具有能量線硬化性基之聚合物(b)] [Polymer (b) without energy ray hardening group]
於保護膜形成用組成物(IV-1)及保護膜形成用膜含有前述化合物(a2)作為前述能量線硬化性成分(a)之情形時，較佳為進一步亦含有不具有能量線硬化性基之聚合物(b)。 In the case where the protective film-forming composition (IV-1) and the protective film-forming film contain the compound (a2) as the energy ray-curable component (a), it is preferable that the compound (a-1) further contain no energy ray-curable Based polymer (b).
前述聚合物(b)可至少一部分藉由交聯劑(f)進行交聯，亦可不進行交聯。 The polymer (b) may be crosslinked at least in part by a crosslinking agent (f), or may not be crosslinked.
作為不具有能量線硬化性基之聚合物(b)，例如可列舉：丙烯酸系聚合物、苯氧基樹脂、胺基甲酸酯樹脂、聚酯、橡膠系樹脂、丙烯酸胺基甲酸酯樹脂、聚乙烯醇(PVA)、丁醛樹脂、聚酯胺基甲酸酯樹脂等。 Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins. , Polyvinyl alcohol (PVA), butyraldehyde resin, polyester urethane resin, etc.
這些之中，前述聚合物(b)較佳為丙烯酸系聚合物(以下，有時簡稱為「丙烯酸系聚合物(b-1)」)。 Among these, the polymer (b) is preferably an acrylic polymer (hereinafter, sometimes referred to simply as "acrylic polymer (b-1)").
丙烯酸系聚合物(b-1)可為公知的聚合物，例如可為1種丙烯酸系單體的均聚物，亦可為2種以上丙烯酸系單體的共聚物，還可為1種或2種以上丙烯酸系單體與1種或2種以上除丙烯酸系單體以外的單體(非丙烯酸系單體)之 共聚物。 The acrylic polymer (b-1) may be a known polymer. For example, the acrylic polymer (b-1) may be a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers. A copolymer of two or more acrylic monomers and one or two or more monomers (non-acrylic monomers) other than the acrylic monomer.
作為構成丙烯酸系聚合物(b-1)之前述丙烯酸系單體，例如可列舉：(甲基)丙烯酸烷基酯、具有環狀骨架之(甲基)丙烯酸酯、含縮水甘油基之(甲基)丙烯酸酯、含羥基之(甲基)丙烯酸酯、含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」如上文所說明。 Examples of the acrylic monomer constituting the acrylic polymer (b-1) include (meth) acrylic acid alkyl esters, (meth) acrylic acid esters having a cyclic skeleton, and (glycidyl group-containing) Group) acrylate, hydroxyl-containing (meth) acrylate, substituted amino group-containing (meth) acrylate, and the like. Here, the "substituted amino group" is as described above.
作為前述(甲基)丙烯酸烷基酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯(亦稱為(甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯(亦稱為(甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯(亦稱為(甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯(亦稱為(甲基)丙烯酸硬脂酯)等構成烷基酯之烷基的碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等。 Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl methacrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, (meth) acrylic acid Hexyl ester, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, Isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (also known as lauryl (meth) acrylate) Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also known as myristyl (meth) acrylate), pentadecyl (meth) acrylate, (methyl Cetyl acrylate (also known as palmitic (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also known as (meth) acrylic acid Alkyl esters (Meth) acrylic acid alkyl esters having a chain structure of 1 to 18 carbon atoms.
作為前述具有環狀骨架之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯基酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯等。 Examples of the (meth) acrylate having a cyclic skeleton include cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentyl (meth) acrylate; (meth) ) Aralkyl (meth) acrylates, such as benzyl acrylate; Cycloalkenyl (meth) acrylates, such as dicyclopentenyl (meth) acrylate; Dicyclopentenyloxyethyl (meth) acrylate, etc. Cycloalkoxyalkyl (meth) acrylate and the like.
作為前述含縮水甘油基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸縮水甘油酯等。 Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate.
作為前述含羥基之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸羥基甲酯、(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3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。 Examples of the hydroxyl-containing (meth) acrylate include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
作為前述含取代胺基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸N-甲基胺基乙酯等。 Examples of the substituted amino group-containing (meth) acrylate include N-methylaminoethyl (meth) acrylate and the like.
作為構成丙烯酸系聚合物(b-1)之前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
作為至少一部分藉由交聯劑(f)進行交聯且不具有前述能量線硬化性基之聚合物(b)，例如可列舉：前述聚合物(b)中的反應性官能基與交聯劑(f)反應之聚合物。 Examples of the polymer (b) which does not have the aforementioned energy ray-curable group and which is crosslinked by a crosslinking agent (f) include, for example, a reactive functional group and a crosslinking agent in the polymer (b). (f) a reactive polymer.
前述反應性官能基根據交聯劑(f)之種類等適宜選擇即可，並無特別限定。例如，於交聯劑(f)為多異氰酸酯化合物之情形時，作為前述反應性官能基，可列舉羥基、羧基、胺基等，這些之中，較佳為與異氰酸酯基之反應性高之羥基。於交聯劑(f)為環氧系化合物之情形時，作為前述反應性官能基，可列舉羧基、胺基、醯胺基等，這些之中，較佳為與環氧基之反應性高之羧基。但是，就防止半導體晶圓或半導體晶片的電路腐蝕之方面而言，前述反應性官能基較佳為羧基以外的基。 The reactive functional group may be appropriately selected depending on the type of the crosslinking agent (f) and the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. . When the crosslinking agent (f) is an epoxy-based compound, examples of the reactive functional group include a carboxyl group, an amine group, and a sulfonylamino group. Among these, a high reactivity with an epoxy group is preferred. The carboxyl group. However, in terms of preventing corrosion of the semiconductor wafer or the circuit of the semiconductor wafer, the reactive functional group is preferably a group other than a carboxyl group.
作為具有前述反應性官能基且不具有能量線硬化性基之聚合物(b)，例如可列舉：至少使具有前述反應性官能基之單體進行聚合而獲得之聚合物。於丙烯酸系聚合物(b-1)之情形時，作為構成該丙烯酸系聚合物(b-1)之單體所列舉之前述丙烯酸系單體及非丙烯酸系單體的任一者或兩者，使用具有前述反應性官能基之單體即可。例如，作為具有羥基作為反應性官能基之前述聚合物(b)，例如可列舉使含羥基之(甲基)丙烯酸酯進行聚合而獲得之聚合物，除此以外，亦可列舉使上文所列舉之前述丙烯酸系單體或非丙烯酸系單體中1個或2個以上氫原子被前述反應性官能基取代而成之單體進行聚合而獲得之聚合物。 Examples of the polymer (b) having the aforementioned reactive functional group and not having an energy ray-curable group include polymers obtained by polymerizing at least a monomer having the aforementioned reactive functional group. In the case of the acrylic polymer (b-1), any one or both of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) What is necessary is just to use the monomer which has the said reactive functional group. For example, as said polymer (b) which has a hydroxyl group as a reactive functional group, the polymer obtained by superposing | polymerizing the hydroxyl-containing (meth) acrylate is mentioned, for example, In addition, the polymer made by the above is mentioned. A polymer obtained by polymerizing a monomer obtained by substituting one or more hydrogen atoms of the aforementioned acrylic monomer or non-acrylic monomer with the aforementioned reactive functional group.
具有反應性官能基之前述聚合物(b)中，由具有反應性官能基之單體衍生之結構單元的量相對於構成該聚合 物(b)之結構單元的全部量之比例(含量)較佳為1質量%至25質量%，更佳為2質量%至20質量%。藉由前述比例為此種範圍，前述聚合物(b)中，交聯程度成為更佳的範圍。 In the aforementioned polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural unit constituting the polymer (b) is smaller. It is preferably 1% to 25% by mass, and more preferably 2% to 20% by mass. When the aforementioned ratio is in such a range, the degree of crosslinking in the aforementioned polymer (b) becomes a more preferable range.
就保護膜形成用組成物(IV-1)的造膜性更良好之方面而言，不具有能量線硬化性基之聚合物(b)的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至1500000。 The polymer (b) having no energy ray-curable group has a weight-average molecular weight (Mw) of 10,000 to 2,000,000 in terms of more favorable film-forming properties of the protective film-forming composition (IV-1). More preferably, it is 100,000 to 1.5 million.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之不具有能量線硬化性基之聚合物(b)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The protective film-forming composition (IV-1) and the protective film-forming film may contain only one type of polymer (b) without an energy ray-curable group, or two or more types; and two types In the above cases, these combinations and ratios can be arbitrarily selected.
作為保護膜形成用組成物(IV-1)，可列舉含有前述聚合物(a1)及前述化合物(a2)的任一者或兩者之組成物。於保護膜形成用組成物(IV-1)含有前述化合物(a2)之情形時，較佳為亦進一步含有不具有能量線硬化性基之聚合物(b)，該情形時，亦較佳為進一步含有前述(a1)。保護膜形成用組成物(IV-1)亦可不含有前述化合物(a2)，且一併含有前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)。 Examples of the protective film-forming composition (IV-1) include a composition containing any one or both of the polymer (a1) and the compound (a2). In the case where the protective film-forming composition (IV-1) contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) having no energy ray-curable group, and in this case, it is also preferred It further contains the aforementioned (a1). The protective film-forming composition (IV-1) may not contain the aforementioned compound (a2), and may also contain the aforementioned polymer (a1) and a polymer (b) having no energy ray-curable group.
於保護膜形成用組成物(IV-1)含有前述聚合物(a1)、前述化合物(a2)及不具有能量線硬化性基之聚合物(b)之 情形時，保護膜形成用組成物(IV-1)中，前述化合物(a2)的含量相對於前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為10質量份至400質量份，更佳為30質量份至350質量份。 When the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the protective film-forming composition ( In IV-1), the content of the compound (a2) is 100 parts by mass, and preferably 10 to 400 parts by mass, relative to the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. It is more preferably 30 parts by mass to 350 parts by mass.
保護膜形成用組成物(IV-1)中，前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量相對於溶劑以外的成分的總含量之比例(亦即保護膜形成用膜中的前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量)較佳為5質量%至90質量%，更佳為10質量%至80質量%，尤佳為15質量%至70質量%。藉由前述合計含量之比例為此種範圍，保護膜形成用膜的能量線硬化性變得更良好。 In the protective film-forming composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (That is, the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the protective film-forming film) is preferably from 5 mass% to 90 mass%, and more preferably It is 10 to 80% by mass, and particularly preferably 15 to 70% by mass. When the ratio of the total content is in such a range, the energy ray hardenability of the protective film-forming film becomes better.
於保護膜形成用組成物(IV-1)含有前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，前述聚合物(b)的含量相對於能量線硬化性成分(a)的含量100質量份，較佳為3質量份至160質量份，更佳為6質量份至130質量份。藉由前述聚合物(b)的前述含量為此種範圍，保護膜形成用膜的能量線硬化性變得更良好。 When the composition (IV-1) for forming a protective film contains the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the composition (IV-1) for forming a protective film ) And the film for forming a protective film, the content of the polymer (b) is 100 parts by mass with respect to the content of the energy ray-curable component (a), preferably 3 parts by mass to 160 parts by mass, and more preferably 6 parts by mass To 130 parts by mass. When the content of the polymer (b) is in such a range, the energy ray hardenability of the protective film-forming film becomes better.
保護膜形成用組成物(IV-1)中，除了能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)以外，亦可根 據目的含有選自由光聚合起始劑(c)、填充材料(d)、偶合劑(e)、交聯劑(f)、著色劑(g)、熱硬化性成分(h)及通用添加劑(z)所組成之群組中的1種或2種以上。例如，藉由使用含有前述能量線硬化性成分(a)及熱硬化性成分(h)之保護膜形成用組成物(IV-1)，所形成之保護膜形成用膜藉由加熱而對被接著體之接著力提高，由該保護膜形成用膜形成之保護膜的強度亦提高。 The protective film-forming composition (IV-1) may contain, in addition to the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, a component selected from a photopolymerization initiator according to the purpose. (c), filler (d), coupling agent (e), cross-linking agent (f), colorant (g), thermosetting component (h), and general additive (z) One or two or more. For example, by using the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h), the formed protective film-forming film is heated against the substrate. The adhesive force of the adhesive body is increased, and the strength of the protective film formed from the protective film-forming film is also improved.
[光聚合起始劑(c)] [Photopolymerization initiator (c)]
作為光聚合起始劑(c)，例如可列舉：安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫化物、一硫化四甲基秋蘭姆等硫化物化合物；1-羥基環己基苯基酮等α-酮醇化合物；偶氮雙異丁腈等偶氮化合物；二茂鈦等二茂鈦化合物；噻噸酮等噻噸酮化合物；二苯甲酮、2-(二甲基胺基)-1-(4-嗎啉(morpholine)基苯基)-2-苄基-1-丁酮、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)等二苯甲酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯；二苯偶醯；2,4-二乙基噻噸酮；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙 烯基)苯基]丙酮；2-氯蒽醌等。 Examples of the photopolymerization initiator (c) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, and the like. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Acetophenone compounds; fluorenyl phosphine oxide compounds such as bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide ; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketoalcohol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene And other dioctocene compounds; thioxanthone compounds such as thioxanthone; benzophenone, 2- (dimethylamino) -1- (4-morpholine (phenyl))-2-benzyl- 1-butanone, ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime) Isobenzophenone compounds; peroxide compounds; diacetone and other diketone compounds; benzoin; dibenzofluorene; 2,4-diethyl Thioxanthone; 1,2-diphenyl methane; hydroxy-2-methyl-1- [4- (1-methyl-vinyl) phenyl] propanone; 2-chloro-anthraquinone.
作為光聚合起始劑(c)，例如亦可使用1-氯蒽醌等醌化合物；胺等光增感劑等。 Examples of the photopolymerization initiator (c) include quinone compounds such as 1-chloroanthraquinone; and photosensitizers such as amines.
保護膜形成用組成物(IV-1)所含有之光聚合起始劑(c)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The photopolymerization initiator (c) contained in the protective film-forming composition (IV-1) may be only one kind, or two or more kinds; in the case of two or more kinds, these combinations and ratios may be arbitrary select.
於使用光聚合起始劑(c)之情形時，保護膜形成用組成物(IV-1)中，光聚合起始劑(c)的含量相對於能量線硬化性化合物(a)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 When the photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the protective film-forming composition (IV-1) is 100 relative to the content of the energy ray-curable compound (a). It is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass.
[填充材料(d)] [Filling material (d)]
藉由保護膜形成用膜含有填充材料(d)，保護膜形成用膜硬化而獲得之保護膜容易調整熱膨脹係數，使該熱膨脹係數對於保護膜之形成對象物而言最佳化，藉此使用保護膜形成用複合片所獲得之封裝的可靠性進一步提高。藉由保護膜形成用膜含有填充材料(d)，可降低保護膜的吸濕率，或提高散熱性。 Since the protective film forming film contains a filler (d), the protective film obtained by curing the protective film forming film can be easily adjusted in thermal expansion coefficient, and the thermal expansion coefficient is optimized for the object of the protective film formation. The reliability of the package obtained by the protective film forming composite sheet is further improved. When the filler (d) is contained in the film for forming a protective film, the moisture absorption of the protective film can be reduced or the heat dissipation property can be improved.
作為填充材料(d)，例如可列舉由導熱性材料構成之材料。 Examples of the filler (d) include a material made of a thermally conductive material.
填充材料(d)可為有機填充材料及無機填充材料之任一者，較佳為無機填充材料。 The filler (d) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.
作為較佳的無機填充材料，例如可列舉：二氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、鐵丹、碳化矽、氮化硼等的粉末；將這些無機填充材料球形化而成之珠粒；這些無機填充材料的表面改質品；這些無機填充材料的單晶纖維；玻璃纖維等。 Preferred inorganic fillers include, for example, powders of silicon dioxide, alumina, talc, calcium carbonate, titanium white, iron white, silicon carbide, boron nitride, etc .; these inorganic fillers are spheroidized Beads; surface modifications of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.
這些之中，無機填充材料較佳為二氧化矽或氧化鋁。 Among these, the inorganic filler is preferably silicon dioxide or aluminum oxide.
填充材料(d)的平均粒徑並無特別限定，較佳為0.01μm至20μm，更佳為0.1μm至15μm，尤佳為0.3μm至10μm。藉由填充材料(d)的平均粒徑為此種範圍，可維持對保護膜之形成對象物之接著性，並且可抑制保護膜之光之透過率之降低。 The average particle diameter of the filler (d) is not particularly limited, but is preferably 0.01 μm to 20 μm, more preferably 0.1 μm to 15 μm, and even more preferably 0.3 μm to 10 μm. When the average particle diameter of the filler (d) is in such a range, the adhesiveness to an object to be formed of the protective film can be maintained, and a decrease in light transmittance of the protective film can be suppressed.
本說明書中，所謂「平均粒徑」，只要無特別說明，則意指藉由雷射繞射散射法所求出之粒度分佈曲線中累計值50%下的粒徑(D50)之值。 In the present specification, the "average particle diameter" means the value of the particle diameter (D 50 ) at a cumulative value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method unless otherwise specified.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之填充材料(d)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition for forming a protective film (IV-1) and the filler (d) contained in the film for forming a protective film may be only one kind, or two or more kinds; in the case of two or more kinds, these combinations and The ratio can be arbitrarily selected.
於使用填充材料(d)之情形時，保護膜形成用組成物(IV-1)中，填充材料(d)的含量相對於溶劑以外的全部成分 的總含量之比例(亦即保護膜形成用膜中的填充材料(d)的含量)較佳為5質量%至83質量%，更佳為7質量%至78質量%。藉由填充材料(d)的含量為此種範圍，更容易調整上述之熱膨脹係數。 When the filler (d) is used, the ratio of the content of the filler (d) to the total content of all components other than the solvent in the protective film-forming composition (IV-1) (that is, for the formation of the protective film) The content of the filler (d) in the film is preferably 5 to 83% by mass, and more preferably 7 to 78% by mass. When the content of the filler (d) is in such a range, it is easier to adjust the above-mentioned thermal expansion coefficient.
[偶合劑(e)] [Coupling agent (e)]
藉由使用具有可與無機化合物或有機化合物反應之官能基之偶合劑作為偶合劑(e)，可提高保護膜形成用膜對被接著體之接著性及密接性。藉由使用偶合劑(e)，保護膜形成用膜硬化而獲得之保護膜無損耐熱性而耐水性提高。 By using a coupling agent having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (e), the adhesiveness and adhesion of the film for forming a protective film to an adherend can be improved. By using a coupling agent (e), the protective film obtained by hardening the film for protective film formation does not impair heat resistance and improves water resistance.
偶合劑(e)較佳為具有可與能量線硬化性成分(a)、不具有能量線硬化性基之聚合物(b)等所具有之官能基反應之官能基之化合物，更佳為矽烷偶合劑。 The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group having an energy ray-curable component (a), a polymer having no energy ray-curable group (b), and the like, and more preferably a silane Coupling agent.
作為較佳的前述矽烷偶合劑，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-(苯基胺基)丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3- 巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。 Examples of the preferable silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyl Diethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinepropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethylsilane Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyl triethoxysilane, imidazole silane, and the like.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之偶合劑(e)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The protective film-forming composition (IV-1) and the coupling agent (e) contained in the protective film-forming film may be only one kind, or two or more kinds; in the case of two or more kinds, these combinations and The ratio can be arbitrarily selected.
於使用偶合劑(e)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，偶合劑(e)的含量相對於能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為0.03質量份至20質量份，更佳為0.05質量份至10質量份，尤佳為0.1質量份至5質量份。藉由偶合劑(e)的前述含量為前述下限值以上，可獲得更顯著的以下由使用偶合劑(e)所帶來之功效：填充材料(d)於樹脂中的分散性提高，或保護膜形成用膜與被接著體之接著性提高等。藉由偶合劑(e)的前述含量為前述上限值以下，可進一步抑制產生逸氣。 When the coupling agent (e) is used, the content of the coupling agent (e) in the protective film-forming composition (IV-1) and the protective film-forming film is relative to the energy ray-curable component (a) and does not have The total content of the energy ray-curable polymer (b) is 100 parts by mass, preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass . When the aforementioned content of the coupling agent (e) is above the aforementioned lower limit, a more remarkable effect brought about by using the coupling agent (e) can be obtained: the dispersibility of the filler (d) in the resin is improved, or The adhesion between the protective film-forming film and the adherend is improved. When the content of the coupling agent (e) is equal to or less than the aforementioned upper limit value, outgassing can be further suppressed.
[交聯劑(f)] [Crosslinking agent (f)]
藉由使用交聯劑(f)，使上述之能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)進行交聯，可調節保護膜形成用膜的初期接著力及凝聚力。 By using a cross-linking agent (f), the aforementioned energy ray-curable component (a) or the polymer (b) having no energy ray-curable group is cross-linked to adjust the initial adhesion of the protective film-forming film And cohesion.
作為交聯劑(f)，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)、氮丙啶系交聯劑(具有氮丙啶基之交聯劑)等。 Examples of the crosslinking agent (f) include organic polyisocyanate compounds, organic polyimide compounds, metal chelate-based crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine-based crosslinking. Agents (crosslinking agents with aziridinyl) and the like.
作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物及脂環族多元異氰酸酯化合物(以下，有時將這些化合物統一簡稱為「芳香族多元異氰酸酯化合物等」)；前述芳香族多元異氰酸酯化合物等的三聚物、異氰脲酸酯體及加合物；使前述芳香族多元異氰酸酯化合物等與多元醇化合物反應而獲得之末端異氰酸酯胺基甲酸酯預聚物等。前述「加合物」意指前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物，與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫之化合物之反應物，作為前述加合物的示例，可列舉如後述之三羥甲基丙烷之苯二甲基二異氰酸酯加成物等。所謂「末端異氰酸酯胺基甲酸酯預聚物」意指具有胺基甲酸酯鍵，並且於分子末端部具有異氰酸酯基之預聚物。 Examples of the organic polyisocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compounds"); Terpolymers, isocyanurates, and adducts of the aromatic polyisocyanate compounds; terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyisocyanate compounds and the like with polyol compounds . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound, and contains ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil, etc. Examples of the reactant of the low-molecular active hydrogen compound include, as examples of the adduct, a xylylene diisocyanate adduct of trimethylolpropane as described later. The "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at a molecular terminal.
作為前述有機多元異氰酸酯化合物，更具體而言，例如可列舉：2,4-甲苯二異氰酸酯；2,6-甲苯二異氰酸酯；1,3-苯二甲基二異氰酸酯；1,4-二甲苯二異氰酸酯；二苯 基甲烷-4,4'-二異氰酸酯；二苯基甲烷-2,4'-二異氰酸酯；3-甲基二苯基甲烷二異氰酸酯；六亞甲基二異氰酸酯；異佛爾酮二異氰酸酯；二環己基甲烷-4,4'-二異氰酸酯；二環己基甲烷-2,4'-二異氰酸酯；對三羥甲基丙烷等多元醇的全部或一部分羥基，加成甲苯二異氰酸酯、六亞甲基二異氰酸酯及苯二甲基二異氰酸酯的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。 Specific examples of the organic polyisocyanate compound include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-benzyl diisocyanate; 1,4-xylene diisocyanate Isocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; all or part of the hydroxyl groups of polyols such as trimethylolpropane, and toluene diisocyanate, Compounds of any one or more of hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.
作為前述有機多元亞胺化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶甲醯胺)、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、四羥甲基甲烷-三-β-氮丙啶基丙酸酯、N,N'-甲苯-2,4-雙(]-氮丙啶甲醯胺)三伸乙基三聚氰胺等。 Examples of the organic polyimide compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamide), and trimethylolpropane-tri-β-nitrogen. Propidyl propionate, tetramethylol methane-tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (]-aziridinecarboxamide) triethylene glycol Melamine and the like.
於使用有機多元異氰酸酯化合物作為交聯劑(f)之情形時，作為能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)，較佳為使用含羥基之聚合物。於交聯劑(f)具有異氰酸酯基，能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)具有羥基之情形時，藉由交聯劑(f)與能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)之反應，可將交聯結構簡便地導入至保護膜形成用膜中。 When an organic polyisocyanate compound is used as the crosslinking agent (f), as the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group, it is preferable to use a polymer containing a hydroxyl group . When the crosslinking agent (f) has an isocyanate group, and the energy ray-curable component (a) or the polymer (b) without an energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray The reaction of the curable component (a) or the polymer (b) which does not have an energy ray-curable group can easily introduce a crosslinked structure into the film for forming a protective film.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有 之交聯劑(f)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The protective film-forming composition (IV-1) and the cross-linking agent (f) contained in the protective film-forming film may be only one kind, or two or more kinds; in the case of two or more kinds, these combinations And the ratio can be arbitrarily selected.
於使用交聯劑(f)之情形時，保護膜形成用組成物(IV-1)中，交聯劑(f)的含量相對於能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為0.01質量份至20質量份，更佳為0.1質量份至10質量份，尤佳為0.5質量份至5質量份。藉由交聯劑(f)的前述含量為前述下限值以上，可獲得更顯著的由使用交聯劑(f)所帶來之功效。藉由交聯劑(f)的前述含量為前述上限值以下，可抑制交聯劑(f)之過量使用。 When a crosslinking agent (f) is used, the content of the crosslinking agent (f) in the protective film-forming composition (IV-1) is relative to the energy-ray-curable component (a) and does not have energy-ray-curable properties. The total content of the base polymer (b) is 100 parts by mass, preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass. When the aforementioned content of the cross-linking agent (f) is equal to or higher than the aforementioned lower limit value, a more significant effect by using the cross-linking agent (f) can be obtained. When the content of the cross-linking agent (f) is equal to or less than the aforementioned upper limit value, the excessive use of the cross-linking agent (f) can be suppressed.
[著色劑(g)] [Colorant (g)]
作為著色劑(g)，例如可列舉：無機系顏料、有機系顏料、有機系染料等公知的著色劑。 Examples of the colorant (g) include known coloring agents such as inorganic pigments, organic pigments, and organic dyes.
作為前述有機系顏料及有機系染料，例如可列舉：銨系色素、花青系色素、部花青系色素、克酮鎓(croconium)系色素、方酸鎓(squalilium)系色素、薁鎓系色素、聚次甲基系色素、萘醌系色素、吡喃鎓系色素、酞菁系色素、萘酞菁系色素、萘內醯胺系色素、偶氮系色素、縮合偶氮系色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁烷系色素、喹吖啶酮系色素、異吲哚啉酮系色素、喹啉黃(quinophthalone)系色素、吡咯系色素、硫代靛藍系色 素、金屬錯合物系色素(金屬錯鹽染料)、二硫醇金屬錯合物系色素、吲哚酚系色素、三烯丙基甲烷系色素、蒽醌系色素、萘酚系色素、次甲基偶氮系色素、苯并咪唑酮系色素、皮蒽酮系色素及士林(threne)系色素等。 Examples of the organic pigments and organic dyes include ammonium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squalilium pigments, and sulfonium pigments. Pigments, polymethine-based pigments, naphthoquinone-based pigments, pyranium-based pigments, phthalocyanine-based pigments, naphthalocyanine-based pigments, naphtholide-based pigments, azo-based pigments, condensed azo-based pigments, indigo Pigments, perinone pigments, perylene pigments, dioxane pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo dyes, metal complex dyes (metal salt dyes), dithiol metal complex dyes, indolophenol dyes, triallyl methane dyes, anthraquinone dyes, naphthol Pigments, methine azo pigments, benzimidazolone pigments, dermatanone pigments, and threne pigments.
作為前述無機系顏料，例如可列舉：碳黑、鈷系色素、鐵系色素、鉻系色素、鈦系色素、釩系色素、鋯系色素、鉬系色素、釕系色素、鉑系色素、ITO(Indium Tin Oxide；氧化銦錫)系色素、ATO(Antimony Tin Oxide；氧化銻錫)系色素等。 Examples of the inorganic pigment include carbon black, cobalt-based pigment, iron-based pigment, chromium-based pigment, titanium-based pigment, vanadium-based pigment, zirconium-based pigment, molybdenum-based pigment, ruthenium-based pigment, platinum-based pigment, and ITO. (Indium Tin Oxide) -based pigments, ATO (Antimony Tin Oxide) -based pigments, and the like.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之著色劑(g)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The protective film-forming composition (IV-1) and the coloring agent (g) contained in the protective film-forming film may be only one kind, or two or more kinds; in the case of two or more kinds, these combinations and The ratio can be arbitrarily selected.
於使用著色劑(g)之情形時，保護膜形成用膜中的著色劑(g)的含量根據目的適宜調節即可。例如，會有藉由雷射照射對保護膜實施印字之情形，藉由調節保護膜形成用膜中的著色劑(g)的含量，調節保護膜的透光性，可調節印字視認性。該情形時，保護膜形成用組成物(IV-1)中，著色劑(g)的含量相對於溶劑以外的全部成分的總含量之比例(亦即保護膜形成用膜中的著色劑(g)的含量)較佳為0.1質量%至10質量%，更佳為0.4質量%至7.5質量%，尤佳為0.8質量%至5質量%。藉由著色劑(g)的前述含量 為前述下限值以上，可獲得更顯著的由使用著色劑(g)所帶來之功效。藉由著色劑(g)的前述含量為前述上限值以下，可抑制著色劑(g)之過量使用。 When the colorant (g) is used, the content of the colorant (g) in the protective film-forming film may be appropriately adjusted according to the purpose. For example, the protective film may be printed by laser irradiation. By adjusting the content of the coloring agent (g) in the protective film-forming film, the transmittance of the protective film may be adjusted, and the visibility of the printing may be adjusted. In this case, in the composition (IV-1) for forming a protective film, the ratio of the content of the colorant (g) to the total content of all components other than the solvent (that is, the coloring agent (g) in the film for forming a protective film The content) is preferably 0.1% by mass to 10% by mass, more preferably 0.4% by mass to 7.5% by mass, and even more preferably 0.8% by mass to 5% by mass. When the content of the colorant (g) is greater than or equal to the aforementioned lower limit, a more significant effect by using the colorant (g) can be obtained. When the content of the colorant (g) is equal to or less than the aforementioned upper limit value, the excessive use of the colorant (g) can be suppressed.
[熱硬化性成分(h)] [Thermosetting component (h)]
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之熱硬化性成分(h)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition (IV-1) for forming a protective film and the thermosetting component (h) contained in the film for forming a protective film may be only one kind, or two or more kinds; in the case of two or more kinds, these The combination and ratio can be selected arbitrarily.
作為熱硬化性成分(h)，例如可列舉：環氧系熱硬化性樹脂、熱硬化性聚醯亞胺、聚胺基甲酸酯、不飽和聚酯、聚矽氧樹脂等，較佳為環氧系熱硬化性樹脂。 Examples of the thermosetting component (h) include an epoxy-based thermosetting resin, a thermosetting polyimide, a polyurethane, an unsaturated polyester, and a silicone resin. Epoxy-based thermosetting resin.
(環氧系熱硬化性樹脂) (Epoxy-based thermosetting resin)
環氧系熱硬化性樹脂係由環氧樹脂(h1)及熱硬化劑(h2)構成。 The epoxy-based thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2).
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之環氧系熱硬化性樹脂可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The epoxy-based thermosetting resin contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, or two or more types; in the case of two or more types, these The combination and ratio can be selected arbitrarily.
．環氧樹脂(h1) ． Epoxy resin (h1)
作為環氧樹脂(h1)，可列舉公知的環氧樹脂，例如可列舉：多官能系環氧樹脂、聯苯化合物、雙酚A二縮水甘油醚及其氫化物、鄰甲酚酚醛清漆環氧樹脂、二環戊二 烯型環氧樹脂、聯苯型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、伸苯基骨架型環氧樹脂等2官能以上之環氧化合物。 Examples of the epoxy resin (h1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydride, and o-cresol novolac epoxy. Resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phenylene skeleton epoxy resin, etc. Compound.
作為環氧樹脂(h1)，亦可使用具有不飽和烴基之環氧樹脂。具有不飽和烴基之環氧樹脂相較於不具有不飽和烴基之環氧樹脂而言，與丙烯酸系樹脂之相容性較高。因此，藉由使用具有不飽和烴基之環氧樹脂，使用保護膜形成用複合片所獲得之封裝的可靠性提高。 As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group is more compatible with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the composite sheet for forming a protective film is improved.
作為具有不飽和烴基之環氧樹脂，例如可列舉：多官能系環氧樹脂的一部分環氧基更換為具有不飽和烴基之基而成之化合物。此種化合物例如藉由使(甲基)丙烯酸或其衍生物與環氧基進行加成反應而獲得。 Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by replacing a part of the epoxy group of the polyfunctional epoxy resin with a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by subjecting (meth) acrylic acid or a derivative thereof to an addition reaction with an epoxy group.
作為具有不飽和烴基之環氧樹脂，例如可列舉：於構成環氧樹脂之芳香環等上直接鍵結有具有不飽和烴基之基之化合物等。 Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
不飽和烴基為具有聚合性之不飽和基，作為該不飽和烴基的具體例，可列舉：次乙基(亦稱為乙烯基)、2-丙烯基(亦稱為烯丙基)、(甲基)丙烯醯基、(甲基)丙烯醯胺基等，較佳為丙烯醯基。 The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include ethylidene (also referred to as vinyl), 2-propenyl (also referred to as allyl), and (formaldehyde). (Meth) acrylfluorenyl, (meth) acrylfluorenylamino and the like are preferably acrylfluorenyl.
環氧樹脂(h1)的數量平均分子量並無特別限定，就保護膜形成用膜的硬化性、以及保護膜的強度及耐熱性之方 面而言，較佳為300至30000，更佳為400至10000，尤佳為500至3000。 The number average molecular weight of the epoxy resin (h1) is not particularly limited, and it is preferably from 300 to 30,000, more preferably from 400 to 30,000 in terms of the hardenability of the film for forming a protective film, and the strength and heat resistance of the protective film. 10,000, particularly preferably 500 to 3000.
本說明書中，所謂「數量平均分子量」，只要無特別說明，則意指藉由凝膠滲透層析(GPC)法所測定且以標準聚苯乙烯換算之值顯示之數量平均分子量。 In the present specification, the "number average molecular weight" means a number average molecular weight measured by a gel permeation chromatography (GPC) method and displayed in terms of a standard polystyrene conversion value unless otherwise specified.
環氧樹脂(h1)的環氧當量較佳為100g/eq至1000g/eq，更佳為150g/eq至800g/eq。 The epoxy equivalent of the epoxy resin (h1) is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 800 g / eq.
本說明書中，所謂「環氧當量」意指包含1克當量的環氧基之環氧化合物的克數(g/eq)，可依據JIS K 7236：2001之方法進行測定。 In this specification, the "epoxy equivalent" means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.
環氧樹脂(h1)可單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些組合及比率可任意選擇。 The epoxy resin (h1) may be used singly or in combination of two or more kinds. When two or more kinds of epoxy resins are used in combination, these combinations and ratios can be arbitrarily selected.
．熱硬化劑(h2) ． Heat hardener (h2)
熱硬化劑(h2)發揮作為針對環氧樹脂(h1)之硬化劑的功能。 The thermal hardener (h2) functions as a hardener for the epoxy resin (h1).
作為熱硬化劑(h2)，例如可列舉：1分子中具有2個以上可與環氧基反應之官能基之化合物。作為前述官能基，例如可列舉：酚性羥基、醇性羥基、胺基、羧基、酸基經酐化而成之基等，較佳為酚性羥基、胺基、或酸基經酐化而成之基，更佳為酚性羥基或胺基。 Examples of the thermosetting agent (h2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and an acidic group obtained by acidification. Preferred is a phenolic hydroxyl group, an amine group, or an acidic group which is anhydrided. The formed group is more preferably a phenolic hydroxyl group or an amine group.
熱硬化劑(h2)中，作為具有酚性羥基之酚系硬化劑， 例如可列舉：多官能酚樹脂、聯苯酚、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基酚樹脂等。 Among the heat curing agents (h2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac phenol resins, dicyclopentadiene phenol resins, and aralkylphenols. Resin, etc.
熱硬化劑(h2)中，作為具有胺基之胺系硬化劑，例如可列舉：二氰二胺(以下，有時簡稱為「DICY」)等。 Among the thermosetting agents (h2), examples of the amine-based curing agent having an amine group include dicyandiamine (hereinafter, sometimes simply referred to as "DICY") and the like.
熱硬化劑(h2)亦可具有不飽和烴基。 The thermosetting agent (h2) may have an unsaturated hydrocarbon group.
作為具有不飽和烴基之熱硬化劑(h2)，例如可列舉：酚樹脂的一部分羥基被具有不飽和烴基之基取代而成之化合物、酚樹脂的芳香環上直接鍵結具有不飽和烴基之基而成之化合物等。 Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include compounds in which a part of hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin. The resulting compounds.
熱硬化劑(h2)中的前述不飽和烴基與上述之具有不飽和烴基之環氧樹脂中的不飽和烴基相同。 The aforementioned unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the aforementioned unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.
於使用酚系硬化劑作為熱硬化劑(h2)之情形時，就保護膜自支持片之剝離性提高之方面而言，熱硬化劑(h2)較佳為軟化點或玻璃轉移溫度高的酚系硬化劑。 When a phenol-based hardener is used as the heat hardener (h2), the heat hardener (h2) is preferably a phenol having a high softening point or a high glass transition temperature in terms of improving the peelability of the protective film from the support sheet. Department of hardener.
本說明書中，所謂「玻璃轉移溫度」係使用示差掃描熱量計測定試樣的DSC(Differential Scanning Calorimetry；示差掃描熱量)曲線並以所獲得之DSC曲線的反曲點溫度顯示。 In the present specification, the "glass transition temperature" refers to a DSC (Differential Scanning Calorimetry) curve of a sample measured using a differential scanning calorimeter, and is displayed as the inflection point temperature of the obtained DSC curve.
熱硬化劑(h2)中，例如，多官能酚樹脂、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基酚樹脂等樹脂成分的數量平均分子量較佳為300至30000，更佳為400至 10000，尤佳為500至3000。 In the heat curing agent (h2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolac phenol resin, dicyclopentadiene-based phenol resin, and aralkylphenol resin is preferably 300 to 30,000, more It is preferably 400 to 10,000, and particularly preferably 500 to 3000.
熱硬化劑(h2)中，例如，聯苯酚、二氰二胺等非樹脂成分的分子量並無特別限定，例如較佳為60至500。 In the thermosetting agent (h2), the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited, but is preferably 60 to 500, for example.
熱硬化劑(h2)可單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些組合及比率可任意選擇。 The thermosetting agent (h2) may be used singly or in combination of two or more kinds. When two or more kinds are used in combination, these combinations and ratios can be arbitrarily selected.
於使用熱硬化性成分(h)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，熱硬化劑(h2)的含量相對於環氧樹脂(h1)的含量100質量份，較佳為0.01質量份至20質量份。 When the thermosetting component (h) is used, in the composition (IV-1) for forming a protective film and the film for forming a protective film, the content of the thermosetting agent (h2) relative to the content of the epoxy resin (h1) 100 parts by mass, preferably 0.01 to 20 parts by mass.
於使用熱硬化性成分(h)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，熱硬化性成分(h)的含量(例如，環氧樹脂(h1)及熱硬化劑(h2)的總含量)相對於不具有能量線硬化性基之聚合物(b)的含量100質量份，較佳為1質量份至500質量份。 When the thermosetting component (h) is used, the content of the thermosetting component (h) in the protective film-forming composition (IV-1) and the protective film-forming film (for example, epoxy resin (h1) And the total content of the thermosetting agent (h2)) based on 100 parts by mass of the content of the polymer (b) having no energy ray-curable group, and preferably 1 to 500 parts by mass.
[通用添加劑(z)] [General additive (z)]
通用添加劑(z)可為公知的通用添加劑，可根據目的而任意選擇，並無特別限定，作為較佳的通用添加劑，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、吸氣劑等。 The general-purpose additive (z) may be a known general-purpose additive, and may be arbitrarily selected according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives include plasticizer, antistatic agent, antioxidant, getter .
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有 之通用添加劑(z)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The protective film-forming composition (IV-1) and the general-purpose additive (z) contained in the protective film-forming film may be only one kind, or two or more kinds; in the case of two or more kinds, these combinations and The ratio can be arbitrarily selected.
於使用通用添加劑(z)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中的通用添加劑(z)的含量並無特別限定，根據目的適宜選擇即可。 When the universal additive (z) is used, the content of the universal additive (z) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited, and may be appropriately selected according to the purpose.
[溶劑] [Solvent]
保護膜形成用組成物(IV-1)較佳為進一步含有溶劑。含有溶劑之保護膜形成用組成物(IV-1)的操作性良好。 The protective film-forming composition (IV-1) preferably further contains a solvent. The solvent-containing composition (IV-1) for forming a protective film has good handleability.
前述溶劑並無特別限定，作為較佳的前述溶劑，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(亦稱為2-甲基丙烷-1-醇)、1-丁醇等醇；乙酸乙酯等酯；丙酮、甲基乙基酮等酮；四氫呋喃等醚；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺(具有醯胺鍵之化合物)等。 The solvent is not particularly limited, and examples of the preferable solvent include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, and isobutanol (also referred to as 2-methylpropane-1-ol). ), Alcohols such as 1-butanol; esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone; ethers such as tetrahydrofuran; amines such as dimethylformamide, N-methylpyrrolidone (with amine Bond compounds) and so on.
保護膜形成用組成物(IV-1)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The solvent contained in the protective film-forming composition (IV-1) may be only one type, or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.
就可將保護膜形成用組成物(IV-1)中的含有成分更均勻地混合之方面而言，保護膜形成用組成物(IV-1)所含有之溶劑較佳為甲基乙基酮、甲苯或乙酸乙酯等。 The solvent contained in the protective film-forming composition (IV-1) is more preferably methyl ethyl ketone in that the components contained in the protective film-forming composition (IV-1) can be more uniformly mixed. , Toluene or ethyl acetate.
本發明之一態樣中，保護膜形成用膜包含：作為能量線硬化性成分(a2)之三環癸烷二羥甲基二丙烯酸酯(含 量：相對於保護膜成形用組成物(IV-1)中的固形物成分的總質量，為5質量%至30質量%，更佳為8質量%至25質量%)；作為不具有能量線硬化性基之聚合物(b)之由源自丙烯酸甲酯之結構單元(相對於丙烯酸系樹脂的總質量，為75質量%至95質量%，更佳為80質量%至90質量%)、及丙烯酸-2-羥基乙酯(相對於丙烯酸系樹脂的總質量，為5質量%至25質量%，更佳為10質量%至20質量%)構成之丙烯酸系樹脂(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為12質量%至32質量%，更佳為17質量%至27質量%)；作為光聚合起始劑(c)之1-羥基-環己基-苯基-酮(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為0.1質量%至1.1質量%，更佳為0.3質量%至0.9質量%)或2-(4-甲基苄基)-2-二甲基胺基-1-(4-嗎啉-4-基-苯基)-丁烷-酮(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為0.1質量%至1.1質量%，更佳為0.3質量%至0.9質量%)；作為填充劑(d)之二氧化矽填料(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為46質量%至66質量%，更佳為51質量%至61質量%)；作為偶合劑(e)之3-甲基丙烯醯氧基丙基三甲氧基矽烷(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為0.1質量%至0.7質量%，更佳為0.3質量%至0.5質量%)；以及作為著色劑(g)之包含酞菁系藍色色素、異吲哚啉酮系黃色色素及蒽醌系紅色色素、以及苯乙烯丙烯 酸樹脂之顏料(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為0.5質量%至3.5質量%，更佳為1.0質量%至3.0質量%)(其中，各成分的含量之和相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量不超過100質量%)。 In one aspect of the present invention, the protective film-forming film includes tricyclodecane dimethylol diacrylate (content: as a protective film-forming composition (IV- The total mass of the solid component in 1) is 5 mass% to 30 mass%, more preferably 8 mass% to 25 mass%); the origin of the polymer (b) which does not have an energy ray-curable group Structural units of methyl acrylate (75% to 95% by mass, more preferably 80% to 90% by mass relative to the total mass of acrylic resin), and 2-hydroxyethyl acrylate (relative to acrylic The total mass of the resin is 5 to 25% by mass, and more preferably 10 to 20% by mass. The acrylic resin (content: based on solids in the protective film-forming composition (IV-1)) The total mass of the components is 12% to 32% by mass, and more preferably 17% to 27% by mass; 1-hydroxy-cyclohexyl-phenyl-one (content: 0.1 mass% to 1.1 mass%, more preferably 0.3 mass% to 0.9 mass% with respect to the total mass of the solid content component in the protective film-forming composition (IV-1)) or 2- (4- Benzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butane-one (content: relative to the composition (IV-1) for forming a protective film The total mass of solid components is 0.1% to 1.1% by mass, and more preferably 0.3% to 0.9% by mass); the silica filler (content: relative to the composition for forming a protective film) as a filler (d) The total mass of the solid component in the substance (IV-1) is 46% by mass to 66% by mass, and more preferably 51% by mass to 61% by mass); 3-methacrylic acid as the coupling agent (e) Propyltrimethoxysilane (content: 0.1% to 0.7% by mass, more preferably 0.3% by mass to 0.5% by mass based on the total mass of the solid component in the protective film-forming composition (IV-1) %); And a pigment containing a phthalocyanine-based blue pigment, an isoindolinone-based yellow pigment, an anthraquinone-based red pigment, and a styrene acrylic resin as a colorant (g) (content: for forming a protective film) The total mass of the solid components in the composition (IV-1) is 0.5% by mass to 3.5% by mass, and more preferably 1.0% by mass to 3.0% by mass) (wherein the sum of the contents of the components relative to the protective film formation Use composition The total mass of solid component (IV-1) is not more than 100 mass%).
<<保護膜形成用組成物的製造方法>> << Manufacturing method of protective film forming composition >>
保護膜形成用組成物(IV-1)等保護膜形成用組成物藉由將用以構成該保護膜形成用組成物之各成分加以調配而獲得。 A protective film-forming composition such as a protective film-forming composition (IV-1) is obtained by blending the components constituting the protective film-forming composition.
調配各成分時的添加順序並無特別限定，亦可同時添加2種以上之成分。 The order of adding the components is not particularly limited, and two or more components may be added simultaneously.
於使用溶劑之情形時，可藉由下述方式使用：將溶劑與溶劑以外的任一種調配成分混合而將該調配成分預先稀釋；亦可藉由下述方式使用：不將溶劑以外的任一種調配成分預先稀釋而將溶劑與這些調配成分混合。 When a solvent is used, it can be used by mixing the solvent with any formulation component other than the solvent and diluting the formulation component in advance; it can also be used by the following method: not using any solvent other than the solvent The preparation ingredients are diluted in advance, and the solvent is mixed with these preparation ingredients.
調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機而進行混合之方法；施加超音波而進行混合之方法等。 There is no particular limitation on the method of mixing the components during preparation, and it may be appropriately selected from the following known methods: a method in which a stirrer or a stirring blade is rotated to perform mixing; a method in which a mixer is used to perform mixing; Method of mixing and the like.
關於添加及混合各成分時的溫度及時間，只要不使各調配成分劣化，則並無特別限定，適宜調節即可，溫度較佳為15℃至30℃。 The temperature and time when each component is added and mixed are not particularly limited as long as the prepared components are not deteriorated, and may be appropriately adjusted, and the temperature is preferably 15 ° C to 30 ° C.
與可用於本發明之保護膜形成用複合片同樣地，作為貼附於半導體晶圓或半導體晶片中的與電路面為相反側的背面，且於支持片上具備顯示接著性之層之複合片，有切割晶粒接合片(dicing die bonding sheet)。 As a composite sheet for forming a protective film that can be used in the present invention, as a composite sheet attached to a semiconductor wafer or a semiconductor wafer on the opposite side to the circuit surface and provided with a layer showing adhesiveness on a supporting sheet, There are dicing die bonding sheets.
但是，切割晶粒接合片所具備之接著劑層發揮以下功能：與半導體晶片一起自支持片拾取後，將該半導體晶片安裝於基板、引線框架、或其他半導體晶片等時，作為接著劑之功能。另一方面，關於可用於本發明之保護膜形成用複合片中的保護膜形成用膜，就與半導體晶片一起自支持片拾取之方面而言，與前述接著劑層相同，但最終藉由硬化而成為保護膜，具有保護所貼附之半導體晶片的背面之功能。如此，本發明中的保護膜形成用膜的用途與切割晶粒接合片中的接著劑層不同，當然所要求之性能亦不同。反映該用途之差異，通常，若與切割晶粒接合片中的接著劑層進行比較，則保護膜形成用膜存在較硬，難以拾取之傾向。因此，通常難以將切割晶粒接合片中的接著劑層直接轉用作保護膜形成用複合片中的保護膜形成用膜。作為可用於本發明之具備能量線硬化性之保護膜形成用膜而成之保護膜形成用複合片，可適宜選擇使用附有保護膜的半導體晶片的拾取適性優異的保護膜形成用複合片。 However, the adhesive layer provided in the dicing die-bonding sheet functions as an adhesive when the semiconductor wafer is mounted on a substrate, a lead frame, or another semiconductor wafer after being picked up from the support sheet together with the semiconductor wafer. . On the other hand, the protective film-forming film that can be used in the protective film-forming composite sheet of the present invention is the same as the aforementioned adhesive layer in that it is picked up from the support sheet together with the semiconductor wafer, but is finally cured by As a protective film, it has the function of protecting the back surface of the attached semiconductor wafer. As described above, the use of the film for forming a protective film in the present invention is different from the adhesive layer in a dicing die-bonding sheet, and of course, the required performance is also different. Reflecting the difference in use, in general, when compared with the adhesive layer in a dicing die-bonding sheet, the protective film-forming film tends to be hard and difficult to pick up. Therefore, it is generally difficult to directly transfer the adhesive layer in a dicing die-bonding sheet to a film for forming a protective film in a composite sheet for forming a protective film. As the protective film-forming composite sheet which can be used for the protective film-forming film with energy ray hardening property of the present invention, a protective film-forming composite sheet having excellent pick-up suitability using a semiconductor wafer with a protective film can be appropriately selected.
◇保護膜形成用複合片的製造方法 ◇ Manufacturing method of composite sheet for protective film formation
可用於本發明之保護膜形成用複合片可藉由將上述 各層以成為對應的位置關係之方式依序積層而製造。各層之形成方法如前文所說明。 The composite sheet for forming a protective film that can be used in the present invention can be produced by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. The formation method of each layer is as described above.
例如，製造支持片時，於基材上積層黏著劑層之情形時，於基材上塗敷上述黏著劑組成物，視需要使黏著劑組成物乾燥即可。 For example, when manufacturing a support sheet, when an adhesive layer is laminated | stacked on a base material, the said adhesive composition can be apply | coated on a base material, and an adhesive composition can be dried as needed.
另一方面，例如，於已積層於基材上之黏著劑層上進而積層保護膜形成用膜之情形時，可於黏著劑層上塗敷保護膜形成用組成物，直接形成保護膜形成用膜。保護膜形成用膜以外之層亦可使用用以形成該層之組成物，利用同樣的方法，於黏著劑層上積層該層。如此，於使用任一種組成物，形成連續之2層之積層結構之情形時，可於由前述組成物形成之層上，進一步塗敷組成物而新形成層。 On the other hand, for example, when a protective film-forming film is laminated on an adhesive layer on a substrate, a protective film-forming composition may be applied on the adhesive layer to directly form a protective film-forming film. . The composition other than the film for protective film formation can also use the composition for forming this layer, and this layer is laminated | stacked on an adhesive layer by the same method. In this way, when any one of the compositions is used to form a continuous two-layer laminated structure, the composition may be further coated on the layer formed of the aforementioned composition to newly form a layer.
但是，較佳為藉由下述方式而形成連續之2層之積層結構：於另一剝離膜上，使用前述組成物，預先形成這些2層中後積層之層，將該已形成之層中的與和前述剝離膜接觸之側為相反側的露出面，與既已形成之其餘層的露出面貼合。此時，前述組成物較佳為塗敷於剝離膜的剝離處理面。形成積層結構後，視需要移除剝離膜即可。 However, it is preferable to form a continuous two-layer laminated structure by using the aforementioned composition on another release film to previously form a layer of these two laminated layers, and to form the formed layer The side that is in contact with the release film is the exposed surface on the opposite side, and adheres to the exposed surfaces of the remaining layers that have already been formed. In this case, the composition is preferably a release-treated surface applied to a release film. After the laminated structure is formed, the release film can be removed as needed.
例如，於製造於基材上積層黏著劑層，於前述黏著劑層上積層保護膜形成用膜而成之保護膜形成用複合片(支持片為基材及黏著劑層之積層物之保護膜形成用複合片)之情形時，於基材上塗敷黏著劑組成物，視需要使黏著劑 組成物乾燥，藉此於基材上預先積層黏著劑層，另行於剝離膜上塗敷保護膜形成用組成物，視需要使保護膜形成用組成物乾燥，藉此於剝離膜上預先形成保護膜形成用膜。然後，將該保護膜形成用膜的露出面與已積層於基材上之黏著劑層的露出面貼合，於黏著劑層上積層保護膜形成用膜，藉此獲得保護膜形成用複合片。 For example, a protective sheet forming composite sheet (a support sheet is a protective film of a laminate of a base material and an adhesive layer) formed by laminating an adhesive layer on a substrate and laminating a protective film-forming film on the aforementioned adhesive layer. In the case of forming a composite sheet), the adhesive composition is coated on the substrate, and if necessary, the adhesive composition is dried, so that the adhesive layer is laminated on the substrate in advance, and a protective film is additionally formed on the release film. The composition is formed by drying the composition for forming a protective film, if necessary, to previously form a film for forming a protective film on the release film. Then, the exposed surface of the protective film-forming film is bonded to the exposed surface of the adhesive layer laminated on the base material, and the protective film-forming film is laminated on the adhesive layer, thereby obtaining a protective film-forming composite sheet. .
於基材上積層黏著劑層之情形時，如上所述，亦可代替於基材上塗敷黏著劑組成物之方法，於剝離膜上塗敷黏著劑組成物，視需要使塗敷黏著劑組成物乾燥，藉此於剝離膜上預先形成黏著劑層，將該層的露出面與基材的一方的表面貼合，藉此於基材上積層黏著劑層。 When the adhesive layer is laminated on the substrate, as described above, instead of applying the adhesive composition on the substrate, the adhesive composition may be applied on the release film, and the adhesive composition may be applied as needed. By drying, an adhesive layer is formed on the release film in advance, and the exposed surface of this layer is bonded to one surface of the substrate, thereby laminating the adhesive layer on the substrate.
任一種方法中，均於形成目標積層結構後的任意時間點移除剝離膜即可。 In either method, the release film may be removed at any time after the target laminated structure is formed.
如此，構成保護膜形成用複合片之基材以外的層均可利用以下方法積層：預先形成於剝離膜上，再貼合於目標層的表面，因此視需要適宜選擇採用此種步驟之層，製造保護膜形成用複合片即可。 In this way, layers other than the base material constituting the protective film-forming composite sheet can be laminated using the following method: formed in advance on the release film and then bonded to the surface of the target layer, so the layer using this step is appropriately selected as needed, It is only necessary to produce a composite sheet for forming a protective film.
再者，保護膜形成用複合片通常以如下狀態保管：於該保護膜形成用複合片中的與支持片為相反側的最表層(例如，保護膜形成用膜)的表面貼合有剝離膜之狀態。因此，亦可藉由下述方式而獲得保護膜形成用複合片：於該 剝離膜(較佳為該剝離膜的剝離處理面)上，塗敷保護膜形成用組成物等用以形成構成最表層之層之組成物，視需要使組成物乾燥，藉此於剝離膜上預先形成構成最表層之層，於該層中的與和剝離膜接觸之側為相反側的露出面上，利用上述任一種方法積層其餘各層，不移除剝離膜而保持貼合狀態不變。 In addition, a protective film-forming composite sheet is generally stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film for protective film formation) on the opposite side to the support sheet in the protective film-forming composite sheet. Of the state. Therefore, a protective film-forming composite sheet can also be obtained by coating the release film (preferably the release-treated surface of the release film) with a composition for forming a protective film and the like to form a composition. For the composition of the surface layer, if necessary, the composition is dried, thereby forming a layer constituting the outermost layer on the release film in advance, and using the above on the exposed surface of the layer opposite to the side in contact with the release film, using the above Either method laminates the remaining layers without removing the release film and maintaining the bonded state.
◇保護膜形成用複合片的使用方法 ◇ How to use the composite sheet for protective film formation
保護膜形成用複合片例如可利用以下所示之方法進行使用。 The composite sheet for protective film formation can be used by the method shown below, for example.
亦即，將保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜，貼附於半導體晶圓的背面(與電極形成面為相反側的面)。接著，對保護膜形成用膜照射能量線，使保護膜形成用膜硬化而成為保護膜。接著，藉由切割，將半導體晶圓連同保護膜一起分割而製成半導體晶片。然後，將半導體晶片在保持貼附有該保護膜之狀態下直接(亦即以附有保護膜的半導體晶片之形式)自支持片拉離而進行拾取。 That is, the composite film for protective film formation and the protective film formation film of the protective film formation composite sheet are attached to the back surface (surface opposite to the electrode formation surface) of the semiconductor wafer. Next, the protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to form a protective film. Next, the semiconductor wafer and the protective film are divided by dicing to produce a semiconductor wafer. Then, the semiconductor wafer is directly picked out from the supporting sheet (that is, in the form of a semiconductor wafer with a protective film) while being picked up by the protective film while being attached.
將所拾取之附有保護膜的半導體晶片101收納於如圖8所示之壓紋載帶102的口袋102a，於口袋102a的開口部貼附蓋帶103，藉此將前述開口部封閉而進行包裝。然後，將壓紋載帶102以捲繞於捲盤之狀態保管、搬送、或商業交易，於下一步驟亦即將附有保護膜的半導體晶片101的半導體晶片倒裝晶片連接於基板的電路面之步驟中 使用。 The picked-up semiconductor wafer 101 with the protective film is stored in a pocket 102a of the embossed carrier tape 102 as shown in FIG. 8, and a cover tape 103 is attached to the opening of the pocket 102a, thereby closing the opening. package. Then, the embossed carrier tape 102 is stored, transported, or traded in a state of being wound on a reel. In the next step, the semiconductor wafer 101 with the protective film-attached semiconductor wafer is flip-chip connected to the circuit surface of the substrate Used in the steps.
本說明書中，所謂「壓紋載帶」係於聚苯乙烯、聚對苯二甲酸乙二酯或聚丙烯等樹脂製之長條狀片形成有以固定間隔成列設置之複數個凹部(有時稱為口袋)之包裝材料，前述複數個各口袋中，例如可收納本發明之附有保護膜的半導體晶片。前述複數個各口袋通常藉由下述方式而封閉遮蓋：於收納本發明之附有保護膜的半導體晶片等被收納物之狀態下，將該開口部貼附長條狀之蓋帶。包裝有附有保護膜的半導體晶片之壓紋載帶可以捲繞於捲盤之狀態使用。例如，可將前述捲盤設置於貼片機，對基板安裝附有保護膜的半導體晶片。壓紋載帶的口袋可根據被收納物之大小進行設計、加工。本說明書中的壓紋載帶的各口袋例如可列舉：縱向尺寸0.5mm至30mm、橫向尺寸0.5mm至30mm及深度0.1mm至10mm之口袋。前述長條狀的蓋帶的厚度為10μm至100μm，由PET(polyethylene terephthalate；聚對苯二甲酸乙二酯)等素材形成。 In the present specification, the "embossed carrier tape" refers to a long sheet made of resin such as polystyrene, polyethylene terephthalate, or polypropylene, and a plurality of recesses (including It is referred to as a pocket), and each of the plurality of pockets described above can store the semiconductor wafer with a protective film of the present invention. Each of the aforementioned plurality of pockets is usually closed and covered by accommodating an object to be stored such as the semiconductor wafer with a protective film of the present invention, and attaching a long cover tape to the opening. An embossed carrier tape with a protective film-attached semiconductor wafer can be used while being wound on a reel. For example, the reel may be set in a mounter, and a semiconductor wafer with a protective film may be mounted on the substrate. The pocket of the embossed carrier tape can be designed and processed according to the size of the object to be stored. Examples of the pockets of the embossed carrier tape in this specification include pockets with a longitudinal dimension of 0.5 mm to 30 mm, a lateral dimension of 0.5 mm to 30 mm, and a depth of 0.1 mm to 10 mm. The strip-shaped cover tape has a thickness of 10 μm to 100 μm and is formed of a material such as PET (polyethylene terephthalate).
以下，利用與先前法相同的方法，將附有保護膜的半導體晶片在保持貼附有該保護膜之狀態下直接自支持片拉離而進行拾取，將所獲得之附有保護膜的半導體晶片的半導體晶片倒裝晶片連接於基板的電路面後，製成半導體封裝。然後，使用該半導體封裝，製作目標半導體裝置即可。 Hereinafter, using the same method as in the previous method, the semiconductor wafer with a protective film is pulled out from the support sheet to pick up the semiconductor wafer with the protective film, and the obtained semiconductor wafer with the protective film is picked up. After the semiconductor wafer is flip-chip connected to the circuit surface of the substrate, a semiconductor package is fabricated. Then, using the semiconductor package, a target semiconductor device may be manufactured.
[實施例] [Example]
以下，藉由具體的實施例，對本發明進行更詳細的說明。但是，本發明並不受以下所示之實施例任何限定。 Hereinafter, the present invention will be described in more detail through specific examples. However, this invention is not limited at all by the Example shown below.
以下顯示用於製造保護膜形成用組成物之成分。 The components for producing the composition for forming a protective film are shown below.
．能量線硬化性成分 ． Energy ray hardening component
(a2)-1：三環癸烷二羥甲基二丙烯酸酯(日本化藥公司製造之「KAYARAD R-684」，2官能紫外線硬化性化合物，分子量304)。 (a2) -1: Tricyclodecane dimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., a bifunctional ultraviolet curable compound, molecular weight 304).
．不具有能量線硬化性基之聚合物 ． Polymer without energy ray hardening group
(b)-2：使丙烯酸甲酯(以下，簡記為「MA」)(85質量份)及丙烯酸-2-羥基乙酯(以下，簡記為「HEA」)(15質量份)進行共聚合而成之丙烯酸系樹脂(重量平均分子量300000)。 (b) -2: Copolymerization of methyl acrylate (hereinafter, abbreviated as "MA") (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter, abbreviated as "HEA") (15 parts by mass) Acrylic resin (weight average molecular weight 300,000).
．光聚合起始劑 ． Photopolymerization initiator
(c)-3：1-羥基-環己基-苯基-酮(BASF公司製造之「Irgacure(註冊商標)184」)。 (c) -3: 1-hydroxy-cyclohexyl-phenyl-one ("Irgacure (registered trademark) 184" manufactured by BASF).
(c)-4：2-(4-甲基苄基)-2-二甲基胺基-1-(4-嗎啉-4-基-苯基)-丁烷-1-酮(BASF公司製造之「Irgacure(註冊商標)379」，分子量380)。 (c) -4: 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butane-1-one (BASF Corporation "Irgacure (registered trademark) 379" (molecular weight: 380).
．填充材料 ． Filler
(d)-1：二氧化矽填料(溶融石英填料，平均粒徑8μm)。 (d) -1: Silica filler (fused silica filler, average particle diameter: 8 μm).
．偶合劑 ． Coupling agent
(e)-1：3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業公司製造之「KBM-503」，矽烷偶合劑)。 (e) -1: 3-Methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., a silane coupling agent).
．著色劑 ． Colorant
(g)-1：將酞菁系藍色色素(Pigment Blue 15：3)32質量份、異吲哚啉酮系黃色色素(Pigment Yellow 139)18質量份、及蒽醌系紅色色素(Pigment Red 177)50質量份進行混合，以前述3種色素的合計量/苯乙烯丙烯酸樹脂量=1/3(質量比)之方式進行顏料化而獲得之顏料。 (g) -1: 32 parts by mass of a phthalocyanine blue pigment (Pigment Blue 15: 3), 18 parts by mass of an isoindolinone yellow pigment (Pigment Yellow 139), and an anthraquinone red pigment (Pigment Red 177) A pigment obtained by mixing 50 parts by mass and performing pigmentation such that the total amount of the three kinds of pigments mentioned above / the amount of styrene acrylic resin = 1/3 (mass ratio).
[實施例1] [Example 1]
<保護膜形成用複合片之製造> <Manufacture of a protective film-forming composite sheet>
(保護膜形成用組成物(IV-1)之製造) (Manufacture of a protective film-forming composition (IV-1))
使能量線硬化性成分(a2)-1、聚合物(b)-2、光聚合起始劑(c)-3、光聚合起始劑(c)-4、填充材料(d)-1、偶合劑(e)-1及著色劑(g)-1，以這些的含量(固形物成分量，質量份)成為表1所示之值之方式溶解或分散於甲基乙基酮中，於23℃下進行攪拌，藉此製備固形物成分濃度為50質量%之保護膜形成用組成物(IV-1)。再者，表1中的含有成分一欄記載為「-」時意指保護膜形成用組成物(IV-1)不含該成分。 Energy ray hardening component (a2) -1, polymer (b) -2, photopolymerization initiator (c) -3, photopolymerization initiator (c) -4, filler (d) -1, The coupling agent (e) -1 and the coloring agent (g) -1 are dissolved or dispersed in methyl ethyl ketone so that the content (amount of solid content, mass parts) of these becomes the values shown in Table 1, and By stirring at 23 ° C., a composition (IV-1) for forming a protective film having a solid content concentration of 50% by mass was prepared. In addition, when "-" is shown in the column of the component contained in Table 1, it means that the composition (IV-1) for protective film formation does not contain this component.
(黏著劑組成物(I-4)之製造) (Manufacture of Adhesive Composition (I-4))
製備固形物成分濃度為30質量%之非能量線硬化性之黏著劑組成物(I-4)，該黏著劑組成物(I-4)含有丙烯酸系聚合物(100質量份，固形物成分)、及3官能苯二甲基二異氰酸酯系交聯劑(三井武田化學公司製造之「Takenate D110N」)(10.7質量份，固形物成分)，進一步含有作為溶劑之甲基乙基酮。前述丙烯酸系聚合物係使丙烯酸-2-乙基己酯(以下，簡記為「2EHA」)(36質量份)、BA(59質量份)、及HEA(5質量份)進行共聚合而成，且重量平均分子量為600000。 A non-energy-ray-curable adhesive composition (I-4) having a solid content concentration of 30% by mass was prepared, and the adhesive composition (I-4) contained an acrylic polymer (100 parts by mass, solid content) And trifunctional xylylene diisocyanate-based cross-linking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and further containing methyl ethyl ketone as a solvent. The acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass), And the weight average molecular weight was 600,000.
(支持片之製造) (Manufacture of supporting film)
於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm)的前述剝離處理面，塗敷上述所獲得之黏著劑組成物(I-4)，於120℃下加熱乾燥2分鐘，藉此形成厚度10μm之非能量線硬化性之黏著劑層。 The above-mentioned release-treated surface of a release film ("SP-PET381031" manufactured by Lintec Corporation, thickness: 38 µm) was subjected to a release treatment on one side of a polyethylene terephthalate film by a polysiloxane treatment, and the above-obtained coating was obtained. The adhesive composition (I-4) was dried by heating at 120 ° C. for 2 minutes, thereby forming a non-energy ray-curable adhesive layer having a thickness of 10 μm.
接著，於該黏著劑層的露出面貼合作為基材之聚丙烯系膜(楊氏率400，厚度80μm)，藉此獲得於前述基材的一方的表面上具備前述黏著劑層之支持片(10)-1。 Next, a polypropylene-based film (Young's rate 400, thickness 80 μm) as a substrate was bonded to the exposed surface of the adhesive layer, thereby obtaining a support sheet having the adhesive layer on one surface of the substrate. (10) -1.
(保護膜形成用複合片之製造) (Manufacture of protective film-forming composite sheet)
於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm)的前述剝離處理面，藉由刀式塗佈機塗敷上述所獲得之保護膜形成用組成物(IV-1)，於100℃下乾燥2分鐘，藉此製作厚度25μm之能量線硬化性之保護膜形成用膜(13)-9。 A peeling film ("SP-PET381031" manufactured by Lintec Corporation, with a thickness of 38 µm) of a peeling film (polyethylene terephthalate film) on one side of which was subjected to a silicone treatment for peeling treatment was applied by a knife method. The cloth was coated with the composition (IV-1) for forming a protective film obtained above and dried at 100 ° C. for 2 minutes, thereby producing an energy-ray-curable protective film (13) -9 having a thickness of 25 μm.
接著，自上述所獲得之支持片(10)-1中的黏著劑層移除剝離膜，於該黏著劑層的露出面貼合上述所獲得之保護膜形成用膜(13)-9的露出面，製作保護膜形成用複合片，該保護膜形成用複合片係基材、黏著劑層、保護膜形成用膜(13)-9及剝離膜於這些的厚度方向上依序積層而成。所獲得之保護膜形成用複合片之構成示於表2。 Next, the release film is removed from the adhesive layer in the support sheet (10) -1 obtained above, and the exposure of the protective film-forming film (13) -9 obtained above is bonded to the exposed surface of the adhesive layer. A composite sheet for forming a protective film is formed on the surface, and the composite sheet for forming a protective film is a base material, an adhesive layer, a film for forming a protective film (13) -9, and a release film which are laminated in this order in the thickness direction. The structure of the obtained protective film-forming composite sheet is shown in Table 2.
<保護膜形成用膜之評價> <Evaluation of Protective Film Forming Film>
以下述方式對保護膜形成用膜(13)-9的拉伸彈性率(楊氏率)進行評價。 The tensile elastic modulus (Young's ratio) of the film (13) -9 for protective film formation was evaluated in the following manner.
亦即，將保護膜形成用片(厚度：25μm)積層2層，藉此成為厚度50μm，將該樣品以15mm×100mm之尺寸進行拉伸試驗(拉伸速度：50mm/min)，根據拉伸初期之應力-應變線之斜率，算出保護膜形成用膜(13)-9的拉伸彈性率。 That is, a protective film-forming sheet (thickness: 25 μm) was laminated into two layers so as to have a thickness of 50 μm. This sample was subjected to a tensile test (drawing speed: 50 mm / min) at a size of 15 mm × 100 mm. The slope of the initial stress-strain line was used to calculate the tensile elastic modulus of the protective film-forming film (13) -9.
評價結果示於表2。 The evaluation results are shown in Table 2.
<保護膜之評價> <Evaluation of protective film>
以下述方式對保護膜形成用膜(13)-9的硬化後之拉伸彈性率(楊氏率)進行評價。 The tensile elastic modulus (Young's ratio) of the protective film-forming film (13) -9 after curing was evaluated in the following manner.
亦即，將保護膜形成用膜(13)-9(厚度：25μm)積層2層，藉此成為厚度50μm，自兩側各照射1次UV(照度：230mW/cm2，光量：170mJ/cm2)使保護膜形成用膜(13)-9硬 化。 (: Thickness of 25 m) 2-layer laminated, whereby a thickness 50 m, is irradiated from both sides of each 1 UV (illuminance: i.e., the film (13) -9 protective film forming 230mW / cm 2, light amount: 170mJ / cm 2 ) The protective film forming film (13) -9 is hardened.
然後，將樣品以15mm×100mm之尺寸進行拉伸試驗(拉伸速度：50mm/min)，根據拉伸初期之應力-應變線之斜率，算出保護膜的拉伸彈性率。 Then, the sample was subjected to a tensile test (tensile speed: 50 mm / min) at a size of 15 mm × 100 mm, and the tensile elastic modulus of the protective film was calculated from the slope of the stress-strain line at the initial stage of stretching.
評價結果示於表2。 The evaluation results are shown in Table 2.
(切割評價) (Cutting evaluation)
將上述所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-9，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 The composite film for forming a protective film obtained above was attached to a # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 μm) through the protective film-forming film (13) -9 of the composite film for forming a protective film. Then, the sheet was fixed to a ring frame and left to stand for 30 minutes.
接著，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-1側對保護膜形成用膜(13)-9照射紫外線，藉此使保護膜形成用膜(13)-9硬化，成為保護膜。 Next, using a UV irradiation device ("RAD2000m / 8" manufactured by Lintec), the protective film-forming film (from the support sheet (10) -1 side) was formed under the conditions of illuminance of 195 mW / cm 2 and light amount of 170 mJ / cm 2 13) -9 is irradiated with ultraviolet rays, whereby the film (13) -9 for forming a protective film is hardened and becomes a protective film.
接著，使用切割刀片，將矽晶圓連同保護膜一起切割而單片化，獲得2mm×2mm之矽晶片。 Next, using a dicing blade, the silicon wafer was diced together with the protective film to be singulated to obtain a 2 mm × 2 mm silicon wafer.
接著，使用黏晶機(Canon Machinery公司製造之「BESTEM-D02」)，拾取20個附有保護膜之矽晶片。此時，使用數位顯微鏡(Keyence公司製造，VHX-100，倍率：100倍)對切割所得之矽晶片之切斷面進行觀察。於確認到20μm以上之寬度或深度之破裂、缺損之情形時，產生碎 片，判定為不良(B)，於未確認到此種缺損之情形時，判定為良好(A)。結果示於表2。表2中的「晶片之破裂、缺損之抑制」一欄之記載為相應的結果。 Next, using a die attach machine ("BESTEM-D02" manufactured by Canon Machinery), 20 silicon wafers with a protective film were picked up. At this time, the cut surface of the diced silicon wafer was observed using a digital microscope (VHX-100, manufactured by Keyence Corporation, magnification: 100 times). When cracks or defects with a width or depth of 20 μm or more are confirmed, fragments are generated and judged to be defective (B). When such defects are not confirmed, they are judged to be good (A). The results are shown in Table 2. The corresponding results are shown in the column of "chip cracking and defect suppression" in Table 2.
(刀片堵塞評價) (Blade blocking evaluation)
利用數位顯微鏡(Keyence公司製造，VHX-100，倍率：100倍)觀察切割後之刀片刀尖，將未附著保護膜之刀片設為「A」，將附著保護膜之刀片設為「B」。 Use a digital microscope (Keyence Corporation, VHX-100, magnification: 100 times) to observe the cutting edge of the razor blade, set the blade without the protective film to "A", and set the blade with the protective film to "B".
(蓋帶附著性評價) (Evaluation of cover tape adhesion)
將上述所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-9，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 The composite film for forming a protective film obtained above was attached to a # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 μm) through the protective film-forming film (13) -9 of the composite film for forming a protective film. Then, the sheet was fixed to a ring frame and left to stand for 30 minutes.
接著，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-1側對保護膜形成用複合片照射紫外線，藉此使保護膜形成用膜(13)-9硬化，成為保護膜。 Subsequently, the ultraviolet irradiation device (manufactured by the Lintec Company "RAD2000m / 8") at an illuminance 195mW / cm 2, light quantity of 170mJ / cm condition 2, the self-supporting sheet (10) -1-side protective film of the composite sheet is formed By irradiating ultraviolet rays, the protective film-forming film (13) -9 is hardened and becomes a protective film.
接著，使用切割刀片，將矽晶圓連同保護膜一起切割而單片化，獲得縱3mm×橫3mm、保護層厚度25μm、Si(矽)層厚350μm之矽晶片。 Next, using a dicing blade, the silicon wafer was singulated with a protective film and singulated to obtain a silicon wafer having a length of 3 mm × a width of 3 mm, a protective layer thickness of 25 μm, and a Si (silicon) layer thickness of 350 μm.
接著，使用黏晶機(Canon Machinery公司製造之「BESTEM-D02」)，拾取20個附有保護膜之矽晶片。 Next, using a die attach machine ("BESTEM-D02" manufactured by Canon Machinery), 20 silicon wafers with a protective film were picked up.
於縱12cm×橫12cm、厚度5mm之鐵板上，以相互間 隔均等之方式將16個前述所獲得之附有保護膜之矽晶片以分別縱4個×橫4個載置於正方形之格子狀之位置，於上述矽晶片上被覆縱12cm×橫3.8cm之蓋帶(Sumitomo Bakelite公司製造，CSL-Z7302)，載置於加熱至40℃之熱盤上，於該熱盤上載置金屬板，並以施加於附有保護膜之矽晶片之壓力成為350gf之方式進行設置，進行一分鐘過熱。然後，移除金屬板，剝離前述蓋帶，檢測附有保護膜之矽晶片是否附著於蓋帶。結果示於表2。 On the iron plate of 12cm × 12cm in thickness and 5mm in thickness, the 16 silicon wafers with the protective film obtained as described above were placed in a square grid shape with 4 × 4 horizontally. At this position, a cover tape (manufactured by Sumitomo Bakelite, CSL-Z7302) of 12 cm by 3.8 cm was covered on the above silicon wafer, placed on a hot plate heated to 40 ° C, and a metal plate was placed on the hot plate. It was set so that the pressure applied to the silicon wafer with a protective film became 350 gf, and overheated for one minute. Then, the metal plate is removed, the cover tape is peeled off, and it is checked whether a silicon wafer with a protective film is attached to the cover tape. The results are shown in Table 2.
作為判定方法，於16個附有保護膜之矽晶片中至少一個附著於蓋帶之情形時判定為「B」，於16個附有保護膜之矽晶片中沒有一個附著於蓋帶之情形時判定為「A」。 As a judgment method, it is judged as "B" when at least one of the 16 silicon wafers with a protective film is attached to the cover tape, and when none of the 16 silicon wafers with a protective film is attached to the cover tape. It is judged as "A".
<保護膜形成用片之製造及評價> <Production and Evaluation of Sheets for Protective Film Formation>
[實施例2] [Example 2]
於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之第1剝離膜(Lintec公司製造之「SP-PET382150」，厚度38μm)的前述剝離處理面，藉由刀式塗佈機塗敷上述所獲得之保護膜形成用組成物(IV-1)，於100℃下乾燥2分鐘，藉此製作厚度25μm之能量線硬化性之保護膜形成用膜(13)-9。 The peeling-treated surface of the first peeling film ("SP-PET382150", manufactured by Lintec Corporation, thickness: 38 μm) on one side of a polyethylene terephthalate film subjected to a silicone treatment for peeling treatment was cut by a knife. The protective film-forming composition (IV-1) obtained above was applied by a type coater, and dried at 100 ° C for 2 minutes, thereby producing a protective film-forming film (13) having an energy ray curability of 25 μm in thickness- 9.
接著，於所獲得之保護膜形成用膜(13)-9的露出面，貼合聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之第2剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm)的剝離面，獲得由第1剝 離膜(圖7中的第1剝離膜15'：25μm)、及第2剝離膜15"構成之保護膜形成用片。 Next, on the exposed surface of the obtained protective film-forming film (13) -9, a second release film (Lintec) having a single surface of a polyethylene terephthalate film subjected to a polysiloxane treatment and subjected to a release treatment was bonded. The release surface of "SP-PET381031" manufactured by the company, with a thickness of 38 µm) was used to form a protective film composed of a first release film (the first release film 15 ': 25 µm in Fig. 7) and a second release film 15 " Tablets.
剝離上述所獲得之保護膜形成用片之第2剝離膜後，將上述所獲得之保護膜形成用膜(13)-9，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，獲得由6吋矽晶圓、保護膜形成用膜(13)-9、及第1剝離膜構成之積層體。 After peeling the second release film of the protective film forming sheet obtained above, the protective film forming film (13) -9 obtained above was attached to a # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 μm). A laminated body composed of a 6-inch silicon wafer, a protective film-forming film (13) -9, and a first release film was obtained.
自上述所獲得之積層體移除第1剝離膜，另外，自以與實施例1相同之方式獲得之支持片(10)-1之黏著劑層移除剝離膜，於支持片(10)-1之黏著劑層的露出面，貼附保護膜形成用膜(13)-9及第1剝離膜，且藉由該保護膜形成用膜(13)-9貼附，進而將該片固定於環狀框，靜置30分鐘。 The first release film was removed from the laminate obtained as described above, and the release film was removed from the adhesive layer of the support sheet (10) -1 obtained in the same manner as in Example 1. The support sheet (10)- The protective film-forming film (13) -9 and the first release film are attached to the exposed surface of the adhesive layer of 1, and the protective film-forming film (13) -9 is attached, and the sheet is further fixed to Ring frame, let stand for 30 minutes.
接著，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-1側對保護膜形成用複合片照射紫外線，藉此使保護膜形成用膜(13)-9硬化，成為保護膜。 Next, using an ultraviolet irradiation device ("RAD2000m / 8" manufactured by Lintec), under the conditions of illuminance of 195 mW / cm 2 and light quantity of 170 mJ / cm 2 , a composite sheet for forming a protective film was supported from the support sheet (10) -1 By irradiating ultraviolet rays, the protective film-forming film (13) -9 is hardened and becomes a protective film.
接著，使用切割刀片，將矽晶圓連同保護膜形成用膜(13)-9一起切割而單片化，獲得2mm×2mm之矽晶片。 Next, using a dicing blade, the silicon wafer and the protective film-forming film (13) -9 were cut and singulated to obtain a 2 mm × 2 mm silicon wafer.
以與實施例1相同的方式，進行由切割引起之晶片之破裂、缺損之抑制之評價，刀片堵塞之抑制之評價，及對蓋帶之附著性之評價。拉伸彈性率與實施例1相同。評價結果示於表2。 In the same manner as in Example 1, the evaluation of the cracking and defect suppression of the wafer caused by the dicing, the evaluation of the suppression of the blade clogging, and the evaluation of the adhesion to the cover tape were performed. The tensile elastic modulus is the same as in Example 1. The evaluation results are shown in Table 2.
[實施例3] [Example 3]
<保護膜形成用複合片之製造> <Manufacture of a protective film-forming composite sheet>
(保護膜形成用組成物(IV-1)之製造) (Manufacture of a protective film-forming composition (IV-1))
如表1所示，將能量線硬化性成分(a2)-1的含量(調配量)設為10質量份代替20質量份，使用光聚合起始劑(c)-4代替光聚合起始劑(c)-3，將光聚合起始劑(c)-4的含量(調配量)設為0.6質量份，除此方面以外，利用與實施例1相同的方法製備保護膜形成用組成物(IV-1)。 As shown in Table 1, the content (blending amount) of the energy ray-curable component (a2) -1 was set to 10 parts by mass instead of 20 parts by mass, and the photopolymerization initiator (c) -4 was used instead of the photopolymerization initiator. (c) -3, except that the content (prepared amount) of the photopolymerization initiator (c) -4 was set to 0.6 parts by mass, a composition for forming a protective film was prepared by the same method as in Example 1 ( IV-1).
(保護膜形成用複合片之製造) (Manufacture of protective film-forming composite sheet)
使用上述所獲得之保護膜形成用組成物(IV-1)，除此方面以外，利用與實施例1相同的方法製作厚度25μm之能量線硬化性之保護膜形成用膜(13)-10。 Except for the above-mentioned composition (IV-1) for forming a protective film, a film (13) -10 for forming an energy-ray-curable protective film with a thickness of 25 μm was prepared by the same method as in Example 1 except for this point.
並且，使用該保護膜形成用膜(13)-10代替保護膜形成用膜(13)-9，除此方面以外，利用與實施例1相同的方法製造保護膜形成用複合片。所獲得之保護膜形成用複合片之構成示於表2。 In addition, this protective film-forming film (13) -10 was used in place of the protective film-forming film (13) -9. Except for this point, a composite film for protective film formation was produced by the same method as in Example 1. The structure of the obtained protective film-forming composite sheet is shown in Table 2.
<保護膜形成用複合片之製造及評價> <Production and Evaluation of Protective Film Forming Composite Sheet>
使用上述所獲得之保護膜形成用複合片，利用與實施例1相同的方法，進行拉伸彈性率之測定，由切割引起之晶片之破裂、缺損之抑制之評價，刀片堵塞之抑制之評價，及對蓋帶之附著性之評價。評價結果示於表2。 Using the composite sheet for protective film formation obtained above, the tensile modulus was measured by the same method as in Example 1, the evaluation of the cracking and defect suppression of the wafer caused by dicing, and the evaluation of the suppression of blockage of the blade, And evaluation of the adhesion of the cover tape. The evaluation results are shown in Table 2.
[比較例1] [Comparative Example 1]
<保護膜形成用複合片之製造及評價> <Production and Evaluation of Protective Film Forming Composite Sheet>
將利用與實施例1相同的方法所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-9，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 A protective film-forming composite sheet obtained by the same method as in Example 1 was attached to a 6-inch silicon wafer (thickness) through the protective film-forming film (13) -9 of the protective film-forming composite sheet. 100 μm) of # 2000 polished surface, the sheet was further fixed to a ring frame, and left to stand for 30 minutes.
接著，使用切割刀片，將矽晶圓連同保護膜形成用膜(13)-9一起切割而單片化，獲得2mm×2mm之矽晶片。 Next, using a dicing blade, the silicon wafer and the protective film-forming film (13) -9 were cut and singulated to obtain a 2 mm × 2 mm silicon wafer.
利用與實施例1相同的方法，進行由切割引起之晶片之破裂、缺損之抑制之評價，刀片堵塞之抑制之評價，及對蓋帶之附著性之評價。切割時之保護膜形成用膜的拉伸彈性率與實施例1之保護膜形成用膜的拉伸彈性率相同。評價結果示於表2。 Using the same method as in Example 1, evaluation of cracking and defect suppression of wafers caused by dicing, evaluation of blade blocking suppression, and evaluation of adhesion to cover tape were performed. The tensile elastic modulus of the film for protective film formation at the time of dicing was the same as the tensile elastic modulus of the film for protective film formation of Example 1. The evaluation results are shown in Table 2.
[比較例2] [Comparative Example 2]
<保護膜形成用片之製造及評價> <Production and Evaluation of Sheets for Protective Film Formation>
利用與實施例2相同的方法製作由6吋矽晶圓、保護膜形成用膜(13)-9、及第1剝離膜構成之積層體。 A laminated body composed of a 6-inch silicon wafer, a protective film-forming film (13) -9, and a first release film was produced by the same method as in Example 2.
自所獲得之積層體移除第1剝離膜，另外，自以與實施例1相同的方式所獲得之支持片(10)-1之黏著劑層移除剝離膜，於支持片(10)-1之黏著劑層的露出面，貼附保護膜形成用膜(13)-9及第1剝離膜，且藉由該保護膜形成用膜(13)-9貼附，進而將該片固定於環狀框，靜置30分鐘。 The first release film was removed from the obtained laminate, and the release film was removed from the adhesive layer of the support sheet (10) -1 obtained in the same manner as in Example 1. The support sheet (10)- The protective film-forming film (13) -9 and the first release film are attached to the exposed surface of the adhesive layer of 1, and the protective film-forming film (13) -9 is attached, and the sheet is further fixed to Ring frame, let stand for 30 minutes.
接著，使用切割刀片，將矽晶圓連同保護膜形成用膜(13)-9一起切割而單片化，獲得2mm×2mm之矽晶片。 Next, using a dicing blade, the silicon wafer and the protective film-forming film (13) -9 were cut and singulated to obtain a 2 mm × 2 mm silicon wafer.
利用與實施例2相同的方法，進行由切割引起之晶片之破裂、缺損之抑制之評價，刀片堵塞之抑制之評價，及對蓋帶之附著性之評價。切割時之保護膜形成用膜的拉伸彈性率與實施例2之保護膜形成用膜的拉伸彈性率相同。評價結果示於表2。 In the same manner as in Example 2, evaluation of cracking and defect suppression of the wafer caused by dicing, evaluation of blocking of the blade, and evaluation of adhesion to the cover tape were performed. The tensile elastic modulus of the film for protective film formation at the time of dicing was the same as the tensile elastic modulus of the film for protective film formation of Example 2. The evaluation results are shown in Table 2.
[比較例3] [Comparative Example 3]
<保護膜形成用複合片之製造及評價> <Production and Evaluation of Protective Film Forming Composite Sheet>
利用與實施例3相同的方法製造保護膜形成用複合片。所獲得之保護膜形成用複合片之構成示於表2。 A composite sheet for forming a protective film was produced by the same method as in Example 3. The structure of the obtained protective film-forming composite sheet is shown in Table 2.
將上述所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-10，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 The composite film for forming a protective film obtained above was attached to a # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 μm) through the protective film-forming film (13) -10 of the composite film for forming a protective film. Then, the sheet was fixed to a ring frame and left to stand for 30 minutes.
接著，使用切割刀片，將矽晶圓連同保護膜形成用膜(13)-10一起切割而單片化，獲得2mm×2mm之矽晶片。 Next, using a dicing blade, the silicon wafer and the protective film-forming film (13) -10 were cut and singulated to obtain a 2 mm × 2 mm silicon wafer.
利用與實施例1相同的方法，進行由切割引起之晶片之破裂、缺損之抑制之評價，刀片堵塞之抑制之評價，及對蓋帶之附著性之評價。切割時之保護膜形成用膜的拉伸彈性率與實施例3之保護膜形成用膜的拉伸彈性率相同。評價結果示於表2。 Using the same method as in Example 1, evaluation of cracking and defect suppression of wafers caused by dicing, evaluation of blade blocking suppression, and evaluation of adhesion to cover tape were performed. The tensile elastic modulus of the film for protective film formation at the time of dicing was the same as the tensile elastic modulus of the film for protective film formation of Example 3. The evaluation results are shown in Table 2.
根據實施例1至實施例3之結果可明確，於對保護膜形成用膜照射能量線而使保護膜形成用膜硬化後，切割半導體晶圓之情形時，切割時切割刀片之堵塞得到抑制，切割適性亦優異。推測實施例1至實施例3中，切割半導體晶圓時保護膜的拉伸彈性率為500MPa以上之相對較高的彈性率，藉此可抑制切割時保護膜之碎片，抑制刀片堵塞。 According to the results of Examples 1 to 3, it is clear that when the protective film forming film is irradiated with energy rays to harden the protective film forming film, and when the semiconductor wafer is cut, clogging of the dicing blade during cutting is suppressed. Cutting suitability is also excellent. It is speculated that in Examples 1 to 3, the tensile elastic modulus of the protective film when dicing the semiconductor wafer is a relatively high elastic modulus of 500 MPa or more, thereby suppressing chipping of the protective film during dicing and blocking of the blade.
相對於此，比較例1至比較例3中，不對保護膜形成用膜照射能量線使保護膜形成用膜硬化，而切割半導體晶圓。該情形時，切割時之保護膜形成用膜的拉伸彈性率(楊氏率)為相對較小的50MPa至90MPa，因此產生由切割引起之晶片之破裂、缺損，容易產生刀片堵塞，另外，產生對蓋帶之附著。 In contrast, in Comparative Examples 1 to 3, the protective film-forming film was not hardened by irradiating the protective film-forming film with energy rays, and the semiconductor wafer was diced. In this case, the tensile elastic modulus (Young's ratio) of the protective film-forming film during dicing is relatively small from 50 MPa to 90 MPa, so cracks and defects of the wafer due to dicing are generated, and blade clogging is likely to occur. Adhesion to cover tape occurs.
(產業可利用性) (Industrial availability)
本發明可用於製造半導體裝置。 The present invention can be used for manufacturing a semiconductor device.
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