TWI790400B - Protective film forming film, composite sheet for forming protective film, method for inspection and method for identification - Google Patents
Protective film forming film, composite sheet for forming protective film, method for inspection and method for identification Download PDFInfo
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
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Abstract
Description
本發明係關於一種保護膜形成用膜、保護膜形成用複合片、檢查方法以及辨識方法。 The present invention relates to a film for forming a protective film, a composite sheet for forming a protective film, an inspection method, and an identification method.
本申請案主張基於2018年9月11日在日本提出申請之日本專利特願2018-169591號的優先權，且將該申請案的內容引用至本文中。 This application claims priority based on Japanese Patent Application No. 2018-169591 filed in Japan on September 11, 2018, and the contents of the application are incorporated herein by reference.
近年來，業界應用稱為所謂的倒裝(face down)方式之安裝方法而製造半導體裝置。倒裝方式中，使用於電路面上具有凸塊等電極之半導體晶片，將前述電極與基板接合。因此，有時半導體晶片中的與電路形成面為相反側的背面裸露。 In recent years, semiconductor devices have been manufactured using a mounting method called a so-called face down method in the industry. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on the circuit surface is used, and the electrodes are bonded to the substrate. Therefore, the back surface of the semiconductor wafer opposite to the circuit formation surface may be exposed.
有時於該裸露的半導體晶片的背面，形成含有有機材料之保護膜，以附保護膜之半導體晶片之形式組入至半導體裝置中。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。 Sometimes, a protective film containing an organic material is formed 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. 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，例如使用於支撐片上具備用以形成保護膜之保護膜形成用膜之保護膜形成用複合片。保護膜形成用膜可藉由硬化而形成保護膜。另外，支撐片可用於將背面具備保護膜形成用膜或保護膜之半導體晶圓分割為半導體晶片時，固定半導體晶圓。進而，支撐片亦可用作切割片，且保護膜形成用複合片亦可用作保護膜形成用膜與切割 片形成為一體之複合片(例如參照專利文獻1)。 In order to form such a protective film, the composite sheet for protective film formation provided with the film for protective film formation for forming a protective film on a support sheet is used, for example. The film for protective film formation can form a protective film by hardening. Moreover, a support sheet can be used for fixing a semiconductor wafer when the semiconductor wafer provided with the film for protective film formation or a protective film on the back surface is divided into semiconductor wafers. Furthermore, the support sheet can also be used as a dicing sheet, and the composite sheet for forming a protective film can also be used as a film for forming a protective film and a dicing sheet. The sheet is formed into an integrated composite sheet (for example, refer to Patent Document 1).
專利文獻1所記載之保護膜形成用膜係使波長1600nm之紅外線光線透過率成為72%以上，使550nm之可見光線透過率成為20%以下。藉此，可藉由照射雷射光而進行印字加工，且可藉由紅外線檢查工件或將該工件加工而獲得之加工物中所存在之龜裂等。 The film for forming a protective film described in Patent Document 1 has an infrared ray transmittance of 72% or more at a wavelength of 1600 nm and a visible ray transmittance of 550 nm of 20% or less. Thereby, printing processing can be performed by irradiating laser light, and cracks, etc. existing in a workpiece or a processed product obtained by processing the workpiece can be inspected by infrared rays.
於使用具備專利文獻1所記載之保護膜形成用膜之保護膜形成用複合片，製造附保護膜之半導體晶片之情形，例如首先於半導體晶圓的背面貼附保護膜形成用複合片。繼而，對保護膜形成用膜進行雷射印字，然後為了提高保護膜形成層的保護性能，視需要經過利用熱或能量線之硬化，藉由切割將半導體晶圓分割為晶片，並進行拾取。繼而，對於所拾取之附保護膜之半導體晶片，通常於將半導體封裝體安裝於基板(母板(mother board)等)時，進行熱處理(雷射標記後進行之回流步驟)。 In the case of manufacturing a protective film-attached semiconductor wafer using a protective film forming composite sheet provided with the protective film forming film described in Patent Document 1, first, for example, the protective film forming composite sheet is attached to the back surface of the semiconductor wafer. Next, laser printing is performed on the film for protective film formation, and then, in order to improve the protective performance of the protective film formation layer, the semiconductor wafer is divided into chips by dicing and picked up after hardening with heat or energy rays as necessary. Next, heat treatment (reflow step performed after laser marking) is usually performed on the picked-up semiconductor wafer with a protective film when the semiconductor package is mounted on a substrate (mother board, etc.).
另外，於使用專利文獻1所記載之保護膜形成用膜，製造附保護膜之半導體晶片之情形，例如，如圖8所示，首先，於半導體晶圓9的背面貼附保護膜形成用膜13(圖8中的(a))。繼而，對保護膜形成用膜13進行雷射印字(圖8中的(b))，然後為了提高保護膜形成層的保護性能，視需要經過利用熱或能量線之硬化(圖8中的(c))，貼附切割帶後藉由切割將半導體晶圓分割為晶片，並進行拾取。繼而，對於所拾取之附保護膜之半導體晶片，於將半導體封裝體安裝於基板時，進行熱處理(回流步驟)(圖8中的(d))。
In addition, in the case of manufacturing a semiconductor wafer with a protective film using the film for forming a protective film described in Patent Document 1, for example, as shown in FIG. 13 ((a) in Figure 8). Next, laser printing is performed on the
[先前技術文獻] [Prior Art Literature]
[專利文獻] [Patent Document]
專利文獻1：國際公開第2015/111632號。 Patent Document 1: International Publication No. 2015/111632.
於使用先前的保護膜形成用膜或保護膜形成用複合片之附保護膜之半導體晶片的製造方法中，對保護膜形成用膜進行雷射印字，於保護膜形成用膜的硬化步驟或將半導體封裝體安裝於基板時的回流步驟中，有雷射印字劣化之虞。對此，考慮以於保護膜形成用膜的硬化步驟或回流步驟中，不使雷射印字劣化之方式，對半導體晶圓的背面進行雷射印字之方法。 In the conventional method of manufacturing a semiconductor wafer with a protective film using a film for forming a protective film or a composite sheet for forming a protective film, laser printing is performed on the film for forming a protective film, and in the step of curing the film for forming a protective film or applying In the reflow step when the semiconductor package is mounted on the substrate, there is a risk of deterioration of the laser marking. On the other hand, a method of performing laser printing on the back surface of the semiconductor wafer is conceivable so as not to degrade the laser printing in the curing step or the reflow step of the film for forming a protective film.
例如，如圖9所示，首先，對半導體晶圓9的背面進行雷射印字(圖9中的(a))，然後於印字面貼附保護膜形成用膜13(圖9中的(b))。繼而，對於保護膜形成用膜13，視需要經過利用熱或能量線之硬化(圖9中的(c))，貼附切割帶後藉由切割將半導體晶圓分割為晶片，並進行拾取。繼而，對於所拾取之附保護膜之半導體晶片，進行熱處理(回流步驟)(圖9中的(d))。
For example, as shown in FIG. 9, at first, laser printing is carried out to the back surface of semiconductor wafer 9 ((a) in FIG. )). Next, the protective
然而，先前的保護膜形成用膜如可藉由照射雷射光而進行印字加工般可見光線透過率低，於對半導體晶圓的背面進行直接雷射印字之用途中，印字被遮蔽，因此欠佳。 However, the conventional film for forming a protective film has a low transmittance of visible light as it can be printed by irradiating laser light, and it is not good for direct laser printing on the back surface of a semiconductor wafer because the printed characters are blocked. .
本發明係鑒於上述情況而完成，提供一種保護膜形成用膜、及具備前述保護膜形成用膜之保護膜形成用複合片、及檢查方法以及辨識方法，前述保護膜形成用膜可用於對半導體晶圓的背面進行雷射印字，保護印字面之用途。 The present invention has been accomplished in view of the above circumstances, and provides a film for forming a protective film, a composite sheet for forming a protective film provided with the film for forming a protective film, an inspection method, and a method for identifying it. The film for forming a protective film can be used for semiconductor The back of the wafer is laser printed to protect the printed surface.
為了解決上述課題，本發明提供下述實施形態。 In order to solve the above-mentioned problems, the present invention provides the following embodiments.
[1]一種保護膜形成用膜，係貼附於半導體晶圓的供雷射印字的背面，而用於製造附保護膜之半導體晶片，且圖像清晰度為110以上。 [1] A film for forming a protective film, which is attached to the back surface of a semiconductor wafer for laser printing, and is used to manufacture a semiconductor wafer with a protective film, and has an image resolution of 110 or higher.
[2]一種保護膜形成用複合片，具備支撐片，且於前述支撐片上具備如前述[1]所記載之保護膜形成用膜。 [2] A composite sheet for forming a protective film, comprising a support sheet, and the film for forming a protective film as described in [1] above on the support sheet.
[3]一種檢查方法，包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附如前述[1]所記載之保護膜形成用膜之步驟；及隔著保護膜，對前述半導體晶圓或前述半導體晶片進行檢查之步驟，前述保護膜係於前述半導體晶圓的背面或將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成之膜。 [3] An inspection method comprising: a step of performing laser printing on the back of the semiconductor wafer; a step of attaching the film for forming a protective film as described in [1] above to the back of the semiconductor wafer; A step of inspecting the aforementioned semiconductor wafer or the aforementioned semiconductor wafer with a protective film attached to the back of the aforementioned semiconductor wafer or the back of a semiconductor wafer obtained by singulating the aforementioned semiconductor wafer. A film formed by forming a film.
[4]如前述[3]所記載之檢查方法，其中前述檢查步驟係如下：隔著保護膜，檢查雷射印字於前述半導體晶圓或前述半導體晶片之印字、前述半導體晶圓或前述半導體晶片的背面的研削痕跡、或者半導體晶圓或前述半導體晶片與前述保護膜之間有無異物，前述保護膜係於前述半導體晶圓的背面或將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成之膜。 [4] The inspection method described in [3] above, wherein the inspection step is as follows: inspecting the laser printing on the semiconductor wafer or the printing of the semiconductor wafer, the semiconductor wafer or the semiconductor wafer through the protective film Grinding marks on the back of the semiconductor wafer, or the presence or absence of foreign matter between the semiconductor wafer or the semiconductor wafer and the protective film on the back of the semiconductor wafer or the semiconductor wafer obtained by singulating the semiconductor wafer A film formed by attaching the aforementioned film for forming a protective film.
[5]一種辨識方法，包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附如前述[1]所記載之保護膜形成用膜之步驟；及隔著保護膜，讀取雷射印字於前述半導體晶片之印字，辨識前述半導體晶片的種類之步驟，前述保護膜係於將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成之膜。 [5] An identification method comprising: a step of laser printing on the back of the semiconductor wafer; a step of attaching the film for forming a protective film as described in [1] above to the back of the semiconductor wafer; Putting on the protective film, reading the laser printing on the semiconductor wafer, and identifying the type of the semiconductor wafer. The protective film is attached to the back of the semiconductor wafer obtained by singulating the semiconductor wafer. A film formed by forming a film.
根據本發明，提供一種保護膜形成用膜、及具備前述保護膜形成用膜之保護膜形成用複合片、及檢查方法以及辨識方法，前述保護膜形成用膜可用於對半導體晶圓的背面進行雷射印字並保護印字面之用途。 According to the present invention, there are provided a film for forming a protective film, a composite sheet for forming a protective film provided with the film for forming a protective film, an inspection method, and a method for identifying the film for forming a protective film, which can be used for performing inspection on the back surface of a semiconductor wafer. Laser printing and protection of the printed surface.
1A、1B、1C、1D、1E、1F:保護膜形成用複合片 1A, 1B, 1C, 1D, 1E, 1F: composite sheet for protective film formation
10:支撐片 10: Support sheet
10a:支撐片的表面(第1面) 10a: The surface of the support sheet (1st surface)
11:基材 11: Substrate
11a:基材的表面(第1面) 11a: The surface of the base material (side 1)
12:黏著劑層 12: Adhesive layer
12a:黏著劑層的表面(第1面) 12a: The surface of the adhesive layer (1st surface)
13、23:保護膜形成用膜 13, 23: Film for protective film formation
13a、23a:保護膜形成用膜的表面(第1面) 13a, 23a: the surface (1st surface) of the film for protective film formation
13b:保護膜形成用膜的表面(第2面) 13b: The surface of the film for protective film formation (2nd surface)
15:剝離膜 15: Peel off film
151:第1剝離膜 151: 1st peeling film
152:第2剝離膜 152: Second release film
16:治具用接著劑層 16: Adhesive layer for jig
16a:治具用接著劑層的表面 16a: The surface of the adhesive layer for jigs
9:半導體晶圓 9: Semiconductor wafer
圖1係以示意方式表示本發明的一實施形態的保護膜形成用膜之剖面圖。 Fig. 1 is a cross-sectional view schematically showing a film for forming a protective film according to an embodiment of the present invention.
圖2係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖面圖。 Fig. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
圖3係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖面圖。 Fig. 3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
圖4係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖面圖。 Fig. 4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
圖5係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖面圖。 Fig. 5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
圖6係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖面圖。 Fig. 6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
圖7係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖面圖。 Fig. 7 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
圖8係以示意方式表示先前的附保護膜之半導體晶片的製造步驟之剖面圖。 Fig. 8 is a cross-sectional view schematically showing the manufacturing steps of a conventional semiconductor wafer with a protective film.
圖9係以示意方式表示本發明的一實施形態的保護膜形成用膜的使用方法之剖面圖。 Fig. 9 is a cross-sectional view schematically showing a method of using a film for forming a protective film according to an embodiment of the present invention.
◇保護膜形成用膜 ◇Film for protective film formation
本發明的保護膜形成用膜係貼附於半導體晶圓的供雷射印字的背面，而用於製造附保護膜之半導體晶片，且圖像清晰度為110以上。保護膜形成用膜的圖像清晰度係指依據JIS K 7374，使用5種狹縫(狹縫寬度：0.125mm、0.25mm、0.5mm、1mm及2mm)所測定之評價值的合計值。 The film for forming a protective film of the present invention is attached to the back surface of a semiconductor wafer for laser printing, and is used to manufacture a semiconductor wafer with a protective film, and has an image resolution of 110 or higher. The image clarity of the film for protective film formation is the total value of the evaluation value measured using 5 types of slits (slit width: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm) based on JIS K 7374.
保護膜形成用膜的圖像清晰度為110以上，較佳為130以上，更佳為150以上，尤佳為170以上。藉由本發明的保護膜形成用膜的圖像清晰度為下限值以上，將保護膜形成用膜貼附於半導體晶圓的背面而形成之保護膜的圖像清晰度亦良好。保護膜形成用膜的圖像清晰度可為500以下，亦可為450以下，亦可為400以下。 The image resolution of the film for protective film formation is 110 or more, Preferably it is 130 or more, More preferably, it is 150 or more, Most preferably, it is 170 or more. When the image clarity of the film for protective film formation of this invention is more than the lower limit, the image clarity of the protective film formed by affixing the film for protective film formation to the back surface of a semiconductor wafer is also favorable. The image clarity of the film for protective film formation may be 500 or less, may be 450 or less, and may be 400 or less.
藉由本發明的保護膜形成用膜的圖像清晰度良好，可隔著保護膜，對前述半導體晶圓或前述半導體晶片進行檢查，前述保護膜係於半導體晶圓的背面或將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成。更具體而言，可隔著保護膜，讀取雷射印字於前述半導體晶圓或前述半導體晶片之文字、符號、花紋等印字，可檢查前述印字、前述半導體晶圓或前述半導體晶片的背面的研削痕跡、或者半導體晶圓或前述半導體晶片與前述保護膜之間有無異物，前述保護膜係於半導體晶圓的背面或將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成。另外，於有異物之情形，可檢查前述異物的狀態。 Since the image definition of the film for forming a protective film of the present invention is good, the aforementioned semiconductor wafer or the aforementioned semiconductor wafer can be inspected through the protective film, the aforementioned protective film is attached to the back surface of the semiconductor wafer or the aforementioned semiconductor wafer The film for protective film formation mentioned above is attached to the back surface of the semiconductor wafer obtained by singulation, and it forms. More specifically, it is possible to read laser-printed characters, symbols, and patterns printed on the aforementioned semiconductor wafer or the aforementioned semiconductor wafer through the protective film, and to inspect the aforementioned printed characters, the aforementioned semiconductor wafer, or the back surface of the aforementioned semiconductor wafer. Grinding traces, or presence or absence of foreign matter on the semiconductor wafer or between the aforementioned semiconductor wafer and the aforementioned protective film attached to the back of the semiconductor wafer or the back of the semiconductor wafer obtained by singulating the aforementioned semiconductor wafer. A film is formed using a film. In addition, in the case of foreign matter, the state of the aforementioned foreign matter can be checked.
保護膜形成用膜的圖像清晰度可藉由後述之保護膜形成用組成物的含有成分而進行調整，其中，可藉由選擇填充材料的種類或尺寸、著色劑的種類或含量而進行細微調整。 The image clarity of the film for forming a protective film can be adjusted by the components contained in the composition for forming a protective film described later, among which, fine adjustment can be made by selecting the type or size of the filler, and the type or content of the colorant. Adjustment.
保護膜形成用膜的波長550nm之光線透過率較佳為30%以上，更佳為40%以上，尤佳為45%以上。藉由保護膜形成用膜的波長550nm之光線透過率為前述下限值以上，可更清晰地讀取雷射印字所得之文字、符號、花紋等印字。保護膜形成用膜的波長550nm之光線透過率可為99.5%以下，亦可為99.0%以下。保護膜形成用膜的波長550nm之光線透過率可藉由後述之保護膜形成用組成物的含有成分、尤其是熱硬化性成分、填充材 料及/或著色劑的種類、含量等而進行調整。 The light transmittance of the film for forming a protective film at a wavelength of 550 nm is preferably at least 30%, more preferably at least 40%, and most preferably at least 45%. When the light transmittance of the film for forming a protective film at a wavelength of 550 nm is equal to or higher than the aforementioned lower limit, it is possible to more clearly read printed characters, symbols, and patterns obtained by laser printing. The light transmittance of the film for protective film formation at a wavelength of 550 nm may be 99.5% or less, and may be 99.0% or less. The light transmittance of the film for forming a protective film at a wavelength of 550 nm can be determined by the components contained in the composition for forming a protective film described later, especially thermosetting components and fillers. Adjust the type and content of the material and/or colorant.
保護膜形成用膜的霧度較佳為40以下，更佳為30以下，進而較佳為20以下，尤佳為10以下。藉由保護膜形成用膜的霧度為前述上限值以下，可更清晰地讀取雷射印字所得之文字、符號、花紋等印字。保護膜形成用膜的霧度可為0.5以上，亦可為1.0以上。所謂「霧度」，只要無特別說明，則意指依據JIS K 7136進行測定而獲得之值。保護膜形成用膜的霧度可藉由後述之保護膜形成用組成物的含有成分、尤其是熱硬化性成分、填充材料及/或著色劑的種類、含量等而進行調整，亦可藉由保護膜形成用膜的表面粗糙度而進行調整。 The haze of the film for protective film formation is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 10 or less. When the haze of the film for protective film formation is below the said upper limit, the printed characters, symbols, patterns, etc. obtained by laser printing can be read more clearly. The haze of the film for protective film formation may be 0.5 or more, and may be 1.0 or more. The term "haze" means a value measured in accordance with JIS K 7136 unless otherwise specified. The haze of the film for forming a protective film can be adjusted by the types and contents of the components contained in the composition for forming a protective film described later, especially thermosetting components, fillers, and/or colorants, and can also be adjusted by The surface roughness of the film for protective film formation was adjusted.
保護膜形成用膜的表面粗糙度較佳為0.090μm以下，更佳為0.070μm以下。保護膜形成用膜的表面粗糙度可為0.009μm以上，亦可為0.010μm以上。藉由保護膜形成用膜的表面粗糙度為前述上限值以下，提高雷射印字所得之文字、符號、花紋等印字的視認性。此外，本說明書中，所謂「表面粗糙度」，只要無特別說明，則意指依據JIS B0601：2001求出之所謂的算術平均粗糙度，有時簡稱為「Ra」。保護膜形成用膜的表面粗糙度可藉由塗敷條件或保護膜形成用組成物的含有成分而進行調整。 The surface roughness of the film for protective film formation is preferably at most 0.090 μm, more preferably at most 0.070 μm. The surface roughness of the film for protective film formation may be 0.009 micrometer or more, and may be 0.010 micrometer or more. When the surface roughness of the film for protective film formation is below the said upper limit, the visibility of printed characters, symbols, patterns, etc. obtained by laser printing improves. In addition, in this specification, "surface roughness" means the so-called arithmetic mean roughness calculated|required based on JISB0601:2001, unless otherwise specified, and it may be abbreviated as "Ra" in some cases. The surface roughness of the film for forming a protective film can be adjusted by coating conditions or the components contained in the composition for forming a protective film.
前述保護膜形成用膜亦可為藉由照射能量線或加熱處理進行硬化而成為保護膜之膜。該保護膜用以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。能量線硬化性的保護膜形成用膜相較於熱硬化性的保護膜形成用膜而言，可藉由短時間內的硬化而形成保護膜。 The film for forming a protective film may be cured by energy ray irradiation or heat treatment to become a protective film. This protective film is used to protect the semiconductor wafer or the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer. The film for protective film formation is soft and can be easily attached to an object to be attached. The film for forming an energy ray curable protective film can form a protective film by curing in a short time compared to the film for forming a thermosetting protective film.
圖1係以示意方式表示本發明的一實施形態的保護膜形成用膜13之剖面圖。此外，以下的說明中所使用之圖中，為了易於理解本發明的特徵，方便起見，有時將成為主要部分之部分放大表示，而並不限於
各構成要素的尺寸比率等與實際相同。
FIG. 1 is a cross-sectional view schematically showing a
此處所示之保護膜形成用膜13於該保護膜形成用膜13的一表面(本說明書中，有時稱為「第1面」)13a上具備第1剝離膜151，於與前述第1面13a為相反側的另一表面(本說明書中，有時稱為「第2面」)13b上具備第2剝離膜152。
The
此種保護膜形成用膜13例如適於製成捲筒狀保管。
Such a protective
保護膜形成用膜13可具有硬化性，亦可為不具有硬化性之非硬化性。
The
另外，於保護膜形成用膜具有硬化性之情形，可為熱硬化性及能量線硬化性中的任一種。 Moreover, when the film for protective film formation has curability, any of thermosetting property and energy ray curability may be sufficient.
非硬化性保護膜形成用膜可使用後述之非硬化性保護膜形成用組成物而形成。 The film for non-curable protective film formation can be formed using the composition for non-curable protective film formation mentioned later.
熱硬化性保護膜形成用膜可使用後述之熱硬化性保護膜形成用組成物而形成。 The film for thermosetting protective film formation can be formed using the composition for thermosetting protective film formation mentioned later.
能量線硬化性保護膜形成用膜可使用後述之能量線硬化性保護膜形成用組成物而形成。 The film for energy ray curable protective film formation can be formed using the composition for energy ray curable protective film formation mentioned later.
第1剝離膜151及第2剝離膜152均可為公知的剝離膜。
Both the
第1剝離膜151及第2剝離膜152可為相互相同的剝離膜，亦可為例如自保護膜形成用膜13剝離時所需之剝離力相互不同等相互不同的剝離膜。
The
圖1所示之保護膜形成用膜13係移除第1剝離膜151及第2剝離膜152中的任一剝離膜，於所產生之露出面貼附半導體晶圓(省略圖示)的背面。然後，移除第1剝離膜151及第2剝離膜152中的剩餘的另一剝離膜，所產生之露出面成為支撐片的貼附面。
The
◇保護膜形成用複合片 ◇Composite sheets for protective film formation
本發明的一實施形態的保護膜形成用複合片具備支撐片，且於前述支撐片上具備前述保護膜形成用膜。 The composite sheet for protective film formation which concerns on one Embodiment of this invention is equipped with a support sheet, and is equipped with the said film for protective film formation on the said support sheet.
本發明中，只要即便於保護膜形成用膜硬化後，亦維持支撐片及保護膜形成用膜之硬化物(換言之，為支撐片及保護膜)之積層結構，則將該積層結構體稱為「保護膜形成用複合片」。 In the present invention, as long as the laminated structure of the hardened product of the support sheet and the protective film forming film (in other words, the support sheet and the protective film) is maintained even after the protective film forming film is cured, the laminated structure is referred to as "Composite sheet for protective film formation".
作為本發明的保護膜形成用複合片之使用對象的半導體晶圓的厚度並無特別限定，就更容易分割為後述之半導體晶片之方面而言，較佳為30μm至1000μm，更佳為30μm至400μm。 The thickness of the semiconductor wafer to which the composite sheet for forming a protective film of the present invention is used is not particularly limited, but is preferably from 30 μm to 1000 μm, more preferably from 30 μm to 400 μm.
以下，對保護膜形成用複合片的構成詳細地進行說明。 Hereinafter, the structure of the composite sheet for protective film formation is demonstrated in detail.
◎支撐片 ◎Support piece
前述支撐片可由1層(單層)所構成，亦可由2層以上之多層所構成。於支撐片由多層所構成之情形，這些多層相互可相同亦可不同，這些多層的組合只要無損本發明的效果，則並無特別限定。可轉用切割帶或半導體加工用之黏著帶。 The aforementioned support sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the support sheet is composed of multiple layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited as long as the effect of the present invention is not impaired. It can be used as dicing tape or adhesive tape for semiconductor processing.
作為較佳的支撐片，例如可列舉：具備基材，且於前述基材上以直接接觸之方式積層黏著劑層而成之支撐片(基材及黏著劑層依序以接觸之方式積層而成之支撐片)；基材、中間層及黏著劑層依序於這些層的厚度方向上以接觸之方式積層而成之支撐片；僅由基材所構成之支撐片等。 As a preferable support sheet, for example, a support sheet having a substrate and an adhesive layer laminated in direct contact with the substrate (the substrate and the adhesive layer are sequentially laminated in contact with each other) support sheet); a support sheet in which the base material, an intermediate layer, and an adhesive layer are sequentially laminated in a contact manner in the thickness direction of these layers; a support sheet composed of only the base material, etc.
以下，一面參照圖式，一面按照此種支撐片的每個種類，說明本發明的保護膜形成用複合片的示例。 Hereinafter, an example of the composite sheet for protective film formation of this invention is demonstrated for each type of such a support sheet, referring drawings.
圖2係以示意方式表示本發明的一實施形態的保護膜形成用複合片之剖面圖。 Fig. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
此外，於圖2以後的圖中，對與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，並省略該構成要素之詳細說明。 In addition, in FIG. 2 and subsequent figures, the same components as those shown in the already-described figures are given the same symbols as those in the already-described figures, and detailed descriptions of the components are omitted.
此處所示之保護膜形成用複合片1A具備基材11，且於基材11上具備黏著劑層12，於黏著劑層12上具備保護膜形成用膜13。支撐片10係基材11及黏著劑層12之積層體，換言之，保護膜形成用複合片1A具有於支撐片10的一表面(本說明書中，有時稱為「第1面」)10a上積層有保護膜形成用膜13之構成。另外，保護膜形成用複合片1A進而於保護膜形成用膜13上具備剝離膜15。
The
保護膜形成用複合片1A中，於基材11的一表面(本說明書中，有時稱為「第1面」)11a積層有黏著劑層12，於黏著劑層12的一表面(本說明書中，有時稱為「第1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的第1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的第1面13a中未積層治具用接著劑層16的面、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
保護膜形成用複合片1A中，保護膜形成用膜13的圖像清晰度為110以上。
In 1 A of composite sheets for protective film formation, the image clarity of the
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多層結構。
The
圖2所示之保護膜形成用複合片1A係以下述方式使用：以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的背面，進而，將治具用接著劑層16的表面16a中的上表面貼附於環狀框架等治具。
The
圖3係以示意方式表示本發明的另一實施形態的保護膜形 成用複合片之剖面圖。 Fig. 3 shows schematically the protective film shape of another embodiment of the present invention. Sectional view of finished composite sheet.
此處所示之保護膜形成用複合片1B除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的第1面11a積層有黏著劑層12，於黏著劑層12的第1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的第1面13a的整個面積層有剝離膜15。
The
保護膜形成用複合片1B中，保護膜形成用膜13的圖像清晰度為110以上。
In the
圖3所示之保護膜形成用複合片1B係以下述方式使用：以移除剝離膜15之狀態，於保護膜形成用膜13的第1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，進而，將周緣部附近的區域貼附於環狀框架等治具。
The
圖4係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖面圖。 Fig. 4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.
此處所示之保護膜形成用複合片1C除不具備黏著劑層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，支撐片10僅由基材11所構成。並且，於基材11的第1面11a(支撐片10的第1面10a)積層有保護膜形成用膜13，於保護膜形成用膜13的第1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的第1面13a中未積層治具用接著劑層16的區域、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。
1 C of composite sheets for protective film formation shown here are the same as 1 A of composite sheets for protective film formation shown in FIG. 2 except the point which does not have the adhesive agent layer 12. That is, in 1 C of composite sheets for protective film formation, the
保護膜形成用複合片1C中，保護膜形成用膜13的圖像清晰度為110以上。
In 1 C of composite sheets for protective film formation, the image resolution of the
圖4所示之保護膜形成用複合片1C與圖2所示之保護膜形
成用複合片1A同樣地以下述方式使用：以移除剝離膜15之狀態，於保護膜形成用膜13的第1面13a貼附半導體晶圓(省略圖示)的背面，進而，將治具用接著劑層16的表面16a中的上表面貼附於環狀框架等治具。
The
圖5係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖面圖。 Fig. 5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.
此處所示之保護膜形成用複合片1D除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的第1面11a積層有保護膜形成用膜13，於保護膜形成用膜13的第1面13a的整個面積層有剝離膜15。
The
保護膜形成用複合片1D中，保護膜形成用膜13的圖像清晰度為110以上。
In the
圖5所示之保護膜形成用複合片1D與圖3所示之保護膜形成用複合片1B同樣地以下述方式使用：以移除剝離膜15之狀態，於保護膜形成用膜13的第1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，進而，將周緣部附近的區域貼附於環狀框架等治具。
The
圖6係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖面圖。 Fig. 6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.
此處所示之保護膜形成用複合片1E除保護膜形成用膜的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具備基材11，且於基材11上具備黏著劑層12，於黏著劑層12上具備保護膜形成用膜23。支撐片10係基材11及黏著劑層12之積層體，換言之，保護膜形成用複合片1E具有於支撐片10的第1面10a上積層有保護膜形成用膜23之構成。另外，保護膜形成用複合片1E進而於保護膜形成用膜23上具備剝離膜15。
The
保護膜形成用複合片1E中，於基材11的第1面11a積層有黏著劑層12，於黏著劑層12的第1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。並且，於黏著劑層12的第1面12a中未積層保護膜形成用膜23的區域、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
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，例如具有圓形狀等形狀。
When the
保護膜形成用複合片1E中，保護膜形成用膜23的圖像清晰度為110以上。
In the
圖6所示之保護膜形成用複合片1E係以下述方式使用：以移除剝離膜15之狀態，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，進而，將黏著劑層12的第1面12a中未積層保護膜形成用膜23的區域貼附於環狀框架等治具。
The
圖7係以示意方式表示本發明的又一實施形態的保護膜形成用複合片之剖面圖。 Fig. 7 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.
此處所示之保護膜形成用複合片1F除於黏著劑層12的第1面12a中未積層保護膜形成用膜23的區域，與圖2及圖4所示同樣地積層有治具用接著劑層16之方面以外，與圖6所示之保護膜形成用複合片1E相同。亦即，保護膜形成用複合片1F係具備基材11，且於基材11上具備黏著劑層12，於黏著劑層12上具備保護膜形成用膜23，於黏著劑層12的第1面12a中未積層保護膜形成用膜23的區域積層治具用接著劑層16而成。支撐片10係基材11及黏著劑層12之積層體，換言之，保護膜形成用複合片1F具有於支撐片10的第1面10a上積層有保護膜形成用膜23之構成。另外，保護膜形成用複合片1F進而於保護膜形成用膜23上具備剝離膜15。
In the protective film forming
保護膜形成用複合片1F中，於基材11的第1面11a積層有黏著劑層12，於黏著劑層12的第1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。並且，於黏著劑層12的第1面12a中未積層保護膜形成用膜23的區域、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
自上方往下俯視保護膜形成用複合片1F時，保護膜形成用膜23的表面積小於黏著劑層12，例如具有圓形狀等形狀。
When the
保護膜形成用複合片1F中，保護膜形成用膜23的圖像清晰度為110以上。
In the
圖7所示之保護膜形成用複合片1F係以下述方式使用：以移除剝離膜15之狀態，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，進而，將治具用接著劑層16的表面16a中的上表面貼附於環狀框架等治具。
The
如此，保護膜形成用複合片無論支撐片及保護膜形成用膜為何種形態，均可為具備治具用接著劑層之複合片。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之複合片。 Thus, the composite sheet for protective film formation may be a composite sheet provided with the adhesive agent layer for jigs regardless of what form the support sheet and the film for protective film formation are. However, generally, as shown in FIG. 2 and FIG. 4 , as the composite sheet for protective film formation provided with the adhesive agent layer for jigs, the composite sheet provided with the adhesive agent layer for jigs on the film for protective film formation is preferable.
本發明的一實施形態的保護膜形成用複合片並不限定於圖2至圖7所示之保護膜形成用複合片，在無損本發明的效果之範圍內，亦可將圖2至圖7所示之保護膜形成用複合片的一部分構成變更或刪除，或者對前文說明之保護膜形成用複合片進一步追加其他構成。 The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to the composite sheet for forming a protective film shown in FIGS. A part of the configuration of the shown composite sheet for forming a protective film is changed or deleted, or other configurations are further added to the composite sheet for forming a protective film 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的中間層。
For example, in the composite sheet for protective film formation shown in FIG. 4 and FIG. 5, an intermediate layer may be provided between the
另外，圖2、圖3、圖6及圖7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，本發明的保護膜形成用複合片中，支撐片亦可為基材、中間層及黏著劑層依序於這些層的厚度方向上積層而成之支撐片。此處，中間層與圖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 addition, in the composite sheet for protective film formation shown in FIG. 2, FIG. 3, FIG. 6, and FIG. 7, an intermediate layer may be provided between the
另外，圖2至圖7所示之保護膜形成用複合片可將前述中間層以外的層設置於任意的部位。 In addition, in the composite sheet for protective film formation shown in FIGS. 2-7, layers other than the said intermediate|middle layer may be provided in arbitrary places.
另外，保護膜形成用複合片中，亦可於剝離膜與直接接觸該剝離膜之層之間產生一部分間隙。 Moreover, in the composite sheet for protective film formation, some gaps may generate|occur|produce between a release film and the layer which directly contacts this release film.
另外，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。 In addition, in the composite sheet for protective film formation, the size and shape of each layer can be adjusted arbitrarily according to the purpose.
本發明的保護膜形成用複合片中，黏著劑層等支撐片中與保護膜形成用膜直接接觸之層可為非能量線硬化性，亦可為能量線硬化性。 In the composite sheet for forming a protective film of the present invention, the layer in direct contact with the film for forming a protective film in the support sheet such as the adhesive layer may be non-energy ray curable or energy ray curable.
於為非能量線硬化性之情形，保護膜形成用複合片可更廉價地製造。 In the case of non-energy ray curing, the composite sheet for forming a protective film can be produced at a lower cost.
於為能量線硬化性之情形，保護膜形成用複合片更容易調整黏著力，變得容易調節切割或拾取的適性。 In the case of energy ray curing, the composite sheet for forming a protective film can be more easily adjusted for adhesive force, and it becomes easier to adjust the suitability for cutting or picking up.
此外，本發明中，所謂「非硬化性」，意指藉由加熱或照射能量線等而不硬化之性質，所謂「熱硬化性」，意指藉由進行加熱而硬化之性質，所謂「能量線硬化性」，意指藉由照射能量線而硬化之性質。 In addition, in the present invention, "non-curable" means the property of not being hardened by heating or irradiating energy rays, etc., the term "thermosetting" means the property of being cured by heating, and the term "energy "Ray curability" refers to the property of hardening by irradiation of energy rays.
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，作為該能量線的示例，可列舉紫外線、放射線、電子束等。 In the present invention, "energy ray" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples of the energy ray include ultraviolet rays, radiation, electron beams, and the like.
紫外線例如可藉由使用高壓水銀燈、融合燈、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產生之電子束。 Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode; Light Emitting Diode) lamp as an ultraviolet source. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like.
支撐片可為透明，亦可為不透明，還可根據目的而著色。 The support sheet may be transparent or opaque, and may be colored according to the purpose.
於保護膜形成用膜具有能量線硬化性之情形，支撐片較佳為使能量線透過之支撐片。 When the film for protective film formation has energy ray curability, the support sheet is preferably a support sheet that allows energy ray to pass through.
例如，支撐片中，波長375nm之光的透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。藉由前述光的透過率為此種範圍，經由支撐片對保護膜形成用膜照射能量線(紫外線)時，保護膜形成用膜的硬化度進一步提高。 For example, in the support sheet, the transmittance of light with a wavelength of 375 nm is preferably at least 30%, more preferably at least 50%, and most preferably at least 70%. When the transmittance of the said light is such a range, when the film for protective film formation is irradiated with an energy ray (ultraviolet ray) via a support sheet, the degree of hardening of the film for protective film formation improves further.
另一方面，支撐片中，波長375nm之光的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 support sheet, the upper limit of the transmittance of light having a wavelength of 375 nm is not particularly limited, and may be 95%, for example.
另外，支撐片中，波長532nm之光的透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。 In addition, in the support sheet, the transmittance of light with a wavelength of 532 nm is preferably at least 30%, more preferably at least 50%, and most preferably at least 70%.
藉由前述光的透過率為此種範圍，可經由支撐片，隔著前述保護膜，讀取雷射印字於前述半導體晶圓或前述半導體晶片之文字、符號、花紋等印字，可檢查前述印字、前述半導體晶圓或前述半導體晶片的背面的研削痕跡、或者半導體晶圓或前述半導體晶片與前述保護膜之間有無異物。另外，於有異物之情形，可檢查前述異物的狀態。 With the transmittance of the aforementioned light in such a range, the laser-printed characters, symbols, patterns, etc. printed on the aforementioned semiconductor wafer or the aforementioned semiconductor wafer can be read through the support sheet through the aforementioned protective film, and the aforementioned printed characters can be inspected. , the grinding marks on the semiconductor wafer or the back surface of the semiconductor wafer, or the presence or absence of foreign matter between the semiconductor wafer or the semiconductor wafer and the protective film. In addition, in the case of foreign matter, the state of the aforementioned foreign matter can be checked.
另一方面，支撐片中，波長532nm之光的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 support sheet, the upper limit of the transmittance of light having a wavelength of 532 nm is not particularly limited, and may be 95%, for example.
另外，支撐片中，波長1064nm之光的透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。藉由前述光的透過率為此種範圍，可經由支撐片，隔著前述保護膜，讀取雷射印字於前述半導體晶圓或前述半導體晶片之文字、符號、花紋等印字，可檢查前述印字、前述半導體晶圓或前述半導體晶片的背面的研削痕跡、或者半導體晶圓或前述半導體晶片與前述保護膜之間有無異物。另外，於有異物之情形，可檢查前述異物 的狀態。 In addition, in the support sheet, the transmittance of light with a wavelength of 1064 nm is preferably at least 30%, more preferably at least 50%, and most preferably at least 70%. With the transmittance of the aforementioned light in such a range, the laser-printed characters, symbols, patterns, etc. printed on the aforementioned semiconductor wafer or the aforementioned semiconductor wafer can be read through the support sheet through the aforementioned protective film, and the aforementioned printed characters can be inspected. , the grinding marks on the semiconductor wafer or the back surface of the semiconductor wafer, or the presence or absence of foreign matter between the semiconductor wafer or the semiconductor wafer and the protective film. In addition, in the case of foreign matter, you can check the aforementioned foreign matter status.
另一方面，支撐片中，波長1064nm之光的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 support sheet, the upper limit of the transmittance of light having a wavelength of 1064 nm is not particularly limited, and may be 95%, for example.
其次，對構成支撐片之各層更詳細地進行說明。 Next, each layer 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 aforementioned base material is in the form of a sheet or a film, and examples of the constituent material of the aforementioned base material 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的聚烯烴；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、聚對苯二甲酸丁二酯、聚間苯二甲酸乙二酯、聚-2,6-萘二甲酸乙二酯、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 aforementioned resins include polyethylenes such as low-density polyethylene (LDPE; Low Density Polyethylene), linear low-density polyethylene (LLDPE; Linear Low Density Polyethylene), and high-density polyethylene (HDPE; High Density Polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- Ethylene-based copolymers such as (meth)acrylate copolymers and ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine ethylene as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate Polyesters such as diesters, polyethylene-2,6-naphthalate, wholly aromatic polyesters having aromatic ring groups in all structural units; copolymers of two or more of the aforementioned polyesters; poly(methyl ) acrylate; polyurethane; polyacrylate urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; Polyester; Polyetherketone, etc.
另外，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的量為相對較少量。 Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, are also mentioned, for example. In the polymer alloy of the aforementioned polyester and a resin other than the aforementioned polyester, it is preferable that the amount of the resin other than the polyester is relatively small.
另外，作為前述樹脂，例如亦可列舉：前文例示之前述樹脂中的1種或2種以上交聯而成之交聯樹脂；使用前文例示之前述樹脂中的1種或2種以上之離子聚合物等改質樹脂。 In addition, examples of the aforementioned resins include: crosslinked resins obtained by crosslinking one or more of the aforementioned resins exemplified above; modified resins.
此外，本說明書中，「(甲基)丙烯酸」的概念包括「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，例如「(甲基)丙烯醯基」的概念包括「丙烯醯基」及「甲基丙烯醯基」兩者，「(甲基)丙烯酸酯」的概念包括「丙烯酸酯」及「甲基丙烯酸酯」兩者。 In addition, in this specification, the concept of "(meth)acryl" includes both "acryl" and "methacryl". The same applies to terms similar to (meth)acrylic acid. For example, the concept of "(meth)acryl" includes both "acryl" and "methacryl", and "(meth)acrylate" The concept includes both "acrylate" and "methacrylate".
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，這些的組合及比率可任意選擇。 The resin constituting the base material may be only one type, or two or more types, and in the case of two or more types, the combination and ratio of these can be selected arbitrarily.
基材可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。 The base material may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.
基材的厚度較佳為50μm以上至300μm以下，更佳為60μm以上至100μm以下。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 not less than 50 μm and not more than 300 μm, more preferably not less than 60 μm and not more than 100 μm. When the thickness of the base material is in such a range, the flexibility of the composite sheet for forming a protective film and the adhesiveness 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，例如所謂由多層所構成之基材的厚度，意指構成基材之全部層的合計厚度。 Here, the "thickness of the substrate" means the thickness of the entire substrate, for example, the thickness of a substrate composed of multiple layers means the total thickness of all the layers constituting the substrate.
基材較佳為厚度精度高之基材，亦即較佳為無論部位如何厚度不均皆得到抑制之基材。作為上述之構成材料中可用於構成此種厚度精度高之基材之材料，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 base material is preferably a base material with high thickness accuracy, that is, a base material in which thickness unevenness is suppressed regardless of the location. Among the above-mentioned constituent materials, materials that can be used to constitute such a base material with high thickness accuracy include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer. wait.
基材中，除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 base material 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 aforementioned resins.
基材的光學特性只要滿足上文說明之支撐片的光學特性即可。亦即，基材可為透明，亦可為不透明，還可根據目的而著色，還可蒸鍍其他層。 The optical properties of the substrate should only satisfy the optical properties of the supporting sheet described above. That is, the base material may be transparent or opaque, may be colored according to the purpose, and may be vapor-deposited with other layers.
並且，於保護膜形成用膜具有能量線硬化性之情形，基材較佳為使能量線透過之基材。 Furthermore, when the film for protective film formation has energy ray curability, it is preferable that a base material is a base material which transmits energy ray.
為了提高基材與設置於該基材上之黏著劑層等其他層之密接性，亦可對基材表面實施利用噴砂處理、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等。 In order to improve the adhesion between the base material and other layers such as the adhesive layer provided on the base material, the surface of the base material can also be subjected to roughening treatment such as 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.
另外，亦可對基材表面實施底塗處理。 In addition, a primer treatment may be performed on the surface of the base material.
另外，基材亦可具有防止於將抗靜電塗佈層、保護膜形成用複合片重疊保存時，基材接著於其他片、或基材接著於吸附台之層等。 In addition, the base material may have a layer that prevents the base material from adhering to other sheets or the base material from adhering to the suction table when the antistatic coating layer and the composite sheet for forming a protective film are stacked for storage.
這些之中，就抑制因切割時的刀片的摩擦而導致基材產生斷片之方面而言，基材尤佳為表面實施過電子束照射處理之基材。 Among these, the base material whose surface is subjected to electron beam irradiation treatment is particularly preferable from the viewpoint of suppressing the breakage of the base material due to the friction of the blade during dicing.
基材可利用公知的方法製造。例如，含有樹脂之基材可藉由將含有前述樹脂之樹脂組成物成形而製造。 The substrate can be produced by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the aforementioned resin.
○黏著劑層 ○Adhesive layer
前述黏著劑層為片狀或膜狀，且含有黏著劑。 The aforementioned 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 aforementioned adhesive include: acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, etc. Resin, preferably acrylic resin.
此外，本發明中，「黏著性樹脂」的概念包括具有黏著性之樹脂及具有接著性之樹脂兩者，例如不僅包括樹脂本身具有黏著性之樹脂，亦包括藉由與添加劑等其他成分併用而顯示黏著性之樹脂、或藉由存 在熱或水等觸發因素(trigger)而顯示接著性之樹脂等。 In addition, in the present invention, the concept of "adhesive resin" includes both adhesive resin and adhesive resin. Resins that exhibit tackiness, or by depositing Resin, etc. that exhibit adhesiveness under triggers such as heat or water.
黏著劑層可由1層(單層)所構成，亦可由2層以上之多層所構成，於由多層所構成之情形，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。 The adhesive layer may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.
黏著劑層的厚度較佳為1μm以上至100μm以下，更佳為1μm以上至60μm以下，尤佳為1μm以上至30μm以下。 The thickness of the adhesive layer is preferably not less than 1 μm and not more than 100 μm, more preferably not less than 1 μm and not more than 60 μm, especially preferably not less than 1 μm and not more than 30 μm.
此處，所謂「黏著劑層的厚度」，意指黏著劑層整體的厚度，例如所謂由多層所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, for example, the thickness of the adhesive layer composed of multiple layers means the total thickness of all the layers constituting the adhesive layer.
黏著劑層的光學特性只要滿足上文說明之支撐片的光學特性即可。亦即，黏著劑層可為透明，亦可根據目的而著色。 The optical properties of the adhesive layer only need to satisfy the optical properties of the supporting sheet described above. That is, the adhesive layer may be transparent or may be colored according to the purpose.
並且，於保護膜形成用膜具有能量線硬化性之情形，黏著劑層較佳為使能量線透過之黏著劑層。 In addition, when the film for protective film formation has energy ray curability, 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。使用能量線硬化性的黏著劑而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 the 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，視需要使之乾燥，藉此可於目標部位形成黏著劑層。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, the adhesive layer can be formed on the target site by applying the adhesive composition on the surface to be formed of the adhesive layer and drying it if necessary. 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 aforementioned components in the adhesive layer. In this specification, "normal temperature" means a temperature that is neither particularly cold nor particularly hot, that is, an ordinary temperature, 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、模頭塗佈機、刀式塗佈機、網版塗佈機、線棒塗佈機、吻合式塗佈機等。 It is enough to apply the adhesive composition by a known method, for example, use The method of the following various coating machines: air knife coater, blade coater, rod coater, gravure coater, roll coater, roll knife coater, curtain coater, mold Head coater, knife coater, screen coater, wire bar coater, kiss coater, etc.
於基材上設置黏著劑層之情形，例如只要於基材上塗敷黏著劑組成物，視需要使之乾燥，藉此於基材上積層黏著劑層即可。另外，於基材上設置黏著劑層之情形，例如亦可於剝離膜上塗敷黏著劑組成物，視需要使之乾燥，藉此於剝離膜上預先形成黏著劑層，使該黏著劑層的露出面與基材的一表面貼合，藉此於基材上積層黏著劑層。 In the case of providing an adhesive layer on a substrate, for example, the adhesive composition may be applied on the substrate, dried if necessary, and the adhesive layer may be laminated on the substrate. In addition, in the case of providing an adhesive layer on a base material, for example, an adhesive composition may be applied on a release film and dried as necessary to form an adhesive layer on the release film in advance, and to make the adhesive layer The exposed surface is bonded to a surface of the base material, so that an adhesive layer is laminated on the base material.
於黏著劑層為能量線硬化性之情形，作為能量線硬化性的黏著劑組成物，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的黏著性樹脂(I-1a)(以下，有時簡稱為「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)，含有於非能量線硬化性的黏著性樹脂(I-1a)的側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(I-2a)(以下，有時簡稱為「黏著性樹脂(I-2a)」)；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。 When the adhesive layer is energy ray curable, examples of the energy ray curable adhesive composition include the following adhesive compositions: Adhesive composition (I-1), containing non-energy ray curable Adhesive resin (I-1a) (hereinafter, sometimes simply referred to as "adhesive resin (I-1a)") and energy ray-curable compound; adhesive composition (I-2), contained in non-energy ray-curable The adhesive resin (I-1a) has an energy-ray-curable adhesive resin (I-2a) having an unsaturated group introduced into the side chain (hereinafter, sometimes simply referred to as "adhesive resin (I-2a)"); The adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a) and an energy ray-curable compound.
於黏著劑層為非能量線硬化性之情形，作為非能量線硬化性的黏著劑組成物，例如可列舉含有前述非能量線硬化性的黏著性樹脂(I-1a)之黏著劑組成物(I-4)等。 In the case where the adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable adhesive composition include an adhesive composition containing the aforementioned non-energy ray-curable adhesive resin (I-1a) ( I-4) etc.
[黏著性樹脂(I-1a)] [Adhesive resin (I-1a)]
前述黏著劑組成物(I-1)、黏著劑組成物(I-2)、黏著劑組成物(I-3)及黏著劑組成物(I-4)(以下，將這些黏著劑組成物總括地簡稱為「黏著劑組成物(I-1)至黏著劑組成物(I-4)」)中的前述黏著性樹脂(I-1a)較佳為丙烯酸系樹脂。 The aforementioned adhesive composition (I-1), adhesive composition (I-2), adhesive composition (I-3) and adhesive composition (I-4) (hereinafter, these adhesive compositions are collectively The aforementioned adhesive resins (I-1a) in the "adhesive composition (I-1) to adhesive composition (I-4)") are preferably acrylic resins.
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 aforementioned acrylic resins include at least An acrylic polymer with structural units of alkyl acrylate.
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 aforementioned alkyl (meth)acrylates include alkyl (meth)acrylates in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the aforementioned alkyl group is preferably linear or branched. shape.
前述丙烯酸系聚合物較佳為除源自(甲基)丙烯酸烷基酯之結構單元以外，進而具有源自含官能基之單體之結構單元。 The aforementioned acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a 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：藉由前述官能基與後述交聯劑反應而成為交聯的起點，或者藉由前述官能基與後述含不飽和基之化合物中的不飽和基反應，可於丙烯酸系聚合物的側鏈導入不飽和基。 As the above-mentioned functional group-containing monomer, for example, the following monomers can be mentioned: the starting point of crosslinking by the reaction of the above-mentioned functional group with the cross-linking agent described later, or The reaction of unsaturated groups can introduce unsaturated groups into the side chains of acrylic polymers.
作為前述含官能基之單體，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。 As said functional group containing monomer, a hydroxyl group containing monomer, a carboxyl group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.
前述丙烯酸系聚合物亦可除源自(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，進而具有源自其他單體之結構單元。 The aforementioned acrylic polymer may further have a structural unit derived from other monomers in addition to the structural unit derived from an alkyl (meth)acrylate and the structural unit derived from a functional group-containing monomer.
前述其他單體只要可與(甲基)丙烯酸烷基酯等共聚，則並無特別限定。 The aforementioned other monomers are not particularly limited as long as they are copolymerizable with alkyl (meth)acrylates and 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 monomers include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.
黏著劑組成物(I-1)至黏著劑組成物(I-4)中，前述丙烯酸系聚合物等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，這些的組合及比率可任意選擇。 In the adhesive composition (I-1) to the adhesive composition (I-4), the structural unit of the aforementioned acrylic resin such as the aforementioned acrylic polymer may be only one type, or may be two or more types. In the case of two or more kinds, the combination and ratio of these can be selected arbitrarily.
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較佳為相對於結構單元的總量為1質量%至35質量%。 In the aforementioned acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1% by mass to 35% by mass relative to the total amount of the structural units.
黏著劑組成物(I-1)或黏著劑組成物(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，這些的組合及比率可任意選擇。 The adhesive resin (I-1a) contained in the adhesive composition (I-1) or adhesive composition (I-4) may be only one type, or may be two or more types, and in the case of two or more types , the combination and ratio of these can be chosen arbitrarily.
黏著劑組成物(I-1)或黏著劑組成物(I-4)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(I-1)或黏著劑組成物(I-4)的總質量之比例較佳為5質量%至99質量%。 In the adhesive composition (I-1) or the adhesive composition (I-4), the content of the adhesive resin (I-1a) is relative to the adhesive composition (I-1) or the adhesive composition (I- The proportion of the total mass of 4) is preferably 5% by mass to 99% by mass.
[黏著性樹脂(I-2a)] [Adhesive resin (I-2a)]
前述黏著劑組成物(I-2)及(I-3)中的前述黏著性樹脂(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 above-mentioned adhesive resin (I-2a) in the above-mentioned adhesive composition (I-2) and (I-3) is, for example, made by combining the functional group in the adhesive resin (I-1a) with an energy ray polymerizable Obtained by the reaction of compounds containing unsaturated groups with saturated groups.
前述含不飽和基之化合物係除前述能量線聚合性不飽和基以外，進而具有藉由與黏著性樹脂(I-1a)中的官能基反應而可與黏著性樹脂(I-1a)鍵結之基之化合物。 The aforementioned unsaturated group-containing compound has, in addition to the aforementioned energy ray polymerizable unsaturated group, a compound capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). The base compound.
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(vinyl；ethenyl)、烯丙基(2-丙烯基)等，較佳為(甲基)丙烯醯基。 Examples of the aforementioned energy ray polymerizable unsaturated group include (meth)acryl, vinyl (ethenyl), allyl (2-propenyl), and the like, preferably (meth)acryl. .
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 groups that can be bonded to the functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups that can be bonded to hydroxyl groups or amine groups, and carboxyl groups or epoxy groups that can be bonded. Hydroxyl and amino groups, etc.
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)acryloxyethyl isocyanate, (meth)acryl isocyanate, and glycidyl (meth)acrylate.
黏著劑組成物(I-2)或(I-3)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，這些的組合及比率可任意選擇。 The adhesive resin (I-2a) contained in the adhesive composition (I-2) or (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination of these And the ratio can be chosen arbitrarily.
黏著劑組成物(I-2)或(I-3)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(I-2)或(I-3)的總質量之比例較佳為5質量%至99質量%。 In the adhesive composition (I-2) or (I-3), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-2) or (I-3) is relatively Preferably, it is 5 mass % to 99 mass %.
[能量線硬化性化合物] [Energy Beam Curing Compound]
作為前述黏著劑組成物(I-1)及(I-3)中的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 aforementioned energy ray-curable compounds in the aforementioned adhesive compositions (I-1) and (I-3) include monomers or Oligomer.
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。 Among the energy ray-curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. base) acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylic acid aminomethyl Ester; Polyester (meth)acrylate; Polyether (meth)acrylate; Epoxy (meth)acrylate, etc.
能量線硬化性化合物中，作為低聚物，例如可列舉上述例示之單體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, and the like.
黏著劑組成物(I-1)或(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，這些的組合及比率可任意選擇。 The aforementioned energy ray-curing compound contained in the adhesive composition (I-1) or (I-3) may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio of these Optional.
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黏著劑組成物(I-1)的總質量之比例較佳為1質量%至95質量%。 In the adhesive composition (I-1), the ratio of the content of the energy ray-curable compound to the total mass of the adhesive composition (I-1) is preferably 1% by mass to 95% by mass.
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較佳為相對於黏著性樹脂(I-2a)的含量100質量份為0.01質量份至400質量份。 In the adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 400 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a).
[交聯劑] [Crosslinking agent]
於使用除源自(甲基)丙烯酸烷基酯之結構單元以外，進而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，黏著劑組成物(I-1)、(I-3)或(I-4)較佳為進而含有交聯劑。 In the case of using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a), the adhesive The agent composition (I-1), (I-3) or (I-4) preferably further contains a crosslinking agent.
另外，例如於使用與黏著性樹脂(I-1a)中的前述丙烯酸系聚合物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，黏著劑組成物(I-2)亦可進而含有交聯劑。 In addition, for example, when the aforementioned acrylic polymer having the same structural unit derived from a functional group-containing monomer as the aforementioned acrylic polymer in the adhesive resin (I-1a) is used as the adhesive resin (I-2a) In this case, the adhesive composition (I-2) may further contain a crosslinking agent.
前述黏著性樹脂(I-1a)及(I-2a)中的前述交聯劑例如與前述官能基反應而使黏著性樹脂(I-1a)彼此或黏著性樹脂(I-2a)彼此交聯。 For example, the crosslinking agent in the adhesive resins (I-1a) and (I-2a) reacts with the functional group to crosslink the adhesive resins (I-1a) or the adhesive resins (I-2a) .
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]三磷醯基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 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); aziridines such as hexa[1-(2-methyl)-aziridinyl]triphosphoryl triazine Crosslinking agent (crosslinking agent with aziridine group); metal chelate crosslinking agent such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanurate crosslinking agent agent (crosslinking agent with isocyanuric acid skeleton), etc.
黏著劑組成物(I-1)至黏著劑組成物(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，這些的組合及比率可任意選擇。 The cross-linking agent contained in the adhesive composition (I-1) to the adhesive composition (I-4) may be only one type, or may be two or more types, and in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.
前述黏著劑組成物(I-1)、(I-3)或(I-4)中，交聯劑的含量較佳為相對於黏著性樹脂(I-1a)的含量100質量份為0.01質量份至50質量份。 In the aforementioned adhesive composition (I-1), (I-3) or (I-4), the content of the crosslinking agent is preferably 0.01 mass parts relative to 100 mass parts of the content of the adhesive resin (I-1a) parts to 50 parts by mass.
前述黏著劑組成物(I-2)中，交聯劑的含量較佳為相對於黏著性樹脂(I-2a)的含量100質量份為0.01質量份至50質量份。 In the adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a).
[光聚合起始劑] [Photopolymerization Initiator]
黏著劑組成物(I-1)、(I-2)及(I-3)(以下，將這些黏著劑組成物總括地簡稱為「黏著劑組成物(I-1)至黏著劑組成物(I-3)」)亦可進而含有光聚合起始劑。含有光聚合起始劑之黏著劑組成物(I-1)至黏著劑組成物(I-3)即便照射紫外線等相對較低能量的能量線，亦充分地進行硬化反應。 Adhesive compositions (I-1), (I-2) and (I-3) (hereinafter, these adhesive compositions are collectively referred to as "adhesive composition (I-1) to adhesive composition ( I-3)") may further contain a photopolymerization initiator. Adhesive composition (I-1) to adhesive composition (I-3) containing a photopolymerization initiator sufficiently progressed hardening reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.
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***、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；苄基苯基硫醚、一硫化四甲基秋蘭姆等硫醚化合物；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；1-氯蒽醌、2-氯蒽醌等醌化合物。 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-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. ketone compound; double Acylphosphine oxide compounds such as (2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzylphenylsulfur Sulfide compounds such as ether and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; Thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzoyl; dibenzoyl; benzophenone; 2,4-diethylthioxanthone; 1,2 -Diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
另外，作為前述光聚合起始劑，例如亦可使用胺等光增感劑等。 Moreover, as said photoinitiator, photosensitizers, such as an amine, etc. can also be used, for example.
黏著劑組成物(I-1)至黏著劑組成物(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，這些的組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-1) to the adhesive composition (I-3) may be only one type, or may be two or more types, and in the case of two or more types, these Combinations and ratios can be chosen arbitrarily.
黏著劑組成物(I-1)中，光聚合起始劑的含量較佳為相對於前述能量線硬化性化合物的含量100質量份為0.01質量份至20質量份。 In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound.
黏著劑組成物(I-2)中，光聚合起始劑的含量較佳為相對於黏著性樹脂(I-2a)的含量100質量份為0.01質量份至20質量份。 In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a).
黏著劑組成物(I-3)中，光聚合起始劑的含量較佳為相對於黏著性樹脂(I-2a)及前述能量線硬化性化合物的總含量100質量份為0.01質量份至20質量份。 In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 parts by mass to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray-curable compound. parts by mass.
[其他添加劑] [Other additives]
黏著劑組成物(I-1)至黏著劑組成物(I-4)亦可在無損本發明的效果之範圍內，含有不對應於上述任一種成分之其他添加劑。 Adhesive composition (I-1) to adhesive composition (I-4) may also contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the effect of the present invention.
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)、防銹劑、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 aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion imparting agents, Known additives such as a reaction delayer and a crosslinking accelerator (catalyst).
此外，所謂反應延遲劑，例如係指抑制因混入至黏著劑組成物(I-1)至黏著劑組成物(I-4)中的觸媒的作用，而導致保存中的黏著劑組成物(I-1)至黏著劑組成物(I-4)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而形成螯合物錯合物之反應延遲劑，更具體而言，可列舉1分子中具有2個以上之羰基(-C(=O)-)之反應延遲劑。 In addition, the so-called reaction delaying agent, for example, means to suppress the action of the catalyst mixed in the adhesive composition (I-1) to adhesive composition (I-4), which causes the adhesive composition ( I-1) Into the adhesive composition (I-4), an unintended crosslinking reaction proceeds. As a reaction delay agent, for example, a reaction delay agent that forms a chelate complex by a chelate against a catalyst, and more specifically, a carbonyl group (-C( =O)-) reaction delay agent.
黏著劑組成物(I-1)至黏著劑組成物(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，這些的組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-1) to the adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio of these Optional.
黏著劑組成物(I-1)至黏著劑組成物(I-4)中的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當選擇即可。 The content of other additives in the adhesive composition (I-1) to adhesive composition (I-4) 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)至黏著劑組成物(I-4)亦可含有溶劑。黏著劑組成物(I-1)至黏著劑組成物(I-4)藉由含有溶劑，提高對塗敷對象面之塗敷適性。 Adhesive composition (I-1) to adhesive composition (I-4) may also contain a solvent. Adhesive composition (I-1) to adhesive composition (I-4) improve the applicability to the surface to be coated by containing a solvent.
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 aforementioned solvent is preferably an organic solvent, and examples of the aforementioned organic solvent include: ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane, Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol, etc.
黏著劑組成物(I-1)至黏著劑組成物(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，這些的組合及比率可任意選擇。 The solvents contained in adhesive composition (I-1) to adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio of these solvents may be Arbitrary choice.
黏著劑組成物(I-1)至黏著劑組成物(I-4)中的溶劑的含量並無特別限定，適當調節即可。 The content of the solvent in the adhesive composition (I-1) to adhesive composition (I-4) is not particularly limited, and may be appropriately adjusted.
○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-4)等黏著劑組成物係藉由調配前述黏著劑及視需要的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而獲得。 Adhesive compositions such as adhesive composition (I-1) to adhesive composition (I-4) are prepared by preparing the aforementioned adhesive and, if necessary, components other than the aforementioned adhesive, etc., to constitute the adhesive composition. obtained from each component.
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 addition of each component is not particularly limited, and two or more components may be added at the same time.
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當選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the ingredients is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; and mixing by applying ultrasonic waves. method etc.
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，適當調節即可，溫度較佳為15℃至30℃。 The temperature and time for adding and mixing the components are not particularly limited as long as the components are not degraded, and may be appropriately adjusted. The temperature is preferably 15°C to 30°C.
○熱硬化性保護膜形成用膜 ○Film for thermosetting protective film formation
作為較佳的熱硬化性保護膜形成用膜，例如可列舉含有聚合物成分(A)及熱硬化性成分(B)之膜。聚合物成分(A)係被視為聚合性化合物進行聚合反應而形成之成分。另外，熱硬化性成分(B)係可將熱作為反應之觸發而進行硬化反應之成分。此外，本發明中，聚合反應中亦包括縮聚反應。 As a preferable film for thermosetting protective film formation, the film containing a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) is regarded as a component formed by polymerizing a polymerizable compound. Moreover, a thermosetting component (B) is a component which can perform a hardening reaction using heat as a reaction trigger. In addition, in the present invention, the polycondensation reaction is also included in the polymerization reaction.
熱硬化性保護膜形成用膜可由1層(單層)所構成，亦可由2層以上之多層所構成。於熱硬化性保護膜形成用膜由多層所構成之情形，這些多層相互可相同亦可不同。此處，所謂「多層相互可相同亦可不同」，意指與上述之基材之情形相同的含義。並且，於多層相互不同之情形，這些多層的組合並無特別限定。 The film for thermosetting protective film formation may consist of 1 layer (single layer), and may consist of multiple layers of 2 or more layers. When the film for thermosetting protective film formation consists of multiple layers, these multiple layers may be mutually same or different. Here, "multilayers may be the same or different from each other" means the same meaning as in the case of the above-mentioned base material. Also, in the case where the layers are different from each other, the combination of these layers is not particularly limited.
熱硬化性保護膜形成用膜的厚度較佳為1μm以上至100μm以下，更佳為5μm以上至75μm以下，尤佳為5μm以上至50μm以下。藉由熱硬化性保護膜形成用膜的厚度為前述下限值以上，於使用熱硬化性保護膜形成用膜作為保護膜之情形，可形成保護能力更高之保護膜。另外，藉由 熱硬化性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 film for forming a thermosetting protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 75 μm, particularly preferably from 5 μm to 50 μm. When the thickness of the film for thermosetting protective film formation is more than the said lower limit, when using the film for thermosetting protective film formation as a protective film, the protective film with higher protective ability can be formed. Additionally, by The thickness of the film for thermosetting protective film formation is below the said upper limit, and thickness can be suppressed from becoming too thick.
此處，所謂「熱硬化性保護膜形成用膜的厚度」，意指熱硬化性保護膜形成用膜整體的厚度，例如所謂由多層所構成之熱硬化性保護膜形成用膜的厚度，意指構成熱硬化性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 thermosetting protective film" means the thickness of the entire film for forming a thermosetting protective film, for example, the thickness of a film for forming a thermosetting protective film composed of multiple layers means It refers to the total thickness of all the layers constituting the film for forming a thermosetting protective film.
關於將熱硬化性保護膜形成用膜貼附於半導體晶圓的背面並使之硬化時的硬化條件，只要保護膜成為充分地發揮該保護膜的功能之程度的硬化度，則並無特別限定，根據熱硬化性保護膜形成用膜的種類適當選擇即可。 There are no particular limitations on the curing conditions when the film for forming a thermosetting protective film is adhered to the back surface of the semiconductor wafer and cured, as long as the protective film has a degree of curing sufficient to exhibit the function of the protective film. , may be appropriately selected according to the type of film for forming a thermosetting protective film.
例如，熱硬化性保護膜形成用膜之硬化時的加熱溫度較佳為100℃以上至200℃以下，更佳為110℃以上至180℃以下，尤佳為120℃以上至170℃以下。並且，前述硬化時的加熱時間較佳為0.5小時以上至5小時以下，更佳為0.5小時以上至3小時以下，尤佳為1小時以上至2小時以下。 For example, the heating temperature for curing the film for forming a thermosetting protective film is preferably from 100°C to 200°C, more preferably from 110°C to 180°C, even more preferably from 120°C to 170°C. In addition, the heating time for curing is preferably not less than 0.5 hours and not more than 5 hours, more preferably not less than 0.5 hours and not more than 3 hours, and most preferably not less than 1 hour and not more than 2 hours.
<<熱硬化性保護膜形成用組成物>> <<Thermosetting protective film forming composition>>
熱硬化性保護膜形成用膜可使用含有該膜的構成材料之熱硬化性保護膜形成用組成物而形成。例如，於熱硬化性保護膜形成用膜之形成對象面塗敷熱硬化性保護膜形成用組成物，視需要使之乾燥，藉此可於目標部位形成熱硬化性保護膜形成用膜。熱硬化性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熱硬化性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」係如上文所說明。 The film for forming a thermosetting protective film can be formed using a composition for forming a thermosetting protective film containing a constituent material of the film. For example, a thermosetting protective film-forming film can be formed on a target portion by applying a thermosetting protective film-forming composition to a surface to be formed of a thermosetting protective film-forming film and drying it if necessary. The content ratio of the components which do not vaporize at normal temperature in the composition for forming a thermosetting protective film is generally the same as the content ratio of the above-mentioned components in the film for forming a thermosetting protective film. Here, the term "normal temperature" is as described above.
例如可利用與上述之黏著劑組成物之塗敷之情形相同的方法塗敷熱硬化性保護膜形成用組成物。 For example, the composition for forming a thermosetting protective film can be applied by the same method as in the case of applying the above-mentioned adhesive composition.
熱硬化性保護膜形成用組成物的乾燥條件並無特別限定，於熱硬化性保護膜形成用組成物含有後述溶劑之情形，較佳為進行加熱乾燥，該情形，例如較佳為於70℃以上至130℃以下、10秒以上至5分鐘以下 之條件下進行乾燥。 The drying conditions of the composition for forming a thermosetting protective film are not particularly limited, but when the composition for forming a thermosetting protective film contains the solvent described later, it is preferable to perform heat drying. In this case, for example, drying at 70°C is preferable. From above to below 130°C, from above 10 seconds to below 5 minutes Dry under conditions.
<熱硬化性保護膜形成用組成物(III-1)> <Thermocurable protective film forming composition (III-1)>
作為熱硬化性保護膜形成用組成物，例如可列舉含有聚合物成分(A)及熱硬化性成分(B)之熱硬化性保護膜形成用組成物(III-1)(本說明書中，有時簡稱為「組成物(III-1)」)等。 As a composition for forming a thermosetting protective film, for example, a composition for forming a thermosetting protective film (III-1) containing a polymer component (A) and a thermosetting component (B) can be mentioned (in this specification, there is sometimes abbreviated as "composition (III-1)") and the like.
[聚合物成分(A)] [Polymer component (A)]
聚合物成分(A)係用以對熱硬化性保護膜形成用膜賦予造膜性或可撓性等之聚合物化合物。 The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, etc. to the film for forming a thermosetting protective film.
組成物(III-1)及熱硬化性保護膜形成用膜所含有之聚合物成分(A)可僅為1種，亦可為2種以上，於為2種以上之情形，這些的組合及比率可任意選擇。 The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types, and in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.
作為聚合物成分(A)，例如可列舉：丙烯酸系樹脂(具有(甲基)丙烯醯基之樹脂)、聚酯、胺基甲酸酯系樹脂(具有胺基甲酸酯鍵之樹脂)、丙烯酸胺基甲酸酯樹脂、聚矽氧系樹脂(具有矽氧烷鍵之樹脂)、橡膠系樹脂(具有橡膠結構之樹脂)、苯氧基樹脂、熱硬化性聚醯亞胺等，較佳為丙烯酸系樹脂。 Examples of the polymer component (A) include: acrylic resin (resin having a (meth)acryl group), polyester, urethane resin (resin having a urethane bond), Acrylic urethane resin, polysiloxane-based resin (resin with siloxane bond), rubber-based resin (resin with rubber structure), phenoxy resin, thermosetting polyimide, etc., are preferred For acrylic resin.
作為聚合物成分(A)中的前述丙烯酸系樹脂，可列舉公知的丙烯酸聚合物。 As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.
丙烯酸系樹脂的重量平均分子量(Mw)較佳為10000以上至2000000以下，更佳為100000以上至1500000以下。藉由丙烯酸系樹脂的重量平均分子量為前述下限值以上，提高熱硬化性保護膜形成用膜的操作性及形狀穩定性(保管時的經時穩定性)。另外，藉由丙烯酸系樹脂的重量平均分子量為前述上限值以下，熱硬化性保護膜形成用膜變得易於追隨被接著體的凹凸 面，可進一步抑制於被接著體與熱硬化性保護膜形成用膜之間產生空隙(void)等。 The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. When the weight average molecular weight of an acrylic resin is more than the said lower limit, the handleability and shape stability (time-dependent stability at the time of storage) of the film for thermosetting protective film formation are improved. Moreover, when the weight average molecular weight of an acrylic resin is below the said upper limit, the film for thermosetting protective film formation becomes easy to follow the unevenness|corrugation of an adherend On the other hand, generation of voids or the like between the adherend and the film for forming a thermosetting protective film can be further suppressed.
此外，本說明書中，所謂重量平均分子量，只要無特別說明，則係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 addition, in this specification, unless otherwise specified, weight average molecular weight means the polystyrene conversion value measured by the gel permeation chromatography (GPC; Gel Permeation Chromatography) method.
丙烯酸系樹脂的玻璃轉移溫度(Tg)較佳為-60℃以上至70℃以下，更佳為-30℃以上至50℃以下。藉由丙烯酸系樹脂的Tg為前述下限值以上，保護膜與支撐片(黏著劑層)之接著力得到抑制，提高支撐片的剝離性。另外，藉由丙烯酸系樹脂的Tg為前述上限值以下，提高保護膜與被接著體之接著力。 The glass transition temperature (Tg) of the acrylic resin is preferably from -60°C to 70°C, more preferably from -30°C to 50°C. When Tg of an acrylic resin is more than the said lower limit, the adhesive force of a protective film and a support sheet (adhesive layer) is suppressed, and the peelability of a support sheet improves. Moreover, when Tg of acrylic resin is below the said upper limit, the adhesive force of a protective film and an adherend improves.
作為丙烯酸系樹脂，例如可列舉：1種或2種以上之(甲基)丙烯酸酯之聚合物；選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的2種以上之單體之共聚物等。 As the acrylic resin, for example, one or more polymers of (meth)acrylates; selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N- Copolymers of two or more monomers such as methylol acrylamide, etc.
作為構成丙烯酸系樹脂之前述(甲基)丙烯酸酯，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((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((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((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((甲基)丙烯酸硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙 烯酸烷基酯；(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；(甲基)丙烯醯亞胺；(甲基)丙烯酸縮水甘油酯等含縮水甘油基之(甲基)丙烯酸酯；(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-羥基丁酯等含羥基之(甲基)丙烯酸酯；(甲基)丙烯酸N-甲基胺基乙酯等含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」，意指胺基的1個或2個氫原子被氫原子以外的基取代而成之基。 Examples of the (meth)acrylate constituting the acrylic resin 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, (meth)acrylate base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-(meth)acrylate Nonyl, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, Myristyl (meth)acrylate (Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Decadecyl (meth)acrylate Hexaalkyl ester (palm (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group is (methyl) propane with a chain structure of 1 to 18 carbons Alkyl enoate; cycloalkyl (meth)acrylate such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc.; aralkyl (meth)acrylate such as benzyl (meth)acrylate Cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; Cycloalkenyloxyalkyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate; (Meth)acryl imide; glycidyl (meth)acrylate and other glycidyl-containing (meth)acrylates; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 3-Hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, 3-Hydroxybutyl (meth)acrylate, 4 (meth)acrylate -Hydroxyl-containing (meth)acrylates such as hydroxybutyl; (meth)acrylates containing substituted amino groups such as N-methylaminoethyl (meth)acrylate. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.
丙烯酸系樹脂例如除前述(甲基)丙烯酸酯以外，亦可為使選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的1種或2種以上之單體進行共聚而成之丙烯酸系樹脂。 The acrylic resin, for example, other than the aforementioned (meth)acrylates, may also be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide. An acrylic resin obtained by copolymerizing one or more than two monomers.
構成丙烯酸系樹脂之單體可僅為1種，亦可為2種以上，於為2種以上之情形，這些的組合及比率可任意選擇。 The monomer which comprises an acrylic resin may be only 1 type, and may be 2 or more types, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.
丙烯酸系樹脂亦可具有乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等可與其他化合物鍵結之官能基。丙烯酸系樹脂的前述官能基可經由後述交聯劑(F)與其他化合物鍵結，亦可不經由交聯劑(F)而與其他化合物直接鍵結。藉由丙烯酸系樹脂經由前述官能基與其他化合物鍵結，有使用保護膜形成用複合片所獲得之封裝體的可靠性提高之傾向。 Acrylic resins may also have functional groups such as vinyl groups, (meth)acryl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can bond with other compounds. The aforementioned functional group of the acrylic resin may be bonded to another compound through a crosslinking agent (F) described later, or may be directly bonded to another compound without passing through a crosslinking agent (F). There exists a tendency for the reliability of the package obtained using the composite sheet for protective film formation to improve by bonding an acrylic resin to another compound via the said functional group.
本發明中，作為聚合物成分(A)，可不使用丙烯酸系樹脂而單獨使用丙烯酸系樹脂以外的熱塑性樹脂(以下，有時僅簡稱為「熱塑性樹脂」)，亦可與丙烯酸系樹脂併用。藉由使用前述熱塑性樹脂，有時保護膜 自支撐片之剝離性提高，或熱硬化性保護膜形成用膜變得易於追隨被接著體的凹凸面，從而可進一步抑制於被接著體與熱硬化性保護膜形成用膜之間產生空隙等。 In the present invention, as the polymer component (A), a thermoplastic resin other than an acrylic resin may be used alone or in combination with an acrylic resin. By using the aforementioned thermoplastic resin, sometimes the protective film The peelability of the self-supporting sheet is improved, or the film for forming a thermosetting protective film becomes easier to follow the uneven surface of the adherend, thereby further suppressing the generation of voids between the adherend and the film for forming a thermosetting protective film, etc. .
前述熱塑性樹脂的重量平均分子量較佳為1000以上至100000以下，更佳為3000以上至80000以下。此處，所謂「重量平均分子量」係如上文所說明。 The weight average molecular weight of the aforementioned thermoplastic resin is preferably from 1,000 to 100,000, more preferably from 3,000 to 80,000. Here, the "weight average molecular weight" is as described above.
前述熱塑性樹脂的玻璃轉移溫度(Tg)較佳為-30以上至150℃以下，更佳為-20以上至120℃以下。 The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably not less than -30 and not more than 150°C, more preferably not less than -20 and not more than 120°C.
作為前述熱塑性樹脂，例如可列舉：聚酯、聚胺基甲酸酯、苯氧基樹脂、聚丁烯、聚丁二烯、聚苯乙烯等。 As said thermoplastic resin, polyester, polyurethane, a phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.
組成物(III-1)及熱硬化性保護膜形成用膜所含有之前述熱塑性樹脂可僅為1種，亦可為2種以上，於為2種以上之情形，這些熱塑性樹脂的組合及比率可任意選擇。 The aforementioned thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio of these thermoplastic resins Optional.
組成物(III-1)中，無論聚合物成分(A)的種類如何，聚合物成分(A)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，熱硬化性保護膜形成用膜中的聚合物成分(A)的含量)均較佳為5質量%以上至85質量%以下，更佳為5質量%以上至80質量%以下。 In the composition (III-1), regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the formation of a thermosetting protective film The content of the polymer component (A) in the film is preferably from 5% by mass to 85% by mass, more preferably from 5% by mass to 80% by mass.
聚合物成分(A)有時亦對應於熱硬化性成分(B)。本發明中，於組成物(III-1)含有此種對應於聚合物成分(A)及熱硬化性成分(B)兩者之成分之情形，組成物(III-1)視為含有聚合物成分(A)及熱硬化性成分(B)。 The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains such components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is regarded as containing the polymer Component (A) and thermosetting component (B).
[熱硬化性成分(B)] [Thermosetting component (B)]
熱硬化性成分(B)係用以使熱硬化性保護膜形成用膜硬化而形成硬質的保護膜之成分。 A thermosetting component (B) is a component for hardening the film for thermosetting protective film formation, and forming a hard protective film.
組成物(III-1)及熱硬化性保護膜形成用膜所含有之熱硬化性成分(B)可僅為1種，亦可為2種以上，於為2種以上之情形，這些的組合及比率可任意選擇。 The thermosetting component (B) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types, and in the case of two or more types, the combination of these And the ratio can be chosen arbitrarily.
作為熱硬化性成分(B)，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 (B) include: epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc., preferably Epoxy based thermosetting resin.
(環氧系熱硬化性樹脂) (Epoxy Thermosetting Resin)
環氧系熱硬化性樹脂由環氧樹脂(B1)及熱硬化劑(B2)所構成。 The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).
組成物(III-1)及熱硬化性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，這些的組合及比率可任意選擇。 The epoxy-based thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types, and in the case of two or more types, the combination of these And the ratio can be chosen arbitrarily.
‧環氧樹脂(B1) ‧Epoxy resin (B1)
作為環氧樹脂(B1)，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 (B1) include known epoxy resins, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, o-cresol novolac epoxy resins, and polyfunctional epoxy resins. Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. compound.
作為環氧樹脂(B1)，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附保護膜之半導體晶片的可靠性提高。 An epoxy resin having an unsaturated hydrocarbon group can also be used as the epoxy resin (B1). Epoxy resins with unsaturated hydrocarbon groups are more compatible with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, the reliability of the semiconductor wafer with a protective film obtained using the composite sheet for protective film formation improves by using the epoxy resin which has an unsaturated hydrocarbon group.
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變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。 As an epoxy resin which has an unsaturated hydrocarbon group, the compound which converted some epoxy groups of a polyfunctional epoxy resin to the group which has an unsaturated hydrocarbon group is mentioned, for example. Such compounds are obtained, for example, by addition reaction of (meth)acrylic acid or derivatives thereof with epoxy groups have to.
另外，作為具有不飽和烴基之環氧樹脂，例如可列舉：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。 Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly bonded to the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
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：乙烯基(vinyl；ethenyl)、2-丙烯基(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, and specific examples of the unsaturated hydrocarbon group include vinyl (vinyl; ethenyl), 2-propenyl (allyl), (meth)acryl, (Meth)acrylamide group etc., Preferably it is acryl group.
環氧樹脂(B1)的數量平均分子量並無特別限定，就熱硬化性保護膜形成用膜的硬化性、以及硬化後的保護膜的強度及耐熱性之方面而言，較佳為300以上至30000以下，更佳為300以上至10000以下，尤佳為300以上至3000以下。 The number average molecular weight of the epoxy resin (B1) is not particularly limited, but it is preferably 300 or more to 300 in terms of the curability of the film for forming a thermosetting protective film, and the strength and heat resistance of the cured protective film. 30,000 or less, more preferably 300 or more and 10,000 or less, especially preferably 300 or more and 3,000 or less.
環氧樹脂(B1)的環氧當量較佳為100g/eq以上至1000g/eq以下，更佳為150g/eq以上至950g/eq以下。 The epoxy equivalent of the epoxy resin (B1) is preferably from 100 g/eq to 1000 g/eq, more preferably from 150 g/eq to 950 g/eq.
環氧樹脂(B1)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，這些的組合及比率可任意選擇。 An epoxy resin (B1) may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, the combination and ratio of these can be chosen arbitrarily.
‧熱硬化劑(B2) ‧Thermal curing agent (B2)
熱硬化劑(B2)發揮針對環氧樹脂(B1)之硬化劑的功能。 The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
作為熱硬化劑(B2)，例如可列舉：1分子中具有2個以上之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。 As a thermosetting agent (B2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the aforementioned functional groups include: phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, groups formed by anhydrided acid groups, etc., preferably phenolic hydroxyl groups, amino groups, or groups formed by anhydrided acid groups. The base is more preferably a phenolic hydroxyl group or an amino group.
熱硬化劑(B2)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、二環戊二烯型酚樹脂、芳烷基型酚樹脂等。 Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Phenolic resin etc.
熱硬化劑(B2)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 (B2), dicyandiamine (hereinafter, may be abbreviated as "DICY" in some cases) etc. are mentioned as an amine-type hardening agent which has an amino group, for example.
熱硬化劑(B2)亦可具有不飽和烴基。 The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
作為具有不飽和烴基之熱硬化劑(B2)，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 (B2) having an unsaturated hydrocarbon group include: a compound in which a part of the hydroxyl groups of a phenol resin is substituted by a group having an unsaturated hydrocarbon group; a group having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin; Compounds etc.
熱硬化劑(B2)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 (B2) is the same as the 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(B2)之情形，就提高保護膜自支撐片之剝離性之方面而言，熱硬化劑(B2)較佳為軟化點或玻璃轉移溫度高的酚系硬化劑。 In the case of using a phenolic curing agent as the thermal curing agent (B2), the thermal curing agent (B2) is preferably a phenolic curing agent with a high softening point or glass transition temperature in terms of improving the peelability of the protective film from the support sheet. hardener.
熱硬化劑(B2)中，例如多官能酚樹脂、酚醛清漆型酚樹脂、二環戊二烯型酚樹脂、芳烷基型酚樹脂等樹脂成分的數量平均分子量較佳為300以上至30000以下，更佳為400以上至10000以下，尤佳為500以上至3000以下。 In the thermosetting agent (B2), the number average molecular weight of resin components such as polyfunctional phenol resins, novolac-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins is preferably from 300 to 30,000. , more preferably from 400 to 10,000, especially preferably from 500 to 3,000.
熱硬化劑(B2)中，例如聯苯酚、雙氰胺等非樹脂成分的分子量並無特別限定，例如較佳為60以上至500以下。 In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 or more and 500 or less, for example.
熱硬化劑(B2)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，這些的組合及比率可任意選擇。 The thermosetting agent (B2) may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, the combination and ratio of these can be chosen arbitrarily.
組成物(III-1)及熱硬化性保護膜形成用膜中，熱硬化劑(B2)的含量相對於環氧樹脂(B1)的含量100質量份，較佳為0.1質量份以上至500質量份以下，更佳為1質量份以上至200質量份以下。藉由熱硬化劑(B2)的前述含量為前述下限值以上，熱硬化性保護膜形成用膜變得更容易硬化。另外，藉由熱硬化劑(B2)的前述含量為前述上限值以下，熱硬化性保護膜 形成用膜的吸濕率降低，使用保護膜形成用複合片所獲得之封裝體的可靠性進一步提高。 In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 mass parts or more to 500 mass parts with respect to 100 mass parts of the content of the epoxy resin (B1) Part or less, more preferably 1 part by mass or more and 200 parts by mass or less. When the said content of a thermosetting agent (B2) is more than the said lower limit, it becomes easy to harden|cure the film for thermosetting protective film formation. Moreover, when the said content of a thermosetting agent (B2) is below the said upper limit, a thermosetting protective film The moisture absorption rate of the film for formation falls, and the reliability of the package obtained using the composite sheet for protective film formation improves further.
組成物(III-1)及熱硬化性保護膜形成用膜中，熱硬化性成分(B)的含量(例如，環氧樹脂(B1)及熱硬化劑(B2)的總含量)相對於聚合物成分(A)的含量100質量份，較佳為20質量份以上至500質量份以下，更佳為30質量份以上至300質量份以下，尤佳為40質量份以上至150質量份以下。藉由熱硬化性成分(B)的前述含量為此種範圍，可抑制保護膜與支撐片之接著力，提高支撐片的剝離性。 In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to the polymerization The content of component (A) is 100 parts by mass, preferably more than 20 parts by mass and less than 500 parts by mass, more preferably more than 30 parts by mass and less than 300 parts by mass, especially preferably more than 40 parts by mass and less than 150 parts by mass. When the said content of a thermosetting component (B) is such a range, the adhesive force of a protective film and a support sheet can be suppressed, and the peelability of a support sheet can be improved.
[硬化促進劑(C)] [Hardening Accelerator (C)]
組成物(III-1)及熱硬化性保護膜形成用膜亦可含有硬化促進劑(C)。硬化促進劑(C)係用以調整組成物(III-1)的硬化速度之成分。 The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (III-1).
作為較佳的硬化促進劑(C)，例如可列舉：三乙二胺、苄基二甲胺、三乙醇胺、二甲胺基乙醇、三(二甲胺基甲基)苯酚等三級胺；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等咪唑類(1個以上之氫原子被氫原子以外的基取代而成之咪唑)；三丁基膦、二苯基膦、三苯基膦等有機膦類(1個以上之氫原子被有機基取代而成之膦)；四苯基硼酸四苯基鏻、四苯基硼酸三苯基膦等四苯基硼鹽等。 Examples of preferred hardening accelerators (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles in which more than one hydrogen atom is replaced by a group other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (more than one hydrogen atom Phosphine in which the hydrogen atom is replaced by an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate and other tetraphenylboron salts, etc.
組成物(III-1)及熱硬化性保護膜形成用膜所含有之硬化促進劑(C)可僅為1種，亦可為2種以上，於為2種以上之情形，這些的組合及比率可任意選擇。 The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or two or more types, and in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.
於使用硬化促進劑(C)之情形，組成物(III-1)及熱硬化性保護膜形成用膜中，硬化促進劑(C)的含量相對於熱硬化性成分(B)的含量100質量份，較佳為0.01質量份以上至10質量份以下，更佳為0.1質量份以上至7 質量份以下。藉由硬化促進劑(C)的前述含量為前述下限值以上，可獲得顯著的由使用硬化促進劑(C)所帶來之效果。另外，藉由硬化促進劑(C)的含量為前述上限值以下，例如抑制高極性的硬化促進劑(C)於高溫、高濕度條件下在熱硬化性保護膜形成用膜中向與被接著體之接著界面側移動而偏析之效果變高，從而使用保護膜形成用複合片所獲得之附保護膜之半導體晶片的可靠性進一步提高。 In the case of using the hardening accelerator (C), in the composition (III-1) and the film for forming a thermosetting protective film, the content of the hardening accelerator (C) is 100% by mass relative to the content of the thermosetting component (B) Parts, preferably more than 0.01 parts by mass to less than 10 parts by mass, more preferably more than 0.1 parts by mass to 7 parts by mass Parts by mass or less. When the said content of a hardening accelerator (C) is more than the said lower limit, the remarkable effect by using a hardening accelerator (C) can be acquired. Moreover, when content of a hardening accelerator (C) is below the said upper limit, for example, the hardening accelerator (C) of high polarity is suppressed in the film for thermosetting protective film formation under high temperature, high humidity conditions The effect of segregation by movement of the adhesive interface side of the adhesive becomes higher, and the reliability of the semiconductor wafer with protective film obtained by using the composite sheet for protective film formation is further improved.
[填充材料(D)] [Filler (D)]
組成物(III-1)及熱硬化性保護膜形成用膜亦可含有填充材料(D)。藉由熱硬化性保護膜形成用膜含有填充材料(D)，使熱硬化性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，藉由使該熱膨脹係數對於保護膜之形成對象物而言最適化，使用保護膜形成用複合片所獲得之附保護膜之半導體晶片的可靠性進一步提高。另外，藉由熱硬化性保護膜形成用膜含有填充材料(D)，亦可降低保護膜的吸濕率，或提高散熱性。 The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). By containing the filler (D) in the film for forming a thermosetting protective film, the thermal expansion coefficient of the protective film obtained by curing the film for forming the thermosetting protective film can be easily adjusted. Optimally, the reliability of the semiconductor wafer with protective film obtained by using the composite sheet for protective film formation improves further. Moreover, when the film for thermosetting protective film formation contains a filler (D), the moisture absorption rate of a protective film can also be reduced, and heat dissipation can be improved.
填充材料(D)可為有機填充材料及無機填充材料中的任一者，較佳為無機填充材料。 The filler (D) may be any one 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。 As preferred inorganic filler materials, for example, powders of silicon dioxide, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be listed; these inorganic filler materials are spheroidized. Beads; surface-modified products 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 silica or alumina.
填充材料(D)的平均粒徑較佳為10μm以下。藉由設為10μm以下之平均粒徑，容易將保護膜形成用膜及保護膜的圖像清晰度調整為110以上。為了進一步提高圖像清晰度，填充材料(D)的平均粒徑更佳為6μm以下。 The average particle size of the filler (D) is preferably 10 μm or less. By setting it as an average particle diameter of 10 micrometers or less, it becomes easy to adjust the image resolution of the film for protective film formation and a protective film to 110 or more. In order to further improve image clarity, the average particle diameter of the filler (D) is more preferably 6 μm or less.
於填充材料大之情形，有圖像清晰度降低之傾向，且即便粒徑小，亦有因光之擴散而導致清晰度降低之傾向。 When the filler is large, the image resolution tends to decrease, and even if the particle size is small, the resolution tends to decrease due to light diffusion.
組成物(III-1)及熱硬化性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，這些的組合及比率可任意選擇。 The filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or two or more types, and in the case of two or more types, the combination and ratio of these Optional.
於使用填充材料(D)之情形，組成物(III-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，熱硬化性保護膜形成用膜中的填充材料(D)的含量)較佳為5質量%以上至80質量%以下，更佳為7質量%以上至60質量%以下，尤佳為15質量%以上至60質量%以下。藉由填充材料(D)的含量為此種範圍，更容易調整上述熱膨脹係數，藉此可製造可靠性高之晶片，可使圖像清晰度成為所要求之範圍。另外，於含有超過80質量%之量之填充材料(D)之情形，雖亦取決於填充材料(D)的粒徑，但有圖像清晰度降低之傾向。 In the case of using the filler (D), in the composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, the film for forming a thermosetting protective film The content of the filler (D) in ) is preferably from 5% by mass to 80% by mass, more preferably from 7% by mass to 60% by mass, most preferably from 15% by mass to 60% by mass. When the content of the filler (D) falls within such a range, it becomes easier to adjust the above-mentioned thermal expansion coefficient, thereby making it possible to manufacture highly reliable wafers and to make the image definition within the desired range. In addition, when the filler (D) is contained in an amount of more than 80% by mass, the image resolution tends to decrease although it also depends on the particle diameter of the filler (D).
[偶合劑(E)] [Coupling agent (E)]
組成物(III-1)及熱硬化性保護膜形成用膜亦可含有偶合劑(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化合物作為偶合劑(E)，可提高熱硬化性保護膜形成用膜對被接著體之接著性及密接性。另外，藉由使用偶合劑(E)，使熱硬化性保護膜形成用膜硬化而獲得之膜不損害耐熱性而提高耐水性。 The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using the compound which has the functional group which can react with an inorganic compound or an organic compound as a coupling agent (E), the adhesiveness and adhesiveness of the film for thermosetting protective film formation to an adherend can be improved. Moreover, by using a coupling agent (E), the film obtained by hardening the film for thermosetting protective film formation improves water resistance, without impairing heat resistance.
偶合劑(E)較佳為具有可與聚合物成分(A)、熱硬化性成分(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 possessed by the polymer component (A) or the thermosetting component (B), 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。 As preferred aforementioned silane coupling agents, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane , 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3 - Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide , Methyltrimethoxysilane, Methyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriacetyloxysilane, Imidazolesilane, etc.
組成物(III-1)及熱硬化性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，這些的組合及比率可任意選擇。 The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio of these Optional.
於使用偶合劑(E)之情形，組成物(III-1)及熱硬化性保護膜形成用膜中，偶合劑(E)的含量相對於聚合物成分(A)及熱硬化性成分(B)的總含量100質量份，較佳為0.03質量份以上至20質量份以下，更佳為0.05質量份以上至10質量份以下，尤佳為0.1質量份以上至5質量份以下。藉由偶合劑(E)的前述含量為前述下限值以上，填充材料(D)於樹脂中之分散性提高，或熱硬化性保護膜形成用膜與被接著體之接著性提高等，可獲得更顯著的由使用偶合劑(E)所帶來之效果。另外，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。 In the case of using the coupling agent (E), in the composition (III-1) and the film for forming a thermosetting protective film, the content of the coupling agent (E) relative to the polymer component (A) and the thermosetting component (B ) total content of 100 parts by mass, preferably more than 0.03 parts by mass and less than 20 parts by mass, more preferably more than 0.05 parts by mass and less than 10 parts by mass, especially preferably more than 0.1 parts by mass and less than 5 parts by mass. When the above-mentioned content of the coupling agent (E) is more than the above-mentioned lower limit, the dispersibility of the filler (D) in the resin is improved, or the adhesiveness between the film for forming a thermosetting protective film and an adherend is improved, etc. A more remarkable effect brought by the use of the coupling agent (E) is obtained. Moreover, when the said content of a coupling agent (E) is below the said upper limit, generation|occurrence|production of outgassing can be suppressed further.
[交聯劑(F)] [Crosslinking agent (F)]
於使用具有可與其他化合物鍵結之官能基，例如乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等之上述丙烯酸系樹脂等作為聚合物成分(A)之情形，組成物(III-1)及熱硬化性保護膜形成用膜亦可含有交聯劑(F)，該交聯劑(F)用以使前述官能基與其他化合物鍵結而進行交聯。藉由 使用交聯劑(F)進行交聯，可調節熱硬化性保護膜形成用膜的初始接著力及凝聚力。 In the case of using the above-mentioned acrylic resin having a functional group that can bond with other compounds, such as vinyl group, (meth)acryl group, amine group, hydroxyl group, carboxyl group, isocyanate group, etc., as the polymer component (A) , The composition (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F) for linking the aforementioned functional group with another compound to perform crosslinking. by Crosslinking using a crosslinking agent (F) can adjust the initial adhesive force and cohesive force of the film for forming a thermosetting protective film.
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 polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents agent (crosslinking agent with aziridine group), etc.
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。另外，所謂「末端異氰酸酯胺基甲酸酯預聚物」係如上文所說明。 Examples of the aforementioned organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to simply as "aromatic polyvalent isocyanate compounds, etc."); Tripolymers, isocyanurate bodies, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc., with polyol compounds, etc. . The aforementioned "adduct" means that the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound is mixed with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Examples of the reactant of the low-molecular active hydrogen compound include xylylene diisocyanate adduct of trimethylolpropane, which will be described later, as examples of the adduct. In addition, the "terminated isocyanate urethane prepolymer" is as described above.
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；對於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中的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。 As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene 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; Toluene diisocyanate, hexa Compounds of any one or two or more of methylene 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(1-氮丙啶甲醯胺)三伸乙基三聚氰胺等。 Examples of the aforementioned organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-nitrogen Pyridylpropionate, tetramethylolmethane-tris-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylene base melamine etc.
於使用有機多元異氰酸酯化合物作為交聯劑(F)之情形，作為聚合物成分(A)，較佳為使用含羥基之聚合物。於交聯劑(F)具有異氰酸酯基，聚合物成分(A)具有羥基之情形，藉由交聯劑(F)與聚合物成分(A)之反應，可將交聯結構簡便地導入至熱硬化性保護膜形成用膜中。 In the case of using an organic polyvalent isocyanate compound as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). In the case where the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be easily introduced into the thermal In the film for forming a curable protective film.
組成物(III-1)及熱硬化性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，這些的組合及比率可任意選擇。 The crosslinking agent (F) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or two or more types, and in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.
於使用交聯劑(F)之情形，組成物(III-1)中，交聯劑(F)的含量相對於聚合物成分(A)的含量100質量份，較佳為0.01質量份以上至20質量份以下，更佳為0.1質量份以上至10質量份以下，尤佳為0.5質量份以上至5質量份以下。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)所帶來之效果。另外，藉由交聯劑(F)的前述含量為前述上限值以下，可抑制使用過量的交聯劑(F)。 In the case of using a crosslinking agent (F), the content of the crosslinking agent (F) in the composition (III-1) is preferably 0.01 parts by mass or more to 100 parts by mass of the content of the polymer component (A). 20 mass parts or less, more preferably 0.1 mass parts or more and 10 mass parts or less, especially preferably 0.5 mass parts or more and 5 mass parts or less. When the said content of a crosslinking agent (F) is more than the said lower limit, the more remarkable effect by using a crosslinking agent (F) can be acquired. Moreover, when the said content of a crosslinking agent (F) is below the said upper limit, use of an excessive crosslinking agent (F) can be suppressed.
[能量線硬化性樹脂(G)] [energy ray curable resin (G)]
組成物(III-1)亦可含有能量線硬化性樹脂(G)。熱硬化性保護膜形成用膜藉由含有能量線硬化性樹脂(G)，可藉由照射能量線而改變特性。 The composition (III-1) may also contain an energy ray curable resin (G). The film for thermosetting protective film formation can change a characteristic by irradiating an energy ray by containing an energy ray curable resin (G).
能量線硬化性樹脂(G)係使能量線硬化性化合物進行聚合(硬化)而獲得。 The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound.
作為前述能量線硬化性化合物，例如可列舉分子內具有至少1個聚合性雙鍵之化合物，較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。 Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, preferably acrylate compounds having a (meth)acryl group.
作為前述丙烯酸酯系化合物，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯等含鏈狀脂肪族骨架之(甲基)丙烯酸酯；二(甲基)丙烯酸二環戊酯等含環狀脂肪族骨架之(甲基)丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯等聚伸烷基二醇(甲基)丙烯酸酯；寡酯(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯低聚物；環氧改質(甲基)丙烯酸酯；前述聚伸烷基二醇(甲基)丙烯酸酯以外的聚醚(甲基)丙烯酸酯；衣康酸低聚物等。 Examples of the acrylate-based compounds include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate. base) acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (Meth)acrylates containing chain aliphatic skeletons such as (meth)acrylates; (meth)acrylates containing cycloaliphatic skeletons such as dicyclopentanyl di(meth)acrylate; polyethylene glycol Di(meth)acrylate and other polyalkylene glycol (meth)acrylates; oligoester (meth)acrylates; (meth)acrylate urethane oligomers; epoxy modified (meth)acrylates base) acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itaconic acid oligomers, etc.
前述能量線硬化性化合物的重量平均分子量較佳為100以上至30000以下，更佳為300以上至10000以下。此處，所謂「重量平均分子量」係如上文所說明。 The weight average molecular weight of the energy ray-curable compound is preferably from 100 to 30,000, more preferably from 300 to 10,000. Here, the "weight average molecular weight" is as described above.
用於聚合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，這些的組合及比率可任意選擇。 The above-mentioned energy ray-curable compound used for polymerization may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these can be selected arbitrarily.
組成物(III-1)所含有之能量線硬化性樹脂(G)可僅為1種，亦可為2種以上，於為2種以上之情形，這些的組合及比率可任意選擇。 The energy ray curable resin (G) contained in the composition (III-1) may be only 1 type, or may be 2 or more types, and in the case of 2 or more types, the combination and ratio of these can be chosen arbitrarily.
組成物(III-1)中，能量線硬化性樹脂(G)的含量較佳為1質量%以上至95質量%以下，更佳為5質量%以上至90質量%以下，尤佳為10質量%以上至85質量%以下。 In the composition (III-1), the content of the energy ray curable resin (G) is preferably at least 1% by mass and at most 95% by mass, more preferably at least 5% by mass and at most 90% by mass, particularly preferably at least 10% by mass. % or more to 85 mass % or less.
[光聚合起始劑(H)] [Photopolymerization initiator (H)]
於組成物(III-1)含有能量線硬化性樹脂(G)之情形，為了使能量線硬化性樹脂(G)高效率地進行聚合反應，亦可含有光聚合起始劑(H)。 When the composition (III-1) contains the energy ray curable resin (G), in order to efficiently polymerize the energy ray curable resin (G), a photopolymerization initiator (H) may also be included.
作為組成物(III-1)中的光聚合起始劑(H)，例如可列舉：安息香、安息香甲醚、安息香***、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；苄基苯基硫醚、一硫化四甲基秋蘭姆等硫醚化合物；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 (H) in the composition (III-1) include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin Benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy Acetophenone compounds such as -1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethyl Acyl phosphine oxide compounds such as benzoyl diphenyl phosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketols such as 1-hydroxycyclohexyl phenyl ketone Compounds; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzoyl; diphenyl Azoyl; Benzophenone; 2,4-Diethylthioxanthone; 1,2-Diphenylmethane; 2-Hydroxy-2-methyl-1-[4-(1-methylvinyl) Phenyl] acetone; 2-chloroanthraquinone, etc.
另外，作為前述光聚合起始劑，例如亦可列舉：1-氯蒽醌等醌化合物；胺等光增感劑等。 Moreover, as said photoinitiator, quinone compounds, such as 1-chloroanthraquinone, photosensitizers, such as an amine, etc. are also mentioned, for example.
組成物(III-1)所含有之光聚合起始劑(H)可僅為1種，亦可為2種以上，於為2種以上之情形，這些的組合及比率可任意選擇。 The photoinitiator (H) contained in composition (III-1) may be only 1 type, and may be 2 or more types, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.
組成物(III-1)中，光聚合起始劑(H)的含量相對於能量線硬化性樹脂(G)的含量100質量份，較佳為0.1質量份以上至20質量份以下，更佳為1質量份以上至10質量份以下，尤佳為2質量份以上至5質量份以下。 In the composition (III-1), the content of the photopolymerization initiator (H) is preferably at least 0.1 parts by mass and at most 20 parts by mass relative to 100 parts by mass of the content of the energy ray-curable resin (G), more preferably at most 20 parts by mass It is not less than 1 part by mass and not more than 10 parts by mass, more preferably not less than 2 parts by mass and not more than 5 parts by mass.
[著色劑(I)] [Color (I)]
組成物(III-1)及熱硬化性保護膜形成用膜亦可在無損發明的效果之範圍內，含有著色劑(I)。 The composition (III-1) and the film for forming a thermosetting protective film may contain a coloring agent (I) within a range that does not impair the effect of the invention.
作為著色劑(I)，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 (I) include known colorants 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、二噁嗪系色素、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 aforementioned organic pigments and organic dyes include ammonium-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squalilium-based dyes, azulenium-based Pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalenamide pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, di Oxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt dyes) ), dithiol metal complex pigments, indoxyl pigments, triallyl methane pigments, anthraquinone pigments, naphthol pigments, methine azo pigments, benzimidazolone pigments , picanthrone-based pigments and threne-based pigments, etc.
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 pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (Indium Tin Oxide; Indium Tin Oxide) pigments, ATO (Antimony Tin Oxide; Antimony Tin Oxide) pigments, etc.
組成物(III-1)及熱硬化性保護膜形成用膜所含有之著色劑(I)可僅為1種，亦可為2種以上，於為2種以上之情形，這些的組合及比率可任意選擇。 The coloring agent (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio of these Optional.
於使用著色劑(I)之情形，熱硬化性保護膜形成用膜中的著色劑(I)的含量根據目的適當調節即可。例如，藉由調節熱硬化性保護膜形成用膜中的著色劑(I)的含量，調節保護膜的透光性，可調節對晶圓進行雷射印字之情形的印字視認性。另外，藉由調節熱硬化性保護膜形成用膜中的著色劑(I)的含量，亦可提高保護膜的設計性，或使得半導體晶圓的背面的研削痕跡不易見。若考慮這一方面，則組成物(III-1)中，著色劑(I)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，熱硬化性保護膜形成用膜中的著色劑(I)的含量)較佳為0.01質量%以上至10質量%以下，更佳為0.1質量%以上至7.5質量%以下，尤佳為0.1質量%以上至5質量%以下。藉由著色劑(I)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(I)所 帶來之效果。另外，藉由著色劑(I)的前述含量為前述上限值以下，可抑制熱硬化性保護膜形成用膜的透光性過度降低。 When using a coloring agent (I), what is necessary is just to adjust content of the coloring agent (I) in the film for thermosetting protective film formation suitably according to the objective. For example, by adjusting the content of the coloring agent (I) in the film for forming a thermosetting protective film, the light transmittance of the protective film can be adjusted, and the visibility of printing in the case of laser printing on a wafer can be adjusted. Moreover, by adjusting content of the coloring agent (I) in the film for thermosetting protective film formation, the designability of a protective film can be improved, and the grinding trace of the back surface of a semiconductor wafer can also be made difficult to see. Considering this point, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all components other than the solvent (that is, the coloring in the film for forming a thermosetting protective film) The content of the agent (I)) is preferably from 0.01% by mass to 10% by mass, more preferably from 0.1% by mass to 7.5% by mass, especially preferably from 0.1% by mass to 5% by mass. By making the aforementioned content of the coloring agent (I) more than the aforementioned lower limit value, a more remarkable effect obtained by using the coloring agent (I) can be obtained. bring about the effect. Moreover, when the said content of a coloring agent (I) is below the said upper limit, it can suppress that the translucency of the film for thermosetting protective film formation falls too much.
[通用添加劑(J)] [General additive (J)]
組成物(III-1)及熱硬化性保護膜形成用膜亦可在無損本發明的效果之範圍內，含有通用添加劑(J)。 The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) within a range not impairing the effect of the present invention.
通用添加劑(J)可為公知的添加劑，可根據目的任意選擇，並無特別限定，作為較佳的通用添加劑(J)，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、吸氣劑(gettering agent)等。 The general-purpose additive (J) can be a known additive, which can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred general-purpose additives (J) include, for example, plasticizers, antistatic agents, antioxidants, and getters. (gettering agent) and so on.
組成物(III-1)及熱硬化性保護膜形成用膜所含有之通用添加劑(J)可僅為1種，亦可為2種以上，於為2種以上之情形，這些的組合及比率可任意選擇。 The general-purpose additive (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio of these Optional.
組成物(III-1)及熱硬化性保護膜形成用膜中的通用添加劑(J)的含量並無特別限定，根據目的適當選擇即可。 The content of the general-purpose additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.
[溶劑] [solvent]
組成物(III-1)較佳為進而含有溶劑。含有溶劑之組成物(III-1)的操作性良好。 The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent has good handleability.
前述溶劑並無特別限定，作為較佳的溶劑，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(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 aforementioned solvents are not particularly limited, and as preferred solvents, for example, hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1- Alcohols such as butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; Amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds) wait.
組成物(III-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，這些的組合及比率可任意選擇。 The solvent contained in composition (III-1) may be only 1 type, and may be 2 or more types, and when there are 2 or more types, the combination and ratio of these can be chosen arbitrarily.
就可使組成物(III-1)中的含有成分更均勻地混合之方面而言，組成物(III-1)所含有之溶劑較佳為甲基乙基酮等。 The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like at the point that the components contained in the composition (III-1) can be more uniformly mixed.
<<熱硬化性保護膜形成用組成物的製造方法>> <<Manufacturing method of thermosetting protective film forming composition>>
組成物(III-1)等熱硬化性保護膜形成用組成物藉由調配用以構成該組成物之各成分而獲得。 Compositions for thermosetting protective film formation, such as composition (III-1), are obtained by preparing each component which comprises this 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 addition of each component is not particularly limited, and two or more components may be added at the same time.
於使用溶劑之情形，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。 In the case of using a solvent, it can be used by mixing the solvent with any compounded component other than the solvent and diluting the compounded component in advance; it can also be used by not mixing any compounded component other than the solvent. The ingredients are pre-diluted and the solvent is mixed with these formulated 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當選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the ingredients is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; and mixing by applying ultrasonic waves. method etc.
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，適當調節即可，溫度較佳為15℃至30℃。 The temperature and time for adding and mixing the components are not particularly limited as long as the components are not degraded, and may be appropriately adjusted. The temperature is preferably 15°C to 30°C.
○能量線硬化性保護膜形成用膜 ○Film for forming energy ray curable protective film
能量線硬化性保護膜形成用膜含有能量線硬化性成分(a)。 The film for forming an energy ray curable protective film contains an energy ray curable component (a).
能量線硬化性保護膜形成用膜中，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。此處，所謂「能量線」及「能量線硬化性」係如上文所說明。 In the film for forming an energy ray curable protective film, the energy ray curable component (a) is preferably uncured, preferably has adhesiveness, more preferably uncured and has adhesiveness. Here, the "energy ray" and "energy ray curability" are as described above.
能量線硬化性保護膜形成用膜可僅為1層(單層)，亦可為2層以上之多層，於為多層之情形，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。 The film for forming an energy ray curable protective film may be one layer (single layer) or two or more layers. In the case of multiple layers, these layers may be the same or different from each other. There is no special combination of these layers. limited.
能量線硬化性保護膜形成用膜的厚度較佳為1μm以上至100μm以下，更佳為5μm以上至75μm以下，尤佳為5μm以上至50μm以下。藉由能量線硬化性保護膜形成用膜的厚度為前述下限值以上，於使用能量 線硬化性保護膜形成用膜作為保護膜之情形，可形成保護能力更高之保護膜。另外，藉由能量線硬化性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 film for forming an energy ray curable protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 75 μm, and particularly preferably from 5 μm to 50 μm. When the thickness of the film for forming a curable protective film by energy rays is not less than the above lower limit value, when the energy used When the film for forming a line-hardening protective film is used as the protective film, a protective film with higher protective ability can be formed. Moreover, when the thickness of the film for energy ray curable protective film formation is below the said upper limit, thickness can be suppressed from becoming too thick.
此處，所謂「能量線硬化性保護膜形成用膜的厚度」，意指能量線硬化性保護膜形成用膜整體的厚度，例如所謂由多層所構成之能量線硬化性保護膜形成用膜的厚度，意指構成能量線硬化性保護膜形成用膜之全部層的合計厚度。 Here, the "thickness of the film for forming an energy ray curable protective film" means the thickness of the entire film for forming an energy ray curable protective film, for example, the so-called thickness of a film for forming an energy ray curable protective film composed of multiple layers. The thickness means the total thickness of all the layers constituting the film for forming an energy ray curable protective film.
關於將能量線硬化性保護膜形成用膜貼附於半導體晶圓的背面並使之硬化而形成保護膜時的硬化條件，只要保護膜成為充分地發揮該保護膜的功能之程度的硬化度，則並無特別限定，根據能量線硬化性保護膜形成用膜的種類適當選擇即可。 Regarding the curing conditions when the film for forming an energy ray-curable protective film is attached to the back surface of the semiconductor wafer and cured to form a protective film, as long as the protective film has a degree of curing to the extent that the function of the protective film can be fully exhibited, Then, it does not specifically limit, What is necessary is just to select suitably according to the kind of film for energy ray curable protective film formation.
例如，能量線硬化性保護膜形成用膜之硬化時的能量線的照度較佳為120mW/cm2以上至280mW/cm2以下。並且，前述硬化時的能量線的光量較佳為200mJ/cm2以上至1000mJ/cm2以下。 For example, the illuminance of energy rays at the time of curing the film for forming an energy ray curable protective film is preferably 120 mW/cm 2 or more and 280 mW/cm 2 or less. In addition, the light quantity of the energy ray at the time of curing is preferably not less than 200 mJ/cm 2 and not more than 1000 mJ/cm 2 .
<<能量線硬化性保護膜形成用組成物>> <<Composition for forming energy ray curable protective film>>
能量線硬化性保護膜形成用膜可使用含有該膜的構成材料之能量線硬化性保護膜形成用組成物而形成。例如，於能量線硬化性保護膜形成用膜之形成對象面塗敷能量線硬化性保護膜形成用組成物，視需要使之乾燥，藉此可於目標部位形成能量線硬化性保護膜形成用膜。能量線硬化性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能量線硬化性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」係如上文所說明。 The film for forming an energy ray curable protective film can be formed using a composition for forming an energy ray curable protective film containing a constituent material of the film. For example, the composition for forming an energy ray curable protective film is applied to the surface to be formed of the film for forming an energy ray curable protective film, and dried as necessary to form an energy ray curable protective film on the target site. membrane. The content ratio of components that do not vaporize at normal temperature in the composition for forming an energy ray curable protective film is generally the same as the content ratio of the aforementioned components in the film for forming an energy ray curable protective film. Here, the term "normal temperature" is as described above.
例如可利用與上述之黏著劑組成物之塗敷之情形相同的方法塗敷能量線硬化性保護膜形成用組成物。 For example, the composition for forming an energy ray-curable protective film can be applied by the same method as in the case of applying the above-mentioned adhesive composition.
能量線硬化性保護膜形成用組成物的乾燥條件並無特別限定，於能量線硬化性保護膜形成用組成物含有後述溶劑之情形，較佳為進行加熱乾燥，該情形，例如較佳為於70℃以上至130℃以下、10秒以上至5分鐘以下之條件下進行乾燥。 The drying conditions of the composition for forming an energy ray curable protective film are not particularly limited, but when the composition for forming an energy ray curable protective film contains the solvent described later, it is preferable to perform heat drying. Drying is carried out under the conditions of 70°C to 130°C and 10 seconds to 5 minutes.
<能量線硬化性保護膜形成用組成物(IV-1)> <Energy ray curable protective film forming composition (IV-1)>
作為能量線硬化性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)之能量線硬化性保護膜形成用組成物(IV-1)(本說明書中，有時僅簡稱為「組成物(IV-1)」)等。 Examples of the composition for forming an energy ray curable protective film include, for example, the composition for forming an energy ray curable protective film (IV-1) containing the aforementioned energy ray curable component (a) (in this specification, sometimes referred to simply as "composition (IV-1)") and the like.
[能量線硬化性成分(a)] [energy ray hardening ingredient (a)]
能量線硬化性成分(a)係藉由照射能量線而硬化之成分，該成分用以對能量線硬化性保護膜形成用膜賦予造膜性或可撓性等，並且於硬化後形成硬質的保護膜。 The energy ray-curable component (a) is a component that is cured by irradiation of energy ray, and is used to impart film-forming properties, flexibility, etc. to the film for forming an energy ray-curable protective film, and to form a hard surface after curing. 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以上至2000000以下之聚合物(a1)、及具有能量線硬化性基且分子量為100以上至80000以下之化合物(a2)。 As the energy ray-curable component (a), for example, a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, and a polymer (a1) having an energy ray-curable group and having a molecular weight of 100 to 2 80000 or less compound (a2).
前述聚合物(a1)可至少一部分藉由交聯劑進行交聯，亦可不進行交聯。 The aforementioned polymer (a1) may be at least partially cross-linked by a cross-linking agent, or may not be cross-linked.
(具有能量線硬化性基且重量平均分子量為80000以上至2000000以下之聚合物(a1)) (Polymer (a1) having an energy ray curable group and having 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以上至2000000以下之聚合物(a1)，例如可列舉丙烯酸系樹脂(a1-1)，該丙烯酸系樹脂(a1-1)係使丙烯酸系聚合物(a11)與能量線硬化性化合物(a12)進行反應而成，該丙烯酸系聚合物(a11)具有可與其他化合物所具有之基反應之官能基，該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) that polymerizes an acrylic resin. The product (a11) is formed by reacting an energy ray-curable compound (a12), the acrylic polymer (a11) has a functional group capable of reacting with groups of other compounds, and the energy ray-curable compound (a12) has An energy ray curable group such as a group reactive with the aforementioned functional group and an energy ray curable double bond.
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 groups that can react with groups of other compounds include hydroxyl, carboxyl, amino, and substituted amino groups (one or two hydrogen atoms of the amino group are replaced by groups other than hydrogen atoms) group), epoxy group, etc. However, the aforementioned functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of a semiconductor wafer or a circuit of a semiconductor wafer or the like.
這些之中，前述官能基較佳為羥基。 Among these, the aforementioned functional group is preferably a hydroxyl group.
‧具有官能基之丙烯酸系聚合物(a11) ‧Acrylic polymer with functional groups (a11)
作為前述具有官能基之丙烯酸系聚合物(a11)，例如可列舉：使具有前述官能基之丙烯酸系單體與不具有前述官能基之丙烯酸系單體進行共聚而成之聚合物，亦可為除這些單體以外，進而使丙烯酸系單體以外的單體(非丙烯酸系單體)進行共聚而成之聚合物。 Examples of the acrylic polymer (a11) having a functional group include polymers obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer not having the functional group. In addition to these monomers, a polymer obtained by further copolymerizing monomers other than acrylic monomers (non-acrylic monomers).
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，關於聚合方法，亦可採用公知的方法。 In addition, the above-mentioned acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method may be employed for the polymerization method.
作為具有前述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 acrylic monomers having the aforementioned functional groups include: hydroxyl-containing monomers, carboxyl-containing monomers, amine-containing monomers, substituted amino-containing monomers, epoxy-containing monomers, etc. .
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 group-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxy (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols (unsaturated alcohols not having a (meth)acryl skeleton) such as allyl alcohol, 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)；富馬酸、衣康酸、馬來酸、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的酐；甲基丙烯酸2-羧基乙酯等(甲基)丙烯 酸羧基烷基酯等。 As the aforementioned carboxyl group-containing monomers, for example, ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Ethylenically unsaturated dicarboxylic acids such as maleic acid and citraconic acid (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. base) propylene Acid carboxyalkyl esters, etc.
具有前述官能基之丙烯酸系單體較佳為含羥基之單體。 The acrylic monomers having the aforementioned functional groups are preferably hydroxyl-containing monomers.
構成前述丙烯酸系聚合物(a11)之具有前述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，這些的組合及比率可任意選擇。 The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these can be selected arbitrarily.
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((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((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((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((甲基)丙烯酸硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等。 Examples of acrylic monomers that do not have the aforementioned functional groups include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 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 (Lauryl (meth)acrylate), ( Tridecyl Methacrylate, Myristyl (Meth)acrylate (Myristyl (Meth)acrylate), Pentadecyl (Meth)acrylate, Hexadecyl (Meth)acrylate Alkyl esters (palm (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. The group is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.
另外，作為不具有前述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-二甲胺基丙酯等的具有非交聯性三級胺基之(甲基)丙烯酸酯等。 Moreover, as an acrylic monomer which does not have the said functional group, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, etc. are also mentioned, for example. (meth)acrylic acid esters containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylate; (meth)acrylate; non-cross-linked (meth)acrylamide and its derivatives; (meth)acrylate N,N-dimethylaminoethyl ester, (meth)acrylate N,N- (Meth)acrylates having non-crosslinkable tertiary amino groups such as dimethylaminopropyl ester, etc.
構成前述丙烯酸系聚合物(a11)之不具有前述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，這些的組合及比率可任意選擇。 The acrylic monomer which does not have the said functional group which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types, and when there are 2 or more types, the combination and ratio of these can be chosen arbitrarily.
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 monomers 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，這些的組合及比率可任意選擇。 The said non-acrylic monomer which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types, and when it is 2 or more types, the combination and ratio of these 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的量相對於構成該丙烯酸系聚合物(a11)之結構單元的總量之比例(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至使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 structural units derived from the acrylic monomer having the aforementioned functional group to the total amount of structural units constituting the aforementioned acrylic polymer (a11) is preferable 0.1% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, most preferably 3% by mass to 30% by mass. With the aforementioned ratio in such a range, the energy ray-curable group in the aforementioned acrylic resin (a1-1) obtained by copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy ray-curable compound (a12) can be reduced The content is easily adjusted to a range in which the degree of hardening of the protective film is preferable.
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，這些的組合及比率可任意選擇。 The said acrylic polymer (a11) which comprises the said acrylic resin (a1-1) may be only 1 type, and may be 2 or more types, and when it is 2 or more types, the combination and ratio of these can be chosen arbitrarily.
組成物(IV-1)中，丙烯酸系樹脂(a1-1)的含量相對於溶劑以外的成分的總含量之比例(亦即，能量線硬化性保護膜形成用膜中的丙烯酸系樹脂(a1-1)的含量)較佳為1質量%以上至70質量%以下，更佳為5質量%以上至60質量%以下，尤佳為10質量%以上至50質量%以下。 In the composition (IV-1), the ratio of the content of the acrylic resin (a1-1) to the total content of the components other than the solvent (that is, the acrylic resin (a1-1) in the film for forming an energy ray curable protective film The content of -1)) is preferably from 1% by mass to 70% by mass, more preferably from 5% by mass to 60% by mass, particularly preferably from 10% by mass to 50% 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，該異氰酸酯基與具有羥基作為前述官能基之丙烯酸系聚合物(a11)的該羥基容易反應。 The aforementioned energy ray-curable compound (a12) preferably has one or more kinds selected from the group consisting of isocyanate group, epoxy group and carboxyl group as a compound capable of combining with the aforementioned acrylic polymer. (a11) The group which reacts with the functional group which it has has an isocyanate group more preferably as said group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group reacts easily with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the 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個以上至5個以下之前述能量線硬化性基，更佳為具有1個以上至3個以下。 The aforementioned energy ray-curable compound (a12) preferably has 1 or more and 5 or less of the aforementioned energy ray-curable groups in 1 molecule, more preferably has 1 or more and 3 or less.
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-curing compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryl isocyanate, allyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate; by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate Acryl monoisocyanate compound obtained; acryl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate, etc.
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 aforementioned 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，這些的組合及比率可任意選擇。 The aforementioned energy ray-curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio of these compounds can be selected arbitrarily.
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%以上至120莫耳%以下，更佳為35莫耳%以上至100莫耳%以下，尤佳為50莫耳%以上至100莫耳%以下。藉由前述含量之比例為此種範圍，硬化後的保護膜的接著力進一步變大。此外，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，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個以上之前述基)化合物之情形，前述含量之比例的上限值有時超過100莫耳%。 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 more than 20 mol% to less than 120 mol%, more preferably more than 35 mol% to less than 100 mol%, and most preferably is more than 50 mol% to less than 100 mol%. When the ratio of the said content is such a range, the adhesive force of the protective film after hardening becomes larger further. In addition, when the aforementioned energy ray-curable compound (a12) is a functional (having one of the aforementioned groups in one molecule) compound In the case of a substance, the upper limit of the ratio of the aforementioned content is 100 mol%, but in the case of the aforementioned energy ray-curable compound (a12) being a polyfunctional (having two or more aforementioned groups in one molecule) compound, the aforementioned The upper limit of the content ratio may exceed 100 mol%.
前述聚合物(a1)的重量平均分子量(Mw)較佳為100000以上至2000000以下，更佳為300000以上至1500000以下。 The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1,500,000.
此處，所謂「重量平均分子量」係如上文所說明。 Here, the "weight average molecular weight" is as described above.
於前述聚合物(a1)的至少一部分藉由交聯劑進行交聯之情形，前述聚合物(a1)可使作為構成前述丙烯酸系聚合物(a11)所說明過之不對應於上述任一單體且具有與交聯劑反應之基之單體進行聚合而在與前述交聯劑反應之基產生交聯者，亦可為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產生交聯者。 In the case where at least a part of the aforementioned polymer (a1) is cross-linked by a cross-linking agent, the aforementioned polymer (a1) may be any one of the above-mentioned compounds described as constituting the aforementioned acrylic polymer (a11). A monomer having a group that reacts with a crosslinking agent is polymerized to generate crosslinking at a group that reacts with the crosslinking agent, or it may be derived from the aforementioned energy ray-curable compound (a12) and the aforementioned functional group The base of the reaction produces cross-linking.
組成物(IV-1)及能量線硬化性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，這些的組合及比率可任意選擇。 The aforementioned polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be only one type, or may be two or more types, and in the case of two or more types, the combination of these And the ratio can be chosen arbitrarily.
(具有能量線硬化性基且分子量為100以上至80000以下之化合物(a2)) (Compound (a2) having an energy ray curable group and having 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以上至80000以下之化合物(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 contained in the compound (a2) having an energy ray curable group and having a molecular weight of 100 to 80000 include a group containing an energy ray curable double bond, and preferable examples include (Meth)acryl, vinyl, etc.
前述化合物(a2)只要滿足上述條件，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 aforementioned compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include low molecular weight compounds having energy ray curable groups, epoxy resins having energy ray curable groups, and phenol resins having energy ray curable groups 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 low-molecular-weight compounds having energy-ray-curable groups include polyfunctional monomers or oligomers, and preferably those having (meth)acrylamide Acrylate-based compounds.
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、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、聚四亞甲基二醇二(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-己內酯改質異氰脲酸三-(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 aforementioned acrylate-based compounds include: 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxy bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A bis(methyl) ) acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloxy Ethoxy)phenyl] fennel, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol 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 ) acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, Neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, etc. ) acrylate; Tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified tris-(2-(meth)acryloxyethyl)isocyanurate base) ester, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(methyl) ) acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Base) acrylates; (meth)acrylate urethane oligomers and other multifunctional (meth)acrylate oligomers, etc.
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「日本專利特開2013-194102號公報」之段落0043等中所記載之樹脂。此種樹脂亦對應於構成後述之熱硬化性成分之樹脂，但本發明中視作前述化合物(a2)。 Among the aforementioned compounds (a2), as the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group, for example, those described in paragraph 0043 of "Japanese Patent Application Laid-Open No. 2013-194102" and the like can be used. of resin. Such a resin also corresponds to a resin constituting a thermosetting component 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以上至30000以下，更佳為300以上至10000以下。此處，所謂「重量平均分子量」係如上文所說明。 The weight average molecular weight of the aforementioned compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000. Here, the "weight average molecular weight" is as described above.
組成物(IV-1)及能量線硬化性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，這些的組合及比率可任意選擇。 The above-mentioned compound (a2) contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination of these and The ratio can be chosen arbitrarily.
[不具有能量線硬化性基之聚合物(b)] [Polymer (b) not having an energy ray curable group]
於組成物(IV-1)及能量線硬化性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，較佳為亦進而含有不具有能量線硬化性基之聚合物(b)。 In the case where the composition (IV-1) and the film for forming an energy ray curable protective film contain the aforementioned compound (a2) as the aforementioned energy ray curable component (a), it is preferable to further contain The polymer (b).
前述聚合物(b)可至少一部分藉由交聯劑進行交聯，亦可不進行交聯。 The aforementioned polymer (b) may be at least partially cross-linked by a cross-linking agent, or may not be cross-linked.
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等。 Examples of the polymer (b) not having an energy ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins. wait.
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 aforementioned polymer (b) is preferably an acrylic polymer (hereinafter, may be simply referred to 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種以上之丙烯酸系單體的共聚物，還可為1種或2種以上之丙烯酸系單體與1種或2種以上之丙烯酸系單體以外的單體(非丙烯酸系單體)的共聚物。 The acrylic polymer (b-1) may be a known polymer, for example, it may be a homopolymer of one type of acrylic monomer, or it may be a copolymer of two or more types of acrylic monomers, or it may be a single type Or a copolymer of two or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).
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」係如上文所說明。 Examples of the acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, glycidyl group-containing (meth)acrylates, base) acrylates, hydroxyl-containing (meth)acrylates, substituted amino-containing (meth)acrylates, etc. Here, the so-called "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((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((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((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((甲基)丙烯酸硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等。 Examples of the aforementioned alkyl (meth)acrylates 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 (lauryl (meth)acrylate), (meth)acrylate base) tridecyl acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Alkyl esters (palm (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. Alkyl (meth)acrylate with 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 (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; ) aralkyl (meth)acrylate such as benzyl acrylate; cycloenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate etc. ( Cycloalkenyloxyalkyl meth)acrylate, etc.
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。 As said glycidyl group containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example.
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 aforementioned hydroxyl group-containing (meth)acrylate include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.
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。 As said substituted amino group containing (meth)acrylate, N-methylamino ethyl (meth)acrylate etc. are mentioned, for example.
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反應而成之聚合物。 Examples of the polymer (b) that is at least partly crosslinked by a crosslinking agent and does not have the aforementioned energy ray-curable groups include those obtained by reacting the reactive functional groups in the aforementioned polymer (b) with a crosslinking agent. of polymers.
前述反應性官能基根據交聯劑的種類等適當選擇即可，並無特別限定。例如，於交聯劑為多異氰酸酯化合物之情形，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。另外，於交聯劑為環氧系化合物之情形，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 crosslinking agent and the like, and is not particularly limited. For example, when a crosslinking agent is a polyisocyanate compound, a hydroxyl group, a carboxyl group, an amino group etc. are mentioned as said reactive functional group, Among these, the hydroxyl group with high reactivity with an isocyanate group is preferable. In addition, when the crosslinking agent is an epoxy-based compound, examples of the reactive functional groups include carboxyl groups, amine groups, and amido groups. Among these, carboxyl groups having high reactivity with epoxy groups are preferred. . However, the aforementioned reactive functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of a semiconductor wafer or a circuit of a semiconductor wafer.
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：使至少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，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中的任一者或兩者，只要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個以上之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。 As a polymer (b) which has the said reactive functional group and does not have an energy-ray curable group, the polymer obtained by polymerizing the monomer which has the said reactive functional group at least is mentioned, for example. 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) , as long as the monomers having the aforementioned reactive functional groups are used. For example, as the above-mentioned polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl-containing (meth)acrylic acid A polymer obtained by polymerizing monomers in which one or more hydrogen atoms of the aforementioned acrylic monomers or non-acrylic monomers are replaced by the aforementioned reactive functional groups.
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)之結構單元的總量之比例(含量)較佳為1質量%以上至20質量%以下，更佳為2質量%以上至10 質量%以下。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 structural units derived from a monomer having a reactive functional group relative to the total amount of structural units constituting the polymer (b) is relatively small. Preferably at least 1% by mass and at most 20% by mass, more preferably at least 2% by mass and at least 10% by mass. Mass% or less. When the ratio is in such a range, the degree of crosslinking in the polymer (b) is in a more preferable range.
就組成物(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以上至2000000以下，更佳為100000以上至1500000以下。此處，所謂「重量平均分子量」係如上文所說明。 In terms of better film-forming properties of the composition (IV-1), the weight average molecular weight (Mw) of the polymer (b) not having an energy ray curable group is preferably 10,000 or more and 2,000,000 or less, more preferably More than 100,000 to less than 1,500,000. Here, the "weight average molecular weight" is as described above.
組成物(IV-1)及能量線硬化性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，這些的組合及比率可任意選擇。 The polymer (b) not having an energy ray curable group contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be only 1 type, or may be 2 or more types, and in this case, 2 types In the above cases, the combination and ratio of these can be selected arbitrarily.
作為組成物(IV-1)，可列舉含有前述聚合物(a1)及前述化合物(a2)中的任一者或兩者之組成物。並且，於組成物(IV-1)含有前述化合物(a2)之情形，較佳為亦進而含有不具有能量線硬化性基之聚合物(b)，該情形，亦較佳為進而含有前述(a1)。另外，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 composition (IV-1) include compositions containing either or both of the aforementioned polymer (a1) and the aforementioned compound (a2). In addition, when the composition (IV-1) contains the aforementioned compound (a2), it is preferable to further include the polymer (b) not having an energy ray curable group. In this case, it is also preferable to further include the aforementioned ( a1). In addition, the composition (IV-1) may not contain the aforementioned compound (a2), but may also contain the aforementioned polymer (a1) and the polymer (b) not having an energy ray curable group.
於組成物(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，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質量份以上至400質量份以下，更佳為30質量份以上至350質量份以下。 In the case where the composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2), and a polymer (b) not having an energy ray curable group, in the composition (IV-1), the aforementioned compound The content of (a2) is preferably 10 parts by mass or more and 400 parts by mass or less, more preferably 30 mass parts or more to 350 mass parts or less.
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，能量線硬化性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%以上至90質量%以下，更佳為10質量%以上至80質量%以下，尤佳為20質量%以上至70 質量%以下。藉由能量線硬化性成分的含量之前述比例為此種範圍，能量線硬化性保護膜形成用膜的能量線硬化性變得更良好。 In the composition (IV-1), the ratio of the total content of the energy ray curable component (a) and the polymer (b) not having an energy ray curable group to the total content of the components other than the solvent (that is, The total content of the energy ray curable component (a) and the polymer (b) not having an energy ray curable group in the film for forming an energy ray curable protective film) is preferably 5% by mass or more and 90% by mass or less , more preferably more than 10% by mass to less than 80% by mass, especially preferably more than 20% by mass to 70% by mass Mass% or less. The energy ray curability of the film for energy ray curable protective film formation becomes more favorable by making the said ratio of content of an energy ray curable component into such a range.
組成物(IV-1)中，除前述能量線硬化性成分以外，亦可根據目的而含有選自由熱硬化性成分、填充材料、偶合劑、交聯劑、光聚合起始劑、著色劑、及通用添加劑所組成之群組中的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及熱硬化性成分之組成物(IV-1)，所形成之能量線硬化性保護膜形成用膜藉由加熱而對被接著體之接著力提高，由該能量線硬化性保護膜形成用膜形成之保護膜的強度亦提高。 In the composition (IV-1), in addition to the above-mentioned energy ray curable components, it may also contain, depending on the purpose, a material selected from a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and one or more of the group consisting of general-purpose additives. For example, by using the composition (IV-1) containing the aforementioned energy ray curable component and thermosetting component, the formed film for forming an energy ray curable protective film has improved adhesive force to the adherend by heating Therefore, the strength of the protective film formed from the film for forming an energy ray curable protective film is also improved.
作為組成物(IV-1)中的前述熱硬化性成分、填充材料、偶合劑、交聯劑、光聚合起始劑、著色劑、及通用添加劑，可列舉分別與組成物(III-1)中的熱硬化性成分(B)、填充材料(D)、偶合劑(E)、交聯劑(F)、光聚合起始劑(H)、著色劑(I)及通用添加劑(J)相同的化合物。 Examples of the above-mentioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives in the composition (IV-1) include: The thermosetting component (B), filler (D), coupling agent (E), crosslinking agent (F), photopolymerization initiator (H), colorant (I) and general additives (J) are the same compound of.
組成物(IV-1)中，前述熱硬化性成分、填充材料、偶合劑、交聯劑、光聚合起始劑、著色劑、及通用添加劑可分別單獨使用1種，亦可併用2種以上，於併用2種以上之情形，這些的組合及比率可任意選擇。 In the composition (IV-1), the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives may be used alone or in combination of two or more , in the case of using two or more kinds together, the combination and ratio of these can be selected arbitrarily.
組成物(IV-1)中的前述熱硬化性成分、填充材料、偶合劑、交聯劑、光聚合起始劑、著色劑、及通用添加劑的含量根據目的適當調節即可，並無特別限定。 The contents of the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general-purpose additives in the composition (IV-1) may be appropriately adjusted according to the purpose, and are not particularly limited. .
就藉由稀釋而提高該組成物的操作性而言，組成物(IV-1)較佳為進而含有溶劑。 The composition (IV-1) preferably further contains a solvent in order to improve the handleability of the composition by dilution.
作為組成物(IV-1)所含有之溶劑，例如可列舉與組成物(III-1)中的溶劑相同的溶劑。 Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
組成物(IV-1)所含有之溶劑可僅為1種，亦可為2種以上。 The solvent contained in the composition (IV-1) may be only one kind, or may be two or more kinds.
<<能量線硬化性保護膜形成用組成物的製造方法>> <<Manufacturing method of energy ray curable protective film forming composition>>
組成物(IV-1)等能量線硬化性保護膜形成用組成物可藉由調配用以構成該組成物之各成分而獲得。 Compositions for forming an energy ray-curable protective film such as the composition (IV-1) can be obtained by preparing each component for constituting the 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 addition of each component is not particularly limited, and two or more components may be added at the same time.
於使用溶劑之情形，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。 In the case of using a solvent, it can be used by mixing the solvent with any compounded component other than the solvent and diluting the compounded component in advance; it can also be used by not mixing any compounded component other than the solvent. The ingredients are pre-diluted and the solvent is mixed with these formulated 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當選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the ingredients is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; and mixing by applying ultrasonic waves. method etc.
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，適當調節即可，溫度較佳為15℃至30℃。 The temperature and time for adding and mixing the components are not particularly limited as long as the components are not degraded, and may be appropriately adjusted. The temperature is preferably 15°C to 30°C.
○非硬化性保護膜形成用膜 ○Film for non-hardening protective film formation
作為較佳的非硬化性保護膜形成用膜，例如含有非硬化性成分(c)。非硬化性保護膜形成用膜中，非硬化性成分(c)較佳為不具有硬化性，且具有對支撐片之黏著性、及對於保護半導體晶圓或晶片而言適度的硬度。此處，所謂「非硬化性」係如上文所說明。 As a preferable film for noncurable protective film formation, a noncurable component (c) is contained, for example. In the film for forming a non-curable protective film, the non-curable component (c) preferably has no curability, has adhesiveness to a support sheet, and has moderate hardness for protecting a semiconductor wafer or wafer. Here, the term "non-curable" is as described above.
非硬化性保護膜形成用膜可僅為1層(單層)，亦可為2層以上之多層，於為多層之情形，這些多層相互可相同亦可不同，這些多層的組合並無特別限定。 The film for forming a non-curable protective film may be one layer (single layer), or two or more layers. In the case of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited. .
非硬化性保護膜形成用膜的厚度較佳為1μm以上至100μm以下，更佳為5μm以上至75μm以下，尤佳為5μm以上至50μm以下。藉由非硬化性保護膜形成用膜的厚度為前述下限值以上，於使用非硬化性保護膜形成用膜作為保護膜之情形，可形成保護能力更高的保護膜。另外，藉由 非硬化性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 film for forming a non-curable protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 75 μm, particularly preferably from 5 μm to 50 μm. When the thickness of the film for non-curable protective film formation is more than the said lower limit, when using the film for non-curable protective film formation as a protective film, the protective film with higher protective ability can be formed. Additionally, by The thickness of the film for non-curable protective film formation is below the said upper limit, and thickness can be suppressed from becoming too thick.
此處，所謂「非硬化性保護膜形成用膜的厚度」，意指非硬化性保護膜形成用膜整體的厚度，例如所謂由多層所構成之非硬化性保護膜形成用膜的厚度，意指構成非硬化性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 non-curable protective film" means the thickness of the entire film for forming a non-curable protective film, for example, the thickness of a film for forming a non-curable protective film composed of multiple layers means It refers to the total thickness of all the layers constituting the film for forming a non-curable protective film.
<<非硬化性保護膜形成用組成物>> <<Non-hardening protective film forming composition>>
非硬化性保護膜形成用膜可使用含有該膜的構成材料之非硬化性保護膜形成用組成物而形成。例如，於非硬化性保護膜形成用膜之形成對象面塗敷非硬化性保護膜形成用組成物，視需要使之乾燥，藉此可於目標部位形成非硬化性保護膜形成用膜。非硬化性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非硬化性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」係如上文所說明。 The film for forming a non-curable protective film can be formed using a composition for forming a non-curable protective film containing a constituent material of the film. For example, a non-curable protective film-forming film can be formed on a target portion by applying a non-curable protective film-forming composition to the surface to be formed of the non-curable protective film-forming film and drying it if necessary. The content ratio of components that do not vaporize at normal temperature in the composition for forming a non-curable protective film is generally the same as the content ratio of the above-mentioned components in the film for forming a non-curable protective film. Here, the term "normal temperature" is as described above.
例如可利用與上述之黏著劑組成物之塗敷之情形相同的方法塗敷非硬化性保護膜形成用組成物。 For example, the composition for forming a non-hardening protective film can be applied by the same method as in the case of applying the above-mentioned adhesive composition.
非硬化性保護膜形成用組成物的乾燥條件並無特別限定，於非硬化性保護膜形成用組成物含有後述溶劑之情形，較佳為進行加熱乾燥，該情形，例如較佳為於70℃以上至130℃以下、10秒以上至5分鐘以下之條件下進行乾燥。 The drying conditions of the composition for forming a non-curable protective film are not particularly limited. When the composition for forming a non-curable protective film contains the solvent described later, it is preferable to dry it by heating. In this case, for example, it is preferably at 70°C. Drying is carried out under the conditions of above to below 130°C and between above 10 seconds and below 5 minutes.
<非硬化性保護膜形成用組成物(V-1)> <Non-hardening protective film forming composition (V-1)>
作為非硬化性保護膜形成用組成物，例如可列舉含有前述非硬化性成分(c)之非硬化性保護膜形成用組成物(V-1)(本說明書中，有時僅簡稱為「組成物(V-1)」)等。 As a non-curable protective film-forming composition, for example, the non-curable protective film-forming composition (V-1) containing the aforementioned non-curable component (c) (in this specification, sometimes simply referred to as "composition Object (V-1)") and so on.
作為非硬化性成分(c)，可列舉丙烯酸系聚合物等，並不限定於這些。 Examples of the non-curable component (c) include acrylic polymers and the like, but are not limited thereto.
組成物(V-1)中，除前述非硬化性成分(c)以外，亦可根據目 的而含有選自由填充材料、偶合劑、交聯劑、著色劑、及通用添加劑所組成之群組中的1種或2種以上。 In the composition (V-1), in addition to the above-mentioned non-hardening component (c), it may also be It contains one or two or more selected from the group consisting of fillers, coupling agents, crosslinking agents, colorants, and general additives.
作為組成物(V-1)中的前述填充材料、偶合劑、交聯劑、著色劑、及通用添加劑，可列舉分別與組成物(III-1)中的填充材料(D)、偶合劑(E)、交聯劑(F)、著色劑(I)及通用添加劑(J)相同的化合物。 As the aforementioned fillers, coupling agents, crosslinking agents, colorants, and general additives in the composition (V-1), the fillers (D) and the coupling agents ( The same compound as E), crosslinking agent (F), colorant (I) and general additive (J).
組成物(V-1)中，前述填充材料、偶合劑、交聯劑、著色劑、及通用添加劑分別可單獨使用1種，亦可併用2種以上，於併用2種以上之情形，這些的組合及比率可任意選擇。 In the composition (V-1), each of the aforementioned fillers, coupling agents, crosslinking agents, colorants, and general additives may be used alone or in combination of two or more. When two or more are used in combination, the Combinations and ratios can be chosen arbitrarily.
組成物(V-1)中的前述填充材料、偶合劑、交聯劑、著色劑、及通用添加劑的含量根據目的適當調節即可，並無特別限定。 The contents of the aforementioned fillers, coupling agents, crosslinking agents, colorants, and general additives in the composition (V-1) may be appropriately adjusted according to the purpose, and are not particularly limited.
就藉由稀釋而提高該組成物的操作性而言，組成物(V-1)較佳為進而含有溶劑。 The composition (V-1) preferably further contains a solvent in order to improve the handleability of the composition by dilution.
作為組成物(V-1)所含有之溶劑，例如可列舉與組成物(III-1)中的溶劑相同的溶劑。 Examples of the solvent contained in the composition (V-1) include the same solvents as those in the composition (III-1).
組成物(V-1)所含有之溶劑可僅為1種，亦可為2種以上。 The solvent contained in the composition (V-1) may be only one kind, or may be two or more kinds.
<<非硬化性保護膜形成用組成物的製造方法>> <<Manufacturing method of non-curable protective film forming composition>>
組成物(V-1)等非硬化性保護膜形成用組成物可藉由調配用以構成該組成物之各成分而獲得。 The non-curable protective film forming composition, such as composition (V-1), can be obtained by preparing each component which comprises this 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 addition of each component is not particularly limited, and two or more components may be added at the same time.
於使用溶劑之情形，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。 In the case of using a solvent, it can be used by mixing the solvent with any compounded component other than the solvent and diluting the compounded component in advance; it can also be used by not mixing any compounded component other than the solvent. The ingredients are pre-diluted and the solvent is mixed with these formulated 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當選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the ingredients is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; and mixing by applying ultrasonic waves. method etc.
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，適當調節即可，溫度較佳為15℃至30℃。 The temperature and time for adding and mixing the components are not particularly limited as long as the components are not degraded, and may be appropriately adjusted. The temperature is preferably 15°C to 30°C.
◇保護膜形成用複合片的製造方法 ◇Manufacturing method of composite sheet for protective film formation
前述保護膜形成用複合片可藉由下述方式進行製造：將上述之各層以成為對應的位置關係及保護膜形成用膜的寬度(TD(Transvcrse Direction；橫向)方向的最大長度)相對於上述支撐片的寬度(TD方向的最大長度)之比之方式依序積層。各層的形成方法如上文所說明。 The composite sheet for forming a protective film can be produced by aligning the respective layers described above in a corresponding positional relationship and the width of the film for forming a protective film (maximum length in the TD (Transverse Direction; transverse) direction) relative to the above-mentioned The ratio of the width of the support sheet (maximum length in the TD direction) is sequentially stacked. The method of forming each layer is as described above.
例如，於製造保護膜形成用複合片時，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，可於黏著劑層上塗敷熱硬化性保護膜形成用組成物、能量線硬化性保護膜形成用組成物、或非硬化性保護膜形成用組成物，直接形成保護膜形成用膜。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，可於由前述組成物形成之層上，進而塗敷組成物而重新形成層。但是，較佳為這些2層中的後積層的層於另一剝離膜上使用前述組成物而預先形成，使該已形成之層中的與接觸於前述剝離膜之側為相反側的露出面來和既已形成之剩餘層的露出面貼合，藉此形成連續之2層之積層結構。此時，前述組成物較佳為塗敷於剝離膜的剝離處理面。於形成積層結構後，視需要移除剝離膜即可。 For example, when manufacturing a composite sheet for forming a protective film, in the case of laminating a film for forming a protective film on an adhesive layer already laminated on a base material, a composition for forming a thermosetting protective film may be applied to the adhesive layer. material, an energy ray curable protective film-forming composition, or a non-curable protective film-forming composition to directly form a protective film-forming film. In this way, when a continuous two-layer laminated structure is formed using any one of the compositions, the composition can be further coated on the layer formed of the aforementioned composition to form a new layer. However, among these two layers, it is preferable that the layer of the latter layer be formed in advance on another release film using the above-mentioned composition, so that the exposed surface of the formed layer is the opposite side to the side contacting the above-mentioned release film. To be attached to the exposed surface of the remaining layer that has already been formed, thereby forming a continuous two-layer laminated structure. At this time, it is preferable that the aforementioned composition is applied to the release-treated surface of the release film. After the laminated structure is formed, the release film can be removed if necessary.
亦即，於製造保護膜形成用複合片之情形，藉由下述方式獲得保護膜形成用複合片：於基材上塗敷黏著劑組成物，視需要使之乾燥，藉此於基材上預先積層黏著劑層，另外於剝離膜上塗敷熱硬化性保護膜形成用組成物、能量線硬化性保護膜形成用組成物、或非硬化性保護膜形成 用組成物，視需要使之乾燥，藉此於剝離膜上預先形成保護膜形成用膜，使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，將保護膜形成用膜積層於黏著劑層上。 That is, in the case of producing a composite sheet for forming a protective film, a composite sheet for forming a protective film is obtained by applying an adhesive composition on a base material and drying it if necessary, thereby pre-applying the adhesive composition on the base material. Laminate an adhesive layer, and apply a composition for forming a thermosetting protective film, a composition for forming an energy ray curable protective film, or a non-curable protective film on the release film Using the composition, drying it if necessary, forming a protective film-forming film on the release film in advance, and bonding the exposed surface of the protective film-forming film to the exposed surface of the adhesive layer laminated on the base material and laminating the film for protective film formation on the adhesive layer.
另一方面，於基材上積層黏著劑層之情形，如上所述，亦可代替於基材上塗敷黏著劑組成物之方法，而是於剝離膜上塗敷黏著劑組成物，視需要使之乾燥，藉此於剝離膜上預先形成黏著劑層，使該黏著劑層的露出面與基材的一表面貼合，藉此將黏著劑層積層於基材上。 On the other hand, in the case of laminating the adhesive layer on the substrate, as described above, instead of applying the adhesive composition on the substrate, the adhesive composition can be applied on the release film, and if necessary, the adhesive composition can be applied. drying, thereby pre-forming an adhesive layer on the release film, and bonding the exposed surface of the adhesive layer to one surface of the base material, thereby laminating the adhesive layer on the base material.
任一方法中，剝離膜均於形成目標積層結構後的任意時間點移除即可。 In either method, the peeling film can be removed at any time point 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(黏著劑層、保護膜形成用膜)均可利用預先形成於剝離膜上，再貼合於目標層的表面之方法進行積層，因此適當選擇視需要採用此種步驟之層，製造保護膜形成用複合片即可。 In this way, the layers (adhesive layer, film for protective film formation) other than the base material constituting the composite sheet for protective film formation can be laminated by the method of forming in advance on the release film and then sticking to the surface of the target layer, so It is sufficient to appropriately select the layer to be used in such a step as necessary, and to manufacture a composite sheet for forming a protective film.
此外，保護膜形成用複合片通常係以於該保護膜形成用複合片中的與支撐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保管。因此，亦可藉由下述方式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)上塗敷熱硬化性保護膜形成用組成物、能量線硬化性保護膜形成用組成物、或非硬化性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，視需要使之乾燥，藉此於剝離膜上預先形成構成最表層之層，於該層中的與接觸於剝離膜之側為相反側的露出面上利用上述任一種方法積層剩餘各層，不移除剝離膜而保持貼合狀態不變。 In addition, the composite sheet for protective film formation is normally stored with the peeling film attached to the surface of the outermost layer (for example, the film for protective film formation) on the side opposite to a support sheet in this composite sheet for protective film formation. Therefore, the composite sheet for forming a protective film can also be obtained by coating the composition for forming a thermosetting protective film, the composition for forming an energy ray curable protective film on the peeling film (preferably the peeling-treated surface of the peeling film), and the composite sheet for forming a protective film. A composition for forming a film, a composition for forming a non-hardening protective film, or the like is used to form a layer constituting the outermost layer, and dried as necessary to form a layer constituting the outermost layer on the release film in advance, and then On the exposed surface of the layer opposite to the side in contact with the release film, the remaining layers are laminated by any of the above methods, and the bonded state is maintained without removing the release film.
◇保護膜形成用膜的使用方法 ◇How to use the film for protective film formation
本發明的保護膜形成用膜例如可用於以下所示之附保護膜之半導體晶片的製造方法或半導體封裝體的製造方法。 The film for protective film formation of this invention can be used for the manufacturing method of the semiconductor wafer with a protective film shown below, or the manufacturing method of a semiconductor package, for example.
亦即，於半導體晶圓的背面(與電極形成面為相反側的面)貼附該保護膜形成用膜(圖9中的(b))。此時，可對半導體晶圓的背面預先進行雷射印字(圖9中的(a))，亦可隔著保護膜形成用複合片，對半導體晶圓的背面進行雷射印字。 That is, the film for protective film formation is attached to the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer ((b) in FIG. 9 ). At this time, laser printing may be performed on the back surface of the semiconductor wafer in advance ((a) in FIG. 9 ), or laser printing may be performed on the back surface of the semiconductor wafer through the protective film forming composite sheet.
繼而，對保護膜形成用膜視需要加熱或照射能量線，使保護膜形成用膜硬化(圖9中的(c))，製成保護膜。或者，於為藉由非硬化性保護膜形成用組成物形成之保護膜形成用膜之情形，亦可以未硬化狀態用作保護膜。藉由對半導體晶圓的背面進行雷射印字，而不對保護膜形成用膜進行雷射印字，即便於使保護膜形成用膜硬化而製成保護膜時，亦可無印字劣化之虞。 Next, the film for protective film formation is heated or irradiated with energy rays as necessary to harden the film for protective film formation ((c) in FIG. 9 ) to form a protective film. Alternatively, in the case of a film for forming a protective film formed from a composition for forming a non-curable protective film, it can also be used as a protective film in an uncured state. By performing laser printing on the back surface of the semiconductor wafer without performing laser printing on the film for forming a protective film, even when the film for forming a protective film is cured to form a protective film, there is no risk of deterioration of the printed characters.
繼而，將切割帶貼附於保護膜，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，針對半導體晶片，於貼附有該保護膜之狀態下(亦即，以附保護膜之半導體晶片之形式)，自基材側施加力而進行延伸，擴寬半導體晶片間的切口寬度後，自支撐片拉離而進行拾取。 Next, a dicing tape is attached to the protective film, and the semiconductor wafer is divided together with the protective film to obtain semiconductor wafers. Then, with the protective film attached to the semiconductor wafer (that is, in the form of a semiconductor wafer with a protective film), a force is applied from the substrate side to extend the width of the slit between the semiconductor wafers. , picked up by pulling away from the support sheet.
繼而，將所獲得之附保護膜之半導體晶片覆晶連接於基板的電路面後，經過熱處理(回流步驟)而製成半導體封裝體(圖9中的(d))。然後，使用該半導體封裝體，製作目標半導體裝置即可。藉由對半導體晶圓的背面進行雷射印字，而不對保護膜形成用膜進行雷射印字，即便於熱處理(回流步驟)中，亦可無印字劣化之虞。 Next, after the obtained semiconductor chip with protective film is flip-chip connected to the circuit surface of the substrate, it is subjected to heat treatment (reflow step) to form a semiconductor package ((d) in FIG. 9 ). Then, using this semiconductor package, it is only necessary to fabricate a target semiconductor device. By performing laser printing on the back surface of the semiconductor wafer without performing laser printing on the film for forming a protective film, there is no risk of deterioration of printing even during heat treatment (reflow step).
此外，於對保護膜形成用膜進行加熱或照射能量線而使之硬化之情形，硬化的時間點如上所述，可為切割之前，亦可為切割之後。其中，對保護膜形成用膜進行加熱或照射能量線而使之硬化之時間點較佳為切割之前。 Moreover, when hardening the film for protective film formation by heating or irradiating energy rays, the timing of hardening may be before dicing or after dicing as mentioned above. Among them, the timing of heating or irradiating the film for protective film formation to harden is preferably before dicing.
◇保護膜形成用複合片的使用方法 ◇How to use the composite sheet for protective film formation
本發明的保護膜形成用複合片例如可用於以下所示之附保護膜之半導體晶片的製造方法或半導體封裝體的製造方法。 The composite sheet for protective film formation of this invention can be used for the manufacturing method of the semiconductor wafer with a protective film or the manufacturing method of a semiconductor package shown below, for example.
亦即，於半導體晶圓的背面(與電極形成面為相反側的面)，藉由該保護膜形成用複合片的保護膜形成用膜貼附保護膜形成用複合片。此時，可對半導體晶圓的背面預先進行雷射印字，亦可隔著保護膜形成用複合片，對半導體晶圓的背面進行雷射印字。 That is, the protective film forming composite sheet is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface) through the protective film forming film of the protective film forming composite sheet. In this case, laser printing may be performed on the back surface of the semiconductor wafer in advance, or laser printing may be performed on the back surface of the semiconductor wafer through the protective film forming composite sheet.
繼而，對保護膜形成用膜視需要進行加熱或照射能量線，使保護膜形成用膜硬化，製成保護膜。或者，於為藉由非硬化性保護膜形成用組成物形成之保護膜形成用膜之情形，亦可以未硬化狀態用作保護膜。 Next, if necessary, the film for protective film formation is heated or irradiated with energy rays to harden the film for protective film formation to form a protective film. Alternatively, in the case of a film for forming a protective film formed from a composition for forming a non-curable protective film, it can also be used as a protective film in an uncured state.
繼而，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。藉由對半導體晶圓的背面進行雷射印字，而不對保護膜形成用膜進行雷射印字，即便於使保護膜形成用膜硬化而製成保護膜時，亦可無印字劣化之虞。 Then, the semiconductor wafer is divided together with the protective film by dicing to produce semiconductor wafers. By performing laser printing on the back surface of the semiconductor wafer without performing laser printing on the film for forming a protective film, even when the film for forming a protective film is cured to form a protective film, there is no risk of deterioration of the printed characters.
以後，利用與前述保護膜形成用膜的使用方法相同的方法，將半導體晶片自支撐片拉離而進行拾取。繼而，將所獲得之附保護膜之半導體晶片覆晶連接於基板的電路面後，經過熱處理(回流步驟)而製成半導體封裝體。然後，使用該半導體封裝體，製作目標半導體裝置即可。藉由對半導體晶圓的背面進行雷射印字，而不對保護膜形成用膜進行雷射印字，即便於熱處理(回流步驟)中，亦可無印字劣化之虞。 Thereafter, the semiconductor wafer is pulled out from the support sheet and picked up by the same method as the method of using the film for protective film formation described above. Then, after the obtained semiconductor chip with protective film is flip-chip connected to the circuit surface of the substrate, it is subjected to heat treatment (reflow step) to form a semiconductor package. Then, using this semiconductor package, it is only necessary to fabricate a target semiconductor device. By performing laser printing on the back surface of the semiconductor wafer without performing laser printing on the film for forming a protective film, there is no risk of deterioration of printing even during heat treatment (reflow step).
於對保護膜形成用膜進行加熱或照射能量線而使之硬化之情形，硬化的時間點如上所述，可為切割之前，亦可為切割之後。其中，將保護膜形成用膜進行加熱或照射能量線而使之硬化之時間點較佳為切割之前。 When the film for protective film formation is hardened by heating or irradiating an energy ray, the time point of hardening is as above-mentioned, and may be before dicing or after dicing. Among them, the timing of heating or irradiating the film for protective film formation to harden is preferably before dicing.
◇檢查方法 ◇Check method
本發明的檢查方法包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附前述保護膜形成用膜之步驟；及隔著保護膜，對前述半導體晶圓或前述半導體晶片進行檢查之步驟，前述保護膜係於前述半導體晶圓的背面或將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成。 The inspection method of the present invention includes: the step of performing laser printing on the back surface of the semiconductor wafer; the step of attaching the film for forming the protective film to the back surface of the semiconductor wafer; Or the step of inspecting the semiconductor wafer, wherein the protective film is formed by attaching the film for forming a protective film to the back surface of the semiconductor wafer or the back surface of a semiconductor wafer obtained by singulating the semiconductor wafer.
前述檢查步驟亦可為如下：隔著保護膜，檢查雷射印字於前述半導體晶圓或前述半導體晶片之印字、前述半導體晶圓或前述半導體晶片的背面的研削痕跡、或者半導體晶圓或前述半導體晶片與前述保護膜之間有無異物，前述保護膜係於前述半導體晶圓的背面或將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成。 The aforementioned inspection step may also be as follows: through the protective film, inspect the laser printing on the aforementioned semiconductor wafer or the printing of the aforementioned semiconductor wafer, the aforementioned semiconductor wafer or the grinding marks on the back of the aforementioned semiconductor wafer, or the semiconductor wafer or the aforementioned semiconductor wafer. There is no foreign matter between the wafer and the protective film formed by attaching the film for forming a protective film to the back surface of the semiconductor wafer or the back surface of a semiconductor wafer obtained by singulating the semiconductor wafer.
本發明的檢查方法可包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附保護膜形成用膜之步驟；及隔著於前述半導體晶圓的背面貼附前述保護膜形成用膜而形成之保護膜，檢查雷射印字於前述半導體晶圓之印字之步驟；亦可包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附保護膜形成用膜之步驟；及隔著於前述半導體晶圓的背面貼附前述保護膜形成用膜而形成之保護膜，檢查前述半導體晶圓的背面的研削痕跡之步驟；還可包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附保護膜形成用膜之步驟；及隔著於前述半導體晶圓的背面貼附前述保護膜形成用膜而形成之保護膜，檢查前述半導體晶圓與前述保護膜之間有無異物之步驟。 The inspection method of the present invention may include: a step of laser printing on the back of the semiconductor wafer; a step of attaching a film for forming a protective film to the back of the semiconductor wafer; The protective film formed by attaching the aforementioned protective film forming film, the step of inspecting the laser printing on the aforementioned semiconductor wafer; may also include: the step of performing laser printing on the back of the semiconductor wafer; a step of attaching a film for forming a protective film on the back of the semiconductor wafer; and a step of inspecting the grinding marks on the back of the semiconductor wafer via the protective film formed by attaching the film for forming a protective film to the back of the semiconductor wafer; It may include: a step of laser printing on the back of the semiconductor wafer; a step of attaching a film for forming a protective film on the back of the semiconductor wafer; and forming the protective film by attaching the back of the semiconductor wafer. A step of inspecting whether there is any foreign matter between the aforementioned semiconductor wafer and the aforementioned protective film for the protective film formed with a film.
另外，本發明的檢查方法可包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附保護膜形成用膜之步驟；及隔著於將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前 述保護膜形成用膜而形成之保護膜，檢查雷射印字於前述半導體晶片之印字之步驟；亦可包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附保護膜形成用膜之步驟；及隔著於將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成之保護膜，檢查前述半導體晶片的背面的研削痕跡之步驟；還可包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附保護膜形成用膜之步驟；及隔著於將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成之保護膜，檢查前述半導體晶片與前述保護膜之間有無異物之步驟。 In addition, the inspection method of the present invention may include: a step of performing laser printing on the back surface of the semiconductor wafer; a step of attaching a film for forming a protective film on the back surface of the semiconductor wafer; Before attaching the back surface of the semiconductor wafer obtained by singulation The protective film formed by the above-mentioned protective film forming film, the step of inspecting the printing of laser printing on the aforementioned semiconductor wafer; may also include: the step of performing laser printing on the back of the semiconductor wafer; on the back of the aforementioned semiconductor wafer A step of attaching a film for forming a protective film; and inspecting the back surface of the semiconductor wafer via the protective film formed by attaching the film for forming a protective film to the back surface of the semiconductor wafer obtained by singulating the semiconductor wafer The step of grinding marks; may also include: a step of laser printing on the back of the semiconductor wafer; a step of attaching a film for forming a protective film on the back of the semiconductor wafer; A step of attaching the protective film formed by attaching the film for forming a protective film to the back surface of the semiconductor wafer obtained by slicing, and inspecting whether there is any foreign matter between the semiconductor wafer and the protective film.
◇辨識方法 ◇Identification method
本發明的辨識方法包含有：對半導體晶圓的背面進行雷射印字之步驟；於前述半導體晶圓的背面貼附保護膜形成用膜之步驟；及隔著保護膜，讀取雷射印字於前述半導體晶片之印字，辨識前述半導體晶片的種類之步驟，前述保護膜係於將前述半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成。 The identification method of the present invention includes: the step of laser printing on the back of the semiconductor wafer; the step of attaching a film for forming a protective film on the back of the semiconductor wafer; and reading the laser printing on the back of the semiconductor wafer through the protective film. The printing of the semiconductor wafer is a step of identifying the type of the semiconductor wafer, and the protective film is formed by attaching the protective film forming film to the back surface of the semiconductor wafer obtained by singulating the semiconductor wafer.
[實施例] [Example]
以下，藉由具體的實施例對本發明更詳細地進行說明。但是，本發明並不受以下所示之實施例的任何限定。 Hereinafter, the present invention will be described in more detail by means of specific examples. However, this invention is not limited at all by the Example shown below.
以下表示用於製造保護膜形成用組成物(III-1)之成分。 Components for producing the composition (III-1) for forming a protective film are shown below.
‧聚合物成分 ‧Polymer composition
(A)-1：使甲基丙烯酸酯85質量份、及丙烯酸2-羥基乙酯15質量份共聚而成之丙烯酸系聚合物(重量平均分子量：37萬) (A)-1: Acrylic polymer obtained by copolymerizing 85 parts by mass of methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 370,000)
(A)-2：使丙烯酸丁酯13質量份、丙烯酸甲酯70質量份、甲基丙烯酸縮水甘油酯5質量份、及丙烯酸2-羥基乙酯12質量份共聚而成之丙烯酸系聚合物(重量平均分子量：42萬) (A)-2: an acrylic polymer ( Weight average molecular weight: 420,000)
‧熱硬化性成分 ‧Thermosetting components
(B1)-1：雙酚A型環氧樹脂(三菱化學製造的JER828，環氧當量184g/eq至194g/eq) (B1)-1: bisphenol A type epoxy resin (JER828 manufactured by Mitsubishi Chemical, epoxy equivalent 184g/eq to 194g/eq)
(B1)-2：雙酚A型環氧樹脂(三菱化學製造的JER1055，環氧當量800g/eq至900g/eq) (B1)-2: bisphenol A type epoxy resin (JER1055 manufactured by Mitsubishi Chemical, epoxy equivalent 800g/eq to 900g/eq)
(B1)-3：二環戊二烯型環氧樹脂(DIC(股)製造的Epiclon HP-7200HH，環氧當量255g/eq至260g/eq) (B1)-3: Dicyclopentadiene-type epoxy resin (Epiclon HP-7200HH manufactured by DIC Co., Ltd., epoxy equivalent 255 g/eq to 260 g/eq)
(B2)-1：熱活性潛伏性環氧樹脂硬化劑(雙氰胺(ADEKA製造的Adeka Hardener EH-3636AS，活性氫量21g/eq)) (B2)-1: Thermally active latent epoxy resin hardener (dicyandiamide (Adeka Hardener EH-3636AS manufactured by ADEKA, active hydrogen content 21 g/eq))
‧硬化促進劑 ‧Hardening Accelerator
(C)-1：2-苯基-4,5-二羥基甲基咪唑(四國化成工業公司製造的Curezol 2PHZ) (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole (Curezol 2PHZ manufactured by Shikoku Chemical Industry Co., Ltd.)
‧填充材料 ‧Filler
(D)-1：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑0.5μm) (D)-1: Silica filler (SC2050MA manufactured by Admatechs, average particle size 0.5 μm)
(D)-2：二氧化矽填料(TATSUMORI公司製造的SV-10，平均粒徑8.0μm) (D)-2: Silica filler (SV-10 manufactured by TATSUMORI Co., Ltd., average particle size 8.0 μm)
‧偶合劑 ‧Coupling agent
(E)-1：矽烷偶合劑(Nippon Unicar製造的A-1110) (E)-1: Silane coupling agent (A-1110 manufactured by Nippon Unicar)
‧著色劑 ‧Colorant
(I)-1：有機系黑色顏料(大日精化工業公司製造的6377黑) (I)-1: Organic black pigment (6377 black made by Dainichi Seika Co., Ltd.)
(I)-2：碳黑(三菱化學公司製造的#MA650，平均粒徑28nm) (1)-2: carbon black (#MA650 manufactured by Mitsubishi Chemical Corporation, average particle diameter 28nm)
[實施例1] [Example 1]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
(保護膜形成用組成物(1)之製造) (Manufacture of protective film forming composition (1))
以固形重量比計，使聚合物成分(A)-1(150質量份)、熱硬化性成分(B1)-1(60質量份)、(B1)-2(10質量份)、(B1)-3(30質量份)、(B2)-1(2.4質量份)、硬化促進劑(C)-1(2.4質量份)、填充材料(D)-1(320質量份)、偶合劑(E)-1(2質量份)、及著色劑(I)-1(15質量份)溶解或分散於甲基乙基酮中，於23℃進行攪拌，藉此獲得熱硬化性的保護膜形成用組成物(1)。 In terms of solid weight ratio, polymer component (A)-1 (150 parts by mass), thermosetting component (B1)-1 (60 parts by mass), (B1)-2 (10 parts by mass), (B1) -3 (30 parts by mass), (B2)-1 (2.4 parts by mass), hardening accelerator (C)-1 (2.4 parts by mass), filler (D)-1 (320 parts by mass), coupling agent (E )-1 (2 parts by mass) and coloring agent (I)-1 (15 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain a thermosetting protective film. Composition (1).
(保護膜形成用膜之製造(1)) (Manufacture of film for protective film formation (1))
於聚對苯二甲酸乙二酯製膜的單面藉由聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造的「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(1)，於100℃乾燥2分鐘，藉此製作厚度25μm之熱硬化性的保護膜形成用膜(1)。 The peeling treatment surface of the peeling film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) which is peeled by silicone treatment on one side of the polyethylene terephthalate film is cut by a knife The protective film-forming composition (1) obtained above was applied by a coater, and dried at 100° C. for 2 minutes to prepare a thermosetting protective film-forming film (1) having a thickness of 25 μm.
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
(圖像清晰度之評價) (Evaluation of image clarity)
使用Suga Test Instruments(股)製造的圖像清晰度測定器「ICM-10P」，依據JISK7374，測定5種狹縫(狹縫寬度：0.125mm、0.25mm、0.5mm、1mm及2mm)的合計值作為保護膜形成用膜(1)的圖像清晰度。測定結果示於表1。 The total value of 5 kinds of slits (slit width: 0.125mm, 0.25mm, 0.5mm, 1mm, and 2mm) was measured in accordance with JISK7374 using the image clarity measuring device "ICM-10P" manufactured by Suga Test Instruments Co., Ltd. As the image clarity of the film (1) for protective film formation. The measurement results are shown in Table 1.
(保護膜形成用膜的波長550nm之光線透過率) (Light transmittance at wavelength 550nm of film for protective film formation)
使用分光光度計(SHIMADZU公司製造，UV-VIS-NIR SPECTROPHOTOMETER UV-3600)，測定保護膜形成用膜的波長550nm之光線透過率。測定結果示於表1。 The light transmittance of the wavelength 550nm of the film for protective film formation was measured using the spectrophotometer (Shimadzu company make, UV-VIS-NIR SPECTROPHOTOMETER UV-3600). The measurement results are shown in Table 1.
(保護膜形成用膜的霧度) (Haze of protective film forming film)
針對保護膜形成用膜，依據JIS K 7136：2000，使用NDH5000(日本電色工業公司製造)，使用白色LED(5V、3W)作為光源，測定霧度(%)。測定結果示於表1。 About the film for protective film formation, haze (%) was measured using NDH5000 (made by Nippon Denshoku Kogyo Co., Ltd.) and white LED (5V, 3W) as a light source based on JISK7136:2000. The measurement results are shown in Table 1.
(保護膜形成用膜的表面粗糙度) (Surface roughness of film for protective film formation)
使用光干涉式表面形狀測定裝置(Veeco Metrology Group公司製造，製品名「WYKO WT1100」)，以PSI(phase shifting interferometry；相移干涉)模式且以倍率10倍，於面內10點測定保護膜形成用膜的表面粗糙度(Ra)，求出平均值。測定結果示於表1。 Using an optical interference type surface profile measurement device (manufactured by Veeco Metrology Group, product name "WYKO WT1100"), in PSI (phase shifting interferometry; phase shift interference) mode and a magnification of 10 times, the protective film formation was measured at 10 points in the plane Using the surface roughness (Ra) of the film, an average value was obtained. The measurement results are shown in Table 1.
(印字視認性之評價) (Evaluation of print visibility)
對8吋的半導體晶圓，使用EO Technics製造的雷射印字裝置CSM300M進行印字，於進行印字之面貼附保護膜形成用膜(1)。雷射印字所得之文字的尺寸係設為0.3mm×0.2mm。 The 8-inch semiconductor wafer was printed using a laser printing device CSM300M manufactured by EO Technics, and the film (1) for forming a protective film was attached to the surface to be printed. The size of the characters obtained by laser printing is set to 0.3mm×0.2mm.
隔著保護膜形成用膜(1)，以目視觀察雷射印字所得之文字時，判定是否可視認文字。評價結果示於表1。 When the characters obtained by laser printing were visually observed through the film (1) for protective film formation, it was judged whether the characters were visible or not. The evaluation results are shown in Table 1.
A：清晰可見。B：些許模糊但可視認。C：無法視認。 A: Clearly visible. B: Slightly blurred but recognizable. C: Not visually recognized.
(保護膜的可靠性之評價) (Evaluation of the reliability of the protective film)
捲出上述所獲得之積層體，自保護膜形成用膜的單面移除一前述剝離膜，於經#2000研磨之矽晶圓(直徑200mm，厚度280μm)的研磨面，使用貼帶機(Lintec公司製造的「Adwill RAD-3600F/12」)，一面將單面具備前述剝離膜之保護膜形成用膜的露出面加熱至70℃一面貼附。繼而，於照度230mW/cm2、光量170mJ/cm2之條件下照射紫外線，藉此使保護膜形成用膜硬化，於矽晶圓的研磨面形成保護膜。 Roll out the laminated body obtained above, remove one of the aforementioned release films from one side of the film for protective film formation, and use a tape mounter ( "Adwill RAD-3600F/12" manufactured by Lintec Co., Ltd.) was attached while heating the exposed surface of the film for forming a protective film having the aforementioned release film on one side to 70°C. Next, ultraviolet rays were irradiated under conditions of illuminance 230mW/cm 2 and light intensity 170mJ/cm 2 , thereby curing the film for forming a protective film and forming a protective film on the polished surface of the silicon wafer.
繼而，自前述保護膜，去除另一剝離膜後，貼附切割片(Lintec公司製造的「Adwill G-562」)，使用切割裝置(DISCO公司製造的 「DFD651」)，將上述之形成有保護膜之矽晶圓切割為3mm×3mm之大小，獲得附保護膜之半導體晶片。 Then, after removing another peeling film from the aforementioned protective film, a dicing sheet ("Adwill G-562" manufactured by Lintec Corporation) was attached, and a dicing device ("Adwill G-562" manufactured by DISCO Corporation) was used. "DFD651"), the above-mentioned silicon wafer formed with a protective film was cut into a size of 3mm×3mm to obtain a semiconductor wafer with a protective film.
繼而，將上述所獲得之附保護膜之半導體晶片置於模仿安裝半導體晶片時的製程之以下所示之預處理中。亦即，將附保護膜之半導體晶片於125℃烘烤20小時後，於85℃、相對濕度85%之條件下吸濕168小時，繼而自該吸濕環境取出，使得剛取出後的附保護膜之半導體晶片通過處於預熱160℃、峰值溫度260℃之條件之IR(infrared radiation；紅外線輻射)回流爐中3次。然後，將進行了上述操作之25個附保護膜之半導體晶片放入至冷熱衝擊裝置(ESPEC公司製造的「TSE-11-A」)中，於-65℃保持10分鐘後，於150℃保持10分鐘，將前述冷熱循環反復進行1000次。 Next, the semiconductor wafer with protective film obtained above was subjected to the following pretreatment imitating the process when mounting the semiconductor wafer. That is to say, after baking the semiconductor wafer with protective film at 125°C for 20 hours, absorb moisture at 85°C and relative humidity of 85% for 168 hours, and then take it out from the moisture-absorbing environment, so that the protective film just after taking it out The semiconductor wafer of the film is passed through an IR (infrared radiation; infrared radiation) reflow furnace with a preheating temperature of 160°C and a peak temperature of 260°C three times. Then, 25 semiconductor wafers with a protective film that were subjected to the above operations were placed in a thermal shock device ("TSE-11-A" manufactured by ESPEC Co., Ltd.), kept at -65°C for 10 minutes, and then kept at 150°C For 10 minutes, the aforementioned heating and cooling cycle was repeated 1000 times.
繼而，自冷熱衝擊裝置取出全部的附保護膜之半導體晶片，針對於半導體晶片與保護膜之接合部有無***、剝離、於半導體晶片有無龜裂，藉由使用掃描型超音波探傷裝置(Sonoscan公司製造的「D9600TMCSAM」)，觀察附保護膜之半導體晶片的剖面而進行確認。然後，計數產生上述之***、剝離及龜裂之至少一者之附保護膜之半導體晶片的個數，將該附保護膜之半導體晶片的數量(NG數)為2個以下之情形判定為可靠性合格(A)，將為3個以上之情形判定為可靠性不合格(B)。結果示於表1。 Then, take out all the semiconductor wafers with the protective film from the thermal shock device, and check whether there are bumps, peeling, or cracks on the semiconductor wafer at the joint between the semiconductor wafer and the protective film, by using a scanning ultrasonic flaw detection device (Sonoscan Corporation "D9600 TM CSAM" produced by the company), and confirmed by observing the cross-section of the semiconductor wafer with protective film. Then, count the number of semiconductor wafers with a protective film on which at least one of the above-mentioned bumps, peeling, and cracks has occurred, and determine that the number of semiconductor wafers with a protective film (NG number) is 2 or less. If the performance is qualified (A), it will be judged as unqualified reliability (B) for more than 3 situations. The results are shown in Table 1.
[實施例2] [Example 2]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
(保護膜形成用組成物(2)之製造) (Manufacture of protective film forming composition (2))
實施例1之保護膜形成用組成物(1)之製造中，將(D)-1：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑0.5μm)(320質量份)變更為(D)-2：二氧化矽填料(TATSUMORI公司製造的SV-10，平均粒徑8.0μm)(320質量 份)，除此以外，以與實施例1相同的方式，獲得熱硬化性的保護膜形成用組成物(2)。 In the production of the protective film-forming composition (1) of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatechs, average particle diameter 0.5 μm) (320 parts by mass) was changed to (D) -2: Silica filler (SV-10 manufactured by TATSUMORI Co., Ltd., average particle diameter 8.0 μm) (320 mass parts), except that, in the same manner as in Example 1, a thermosetting protective film-forming composition (2) was obtained.
(保護膜形成用膜(2)之製造) (Manufacture of protective film forming film (2))
實施例1之保護膜形成用膜之製造中，將保護膜形成用組成物(1)變更為保護膜形成用組成物(2)，除此以外，以與實施例1相同的方式，獲得保護膜形成用膜(2)。 In the production of the film for protective film formation in Example 1, except that the composition for protective film formation (1) was changed to the composition for protective film formation (2), in the same manner as in Example 1, protection was obtained. Film for film formation (2).
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
使用與實施例1相同的方法，評價保護膜形成用膜(2)的圖像清晰度、波長550nm之光線透過率、霧度、表面粗糙度及印字視認性、以及保護膜的可靠性。結果示於以下之表1。填料直徑小之實施例1的保護膜形成用膜的圖像清晰度的數值大，視認性優異。 Using the same method as in Example 1, the film for protective film formation (2) was evaluated for image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness, and print visibility, and reliability of the protective film. The results are shown in Table 1 below. The film for protective film formation of Example 1 whose filler diameter was small had a large numerical value of image clarity, and was excellent in visibility.
[實施例3] [Example 3]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
(保護膜形成用組成物(4)之製造) (Manufacture of protective film forming composition (4))
實施例1之保護膜形成用組成物(1)之製造中，不使用(I)-1：有機系黑色顏料(大日精化工業公司製造的CF3-4)(15質量份)，除此以外，以與實施例1相同的方式，獲得熱硬化性的保護膜形成用組成物(4)。 In the manufacture of the protective film forming composition (1) of Example 1, (I)-1: organic black pigment (CF3-4 manufactured by Dainichi Seika Co., Ltd.) (15 parts by mass) was not used, except that , in the same manner as in Example 1, a thermosetting protective film-forming composition (4) was obtained.
(保護膜形成用膜(4)之製造) (Manufacture of protective film forming film (4))
實施例1之保護膜形成用膜之製造中，將保護膜形成用組成物(1)變更為保護膜形成用組成物(4)，除此以外，以與實施例1相同的方式，獲得保護膜形成用膜(4)。 In the production of the film for protective film formation in Example 1, except that the composition for protective film formation (1) was changed to the composition for protective film formation (4), in the same manner as in Example 1, protection was obtained. Film for film formation (4).
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
使用與實施例1相同的方法，評價保護膜形成用膜(4)的圖像清晰度、波長550nm之光線透過率、霧度、表面粗糙度及印字視認性、以及保護膜的可靠性。結果示於以下之表2。 Using the same method as in Example 1, the film for protective film formation (4) was evaluated for image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness, and print visibility, and reliability of the protective film. The results are shown in Table 2 below.
[比較例1] [Comparative example 1]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
(保護膜形成用組成物(5)之製造) (Manufacture of protective film forming composition (5))
實施例1之保護膜形成用組成物(1)之製造中，將(D)-1：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑0.5μm)(320質量份)變更為(D)-3：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑8.0μm)(320質量份)，將(I)-1：有機系黑色顏料(大日精化工業公司製造的CF3-4)(15質量份)變更為(I)-3：碳黑(三菱化學公司製造的#MA650，平均粒徑28nm)(5.0質量份)，除此以外，以與實施例1相同的方式，獲得熱硬化性的保護膜形成用組成物(5)。 In the production of the protective film-forming composition (1) of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatechs, average particle diameter 0.5 μm) (320 parts by mass) was changed to (D) -3: Silica filler (SC2050MA manufactured by Admatechs, average particle diameter 8.0 μm) (320 parts by mass), (I)-1: organic black pigment (CF3-4 manufactured by Dainichi Seika Co., Ltd.) (15 Parts by mass) is changed to (1)-3: carbon black (#MA650 manufactured by Mitsubishi Chemical Corporation, average particle diameter 28nm) (5.0 parts by mass), except that, in the same manner as in Example 1, obtain thermosetting composition (5) for forming a protective film.
(保護膜形成用膜(5)之製造) (Manufacture of protective film forming film (5))
實施例1之保護膜形成用膜之製造中，將保護膜形成用組成物(1)變更為保護膜形成用組成物(5)，除此以外，以與實施例1相同的方式，獲得保護膜形成用膜(5)。 In the production of the film for protective film formation in Example 1, except that the composition for protective film formation (1) was changed to the composition for protective film formation (5), in the same manner as in Example 1, protection was obtained. Film for film formation (5).
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
使用與實施例1相同的方法，評價保護膜形成用膜(4)的圖像清晰度、波長550nm之光線透過率、霧度、表面粗糙度及印字視認性、以及保護膜的可靠性。結果示於以下之表2。 Using the same method as in Example 1, the film for protective film formation (4) was evaluated for image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness, and print visibility, and reliability of the protective film. The results are shown in Table 2 below.
[比較例2] [Comparative example 2]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
(保護膜形成用組成物(6)之製造) (Manufacture of protective film forming composition (6))
實施例1之保護膜形成用組成物(1)之製造中，將(D)-1：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑0.5μm)(320質量份)變更為(D)-2：二氧化矽填料(TATSUMORI公司製造的SV-10，平均粒徑8.0μm)(320質量份)，將(I)-1：有機系黑色顏料(大日精化工業公司製造的CF3-4)(15質量份)變更為(I)-3：碳黑(三菱化學公司製造的#MA650，平均粒徑28nm)(10.0質量份)，除此以外，以與實施例1相同的方式，獲得熱硬化性的保護膜形成用組成物(6)。 In the production of the protective film-forming composition (1) of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatechs, average particle diameter 0.5 μm) (320 parts by mass) was changed to (D) -2: Silica filler (SV-10 manufactured by TATSUMORI, average particle diameter 8.0 μm) (320 parts by mass), (I)-1: organic black pigment (CF3-4 manufactured by Dainichi Seika Co., Ltd. ) (15 parts by mass) is changed to (1)-3: carbon black (#MA650 manufactured by Mitsubishi Chemical Corporation, average particle diameter 28nm) (10.0 parts by mass), except that, in the same manner as in Example 1, obtain A composition (6) for forming a thermosetting protective film.
(保護膜形成用膜(6)之製造) (Manufacture of protective film forming film (6))
實施例1之保護膜形成用膜之製造中，將保護膜形成用組成物(1)變更為保護膜形成用組成物(6)，除此以外，以與實施例1相同的方式，獲得保護膜形成用膜(6)。 In the production of the film for protective film formation in Example 1, except that the composition for protective film formation (1) was changed to the composition for protective film formation (6), in the same manner as in Example 1, protection was obtained. Film for film formation (6).
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
使用與實施例1相同的方法，評價保護膜形成用膜(6)的圖像清晰度、波長550nm之光線透過率、霧度、表面粗糙度及印字視認性、以及保護膜的可靠性。結果示於以下之表2。 Using the same method as in Example 1, the film for protective film formation (6) was evaluated for image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness, and print visibility, and reliability of the protective film. The results are shown in Table 2 below.
[實施例4] [Example 4]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
(保護膜形成用組成物(7)之製造) (Manufacture of protective film forming composition (7))
實施例1之保護膜形成用組成物(1)之製造中，將(D)-1：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑0.5μm)(320質量份)變更為(D)-1：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑0.5μm)(10質量份)，除此以外，以與實施例1相同的方式，獲得熱硬化性的保護膜形成用組成物(7)。 In the production of the protective film-forming composition (1) of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatechs, average particle diameter 0.5 μm) (320 parts by mass) was changed to (D) -1: Silica filler (SC2050MA manufactured by Admatechs, average particle size 0.5 μm) (10 parts by mass), except that, in the same manner as in Example 1, a composition for forming a thermosetting protective film ( 7).
(保護膜形成用膜(7)之製造) (Manufacture of protective film forming film (7))
實施例1之保護膜形成用膜之製造中，將保護膜形成用組成物(1)變更為保護膜形成用組成物(7)，除此以外，以與實施例1相同的方式，獲得保護膜形成用膜(7)。 In the production of the film for protective film formation in Example 1, except that the composition for protective film formation (1) was changed to the composition for protective film formation (7), in the same manner as in Example 1, protection was obtained. Film for film formation (7).
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
使用與實施例1相同的方法，評價保護膜形成用膜(7)的圖像清晰度、波長550nm之光線透過率、霧度、表面粗糙度及印字視認性、以及保護膜的可靠性。結果示於以下之表3。 Using the same method as in Example 1, the film for protective film formation (7) was evaluated for image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness, and print visibility, and reliability of the protective film. The results are shown in Table 3 below.
[實施例5] [Example 5]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
(保護膜形成用組成物(8)之製造) (Manufacture of protective film forming composition (8))
實施例1之保護膜形成用組成物(1)之製造中，將(D)-1：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑0.5μm)(320質量份)變更為(D)-1：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑0.5μm)(10質量份)，且不使用(I)-1：有機系黑色顏料(大日精化工業公司製造的6377黑)(15質量份)，除此以外，以與實施例1相同的方式，獲得熱硬化性的保護膜形成用組成物(8)。 In the production of the protective film-forming composition (1) of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatechs, average particle diameter 0.5 μm) (320 parts by mass) was changed to (D) -1: Silica filler (SC2050MA manufactured by Admatechs, average particle size 0.5 μm) (10 parts by mass), and not used (I)-1: Organic black pigment (6377 black manufactured by Dainichi Seika Co., Ltd.) ( 15 parts by mass), except that, in the same manner as in Example 1, a thermosetting protective film forming composition (8) was obtained.
(保護膜形成用膜(8)之製造) (Manufacture of protective film forming film (8))
實施例1之保護膜形成用膜之製造中，將保護膜形成用組成物(1)變更為保護膜形成用組成物(8)，除此以外，以與實施例1相同的方式，獲得保護膜形成用膜(8)。 In the production of the film for protective film formation in Example 1, except that the composition for protective film formation (1) was changed to the composition for protective film formation (8), in the same manner as in Example 1, protection was obtained. Film for film formation (8).
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
使用與實施例1相同的方法，評價保護膜形成用膜(8)的圖像清晰度、波長550nm之光線透過率、霧度、表面粗糙度及印字視認性、以及保護膜的可靠性。結果示於以下之表3。 Using the same method as in Example 1, the film for protective film formation (8) was evaluated for image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness, and print visibility, and reliability of the protective film. The results are shown in Table 3 below.
[實施例6] [Example 6]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
(保護膜形成用組成物(9)之製造) (Manufacture of protective film forming composition (9))
實施例1之保護膜形成用組成物(1)之製造中，將(I)-1：有機系黑色顏料(大日精化工業公司製造的6377黑)(15質量份)變更為(I)-1：有機系黑色顏料(大日精化工業公司製造的6377黑)(32質量份)，除此以外，以與實施例1相同的方式，獲得熱硬化性的保護膜形成用組成物(9)。 In the manufacture of the protective film forming composition (1) of Example 1, (I)-1: organic black pigment (6377 black manufactured by Dainichi Seika Co., Ltd.) (15 parts by mass) was changed to (I)- 1: Organic black pigment (6377 black manufactured by Dainichi Seika Co., Ltd.) (32 parts by mass), except that, in the same manner as in Example 1, a composition (9) for forming a thermosetting protective film was obtained .
(保護膜形成用膜(9)之製造) (Manufacture of protective film forming film (9))
實施例1之保護膜形成用膜之製造中，將保護膜形成用組成物(1)變更為保護膜形成用組成物(9)，除此以外，以與實施例1相同的方式，獲得保護膜形成用膜(9)。 In the production of the film for protective film formation in Example 1, except that the composition for protective film formation (1) was changed to the composition for protective film formation (9), in the same manner as in Example 1, protection was obtained. Film for film formation (9).
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
使用與實施例1相同的方法，評價保護膜形成用膜(9)的圖像清晰度、波長550nm之光線透過率、霧度、表面粗糙度及印字視認性、以及保護膜的可靠性。結果示於以下之表3。 Using the same method as in Example 1, the film for protective film formation (9) was evaluated for image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness, and print visibility, and reliability of the protective film. The results are shown in Table 3 below.
[實施例7] [Example 7]
<保護膜形成用膜之製造> <Manufacture of film for protective film formation>
(保護膜形成用組成物(10)之製造) (Manufacture of protective film forming composition (10))
實施例1之保護膜形成用組成物(1)之製造中，將(A)-1之丙烯酸系聚合物(重量平均分子量：37萬)(150質量份)變更為(A)-2之丙烯酸系聚合物(重量平均分子量：42萬)(150質量份)，除此以外，以與實施例1相同的方式，獲得熱硬化性的保護膜形成用組成物(10)。 In the production of the protective film-forming composition (1) of Example 1, the acrylic polymer (weight average molecular weight: 370,000) (150 parts by mass) of (A)-1 was changed to acrylic acid of (A)-2 Except having been based on a polymer (weight average molecular weight: 420,000) (150 mass parts), it carried out similarly to Example 1, and obtained the thermosetting composition (10) for protective film formation.
(保護膜形成用膜(10)之製造) (Manufacture of protective film forming film (10))
實施例1之保護膜形成用膜之製造中，將保護膜形成用組成物(1)變更為保護膜形成用組成物(10)，除此以外，以與實施例1相同的方式，獲得保護膜形成用膜(10)。 In the production of the film for forming a protective film in Example 1, except that the composition (1) for forming a protective film was changed to the composition (10) for forming a protective film, in the same manner as in Example 1, protection was obtained. A film for film formation (10).
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
使用與實施例1相同的方法，評價保護膜形成用膜(10)的圖像清晰度、波長550nm之光線透過率、霧度、表面粗糙度及印字視認性、以及保護膜的可靠性。結果示於以下之表4。 Using the same method as in Example 1, the film for protective film formation (10) was evaluated for image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness, and print visibility, and reliability of the protective film. The results are shown in Table 4 below.
[比較例3] [Comparative example 3]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
(保護膜形成用組成物(11)之製造) (Manufacture of protective film forming composition (11))
實施例1之保護膜形成用組成物(1)之製造中，將(D)-1：二氧化矽填料(Admatechs製造的SC2050MA，平均粒徑0.5μm)(320質量份)變更為(D)-2：二氧化矽填料(TATSUMORI公司製造的SV-10，平均粒徑8.0μm)(320質量份)，將(I)-1：有機系黑色顏料(大日精化工業公司製造的6377黑)(15質量份) 變更為(I)-1：有機系黑色顏料(大日精化工業公司製造的6377黑)(32質量份)，除此以外，以與實施例1相同的方式，獲得熱硬化性的保護膜形成用組成物(11)。 In the production of the protective film-forming composition (1) of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatechs, average particle diameter 0.5 μm) (320 parts by mass) was changed to (D) -2: Silica filler (SV-10 manufactured by TATSUMORI, average particle diameter 8.0 μm) (320 parts by mass), (I)-1: organic black pigment (6377 black manufactured by Dainichi Seika Co., Ltd.) (15 parts by mass) Change to (I)-1: organic black pigment (6377 black manufactured by Dainichi Seika Co., Ltd.) (32 parts by mass), except that, in the same manner as in Example 1, obtain a thermosetting protective film formation Use composition (11).
(保護膜形成用膜(11)之製造) (Manufacture of protective film forming film (11))
實施例1之保護膜形成用膜之製造中，將保護膜形成用組成物(1)變更為保護膜形成用組成物(11)，除此以外，以與實施例1相同的方式，獲得保護膜形成用膜(11)。 In the production of the film for forming a protective film in Example 1, except that the composition (1) for forming a protective film was changed to the composition (11) for forming a protective film, in the same manner as in Example 1, protection was obtained. A film for film formation (11).
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
使用與實施例1相同的方法，評價保護膜形成用膜(11)的圖像清晰度、波長550nm之光線透過率、霧度、表面粗糙度及印字視認性、以及保護膜的可靠性。結果示於以下之表4。 Using the same method as in Example 1, the film for protective film formation (11) was evaluated for image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness, and print visibility, and reliability of the protective film. The results are shown in Table 4 below.
由表1至表4可明確，藉由保護膜形成用膜的圖像清晰度為110以上，印字視認性良好。 As is clear from Table 1 to Table 4, when the image resolution of the film for protective film formation is 110 or more, printed character visibility is favorable.
[產業可利用性] [Industrial availability]
本發明的保護膜形成用膜除直接貼附於半導體晶圓而用於製造半導體裝置以外，可作為貼附於切割帶等支撐片之保護膜形成用複合片用於製造半導體裝置。 The film for forming a protective film of the present invention can be used for manufacturing a semiconductor device as a composite sheet for forming a protective film attached to a support sheet such as a dicing tape, in addition to being directly attached to a semiconductor wafer to manufacture a semiconductor device.
藉由本發明的保護膜形成用膜的圖像清晰度為110以上，印字視認性良好，因此可隔著於半導體晶圓的背面或將半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成之保護膜，對前述半導體晶圓或前述半導體晶片較佳地進行檢查。 Since the image resolution of the protective film forming film of the present invention is 110 or more, the visibility of printed characters is good, so it can be attached via the back surface of a semiconductor wafer or the back surface of a semiconductor wafer obtained by singulating a semiconductor wafer. The protective film formed from the protective film forming film is preferably used for inspection of the aforementioned semiconductor wafer or the aforementioned semiconductor wafer.
另外，藉由本發明的保護膜形成用膜的圖像清晰度為110以上，印字視認性良好，因此可隔著於將半導體晶圓單片化而獲得之半導體晶片的背面貼附前述保護膜形成用膜而形成之保護膜，讀取雷射印字於前述半導體晶片之印字，較佳地辨識前述半導體晶片的種類。 In addition, since the image resolution of the film for forming a protective film of the present invention is 110 or more, the visibility of printed characters is good, so it can be formed by attaching the protective film to the back surface of a semiconductor wafer obtained by singulating a semiconductor wafer. The protective film formed with a film can read the laser printing on the aforementioned semiconductor chip, and preferably identify the type of the aforementioned semiconductor chip.
13:保護膜形成用膜 13: Film for protective film formation
13a:保護膜形成用膜的表面(第1面) 13a: The surface of the film for protective film formation (1st surface)
13b:保護膜形成用膜的表面(第2面) 13b: The surface of the film for protective film formation (2nd surface)
151:第1剝離膜 151: 1st peeling film
152:第2剝離膜 152: Second release film
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2018-169591 | 2018-09-11 | ||
| JP2018169591 | 2018-09-11 |
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| KR (1) | KR102596665B1 (en) |
| CN (1) | CN112154536A (en) |
| SG (1) | SG11202012966XA (en) |
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| WO (1) | WO2020054355A1 (en) |
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| TW202204150A (en) * | 2020-03-27 | 2022-02-01 | 日商琳得科股份有限公司 | Semiconductor device manufacturing sheet, method for manufacturing semiconductor device manufacturing sheet, and method for manufacturing semiconductor chip having film adhesive attached thereto |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007184658A (en) * | 2007-04-12 | 2007-07-19 | Casio Micronics Co Ltd | Semiconductor device |
| TW201532837A (en) * | 2014-01-08 | 2015-09-01 | Lintec Corp | Composite sheet for protective-film formation |
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| JPS5146258U (en) * | 1974-10-02 | 1976-04-05 | ||
| JP3841060B2 (en) * | 2003-04-03 | 2006-11-01 | 松下電器産業株式会社 | Semiconductor device and manufacturing method thereof |
| JP2007193271A (en) * | 2006-01-23 | 2007-08-02 | Lintec Corp | Method for producing antiglare film and antiglare film |
| JP5124778B2 (en) * | 2008-09-18 | 2013-01-23 | リンテック株式会社 | Laser dicing sheet and semiconductor chip manufacturing method |
| CN106415819A (en) | 2014-01-22 | 2017-02-15 | 琳得科株式会社 | Protective-membrane-forming film, sheet for forming protective membrane, compound sheet for forming protective membrane, and inspection method |
| WO2016195071A1 (en) * | 2015-06-05 | 2016-12-08 | リンテック株式会社 | Composite sheet for forming protective film |
| WO2017149926A1 (en) * | 2016-03-04 | 2017-09-08 | リンテック株式会社 | Semiconductor processing sheet |
| JP6298226B1 (en) * | 2017-03-30 | 2018-03-20 | リンテック株式会社 | Composite sheet for protective film formation |
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- 2019-08-23 WO PCT/JP2019/032962 patent/WO2020054355A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007184658A (en) * | 2007-04-12 | 2007-07-19 | Casio Micronics Co Ltd | Semiconductor device |
| TW201532837A (en) * | 2014-01-08 | 2015-09-01 | Lintec Corp | Composite sheet for protective-film formation |
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| JPWO2020054355A1 (en) | 2020-10-22 |
| JP6686241B1 (en) | 2020-04-22 |
| TW202025264A (en) | 2020-07-01 |
| SG11202012966XA (en) | 2021-02-25 |
| WO2020054355A1 (en) | 2020-03-19 |
| CN112154536A (en) | 2020-12-29 |
| KR20210057703A (en) | 2021-05-21 |
| KR102596665B1 (en) | 2023-11-01 |
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