TWI761335B - Supporting sheet and composite sheet for forming protective film - Google Patents
Supporting sheet and composite sheet for forming protective film Download PDFInfo
- Publication number
- TWI761335B TWI761335B TW106108951A TW106108951A TWI761335B TW I761335 B TWI761335 B TW I761335B TW 106108951 A TW106108951 A TW 106108951A TW 106108951 A TW106108951 A TW 106108951A TW I761335 B TWI761335 B TW I761335B
- Authority
- TW
- Taiwan
- Prior art keywords
- protective film
- adhesive layer
- forming
- film
- meth
- Prior art date
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- 230000001681 protective effect Effects 0.000 title claims abstract description 507
- 239000002131 composite material Substances 0.000 title claims abstract description 178
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- 239000000758 substrate Substances 0.000 claims abstract description 66
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- 238000003860 storage Methods 0.000 claims description 21
- 239000002585 base Substances 0.000 description 215
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- 238000000034 method Methods 0.000 description 86
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dicing (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明係關於一種支撐片及保護膜形成用複合片。 The present invention relates to a support sheet and a composite sheet for forming a protective film.
本申請案主張基於2016年3月24日在日本提出申請之日本特願2016-060577號的優先權，並將該申請案的內容引用至本文中。 This application claims priority based on Japanese Patent Application No. 2016-060577 for which it applied in Japan on March 24, 2016, and the content of the application is incorporated herein by reference.
近年來，業界使用稱為所謂的倒裝(face down)方式之安裝方法製造半導體裝置。倒裝方式中，使用於電路面上具有凸塊等電極之半導體晶片，將前述電極與基板接合。因此，會有半導體晶片中的與電路面為相反側的背面成為裸露之情形。 In recent years, the industry has used a mounting method called a so-called face down method to manufacture semiconductor devices. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. Therefore, the back surface of the semiconductor wafer on the opposite side to the circuit surface may be exposed.
會有於該裸露之半導體晶片的背面形成由有機材料所構成之樹脂膜作為保護膜，並將如此形成保護膜而獲得之附有保護膜之半導體晶片組入至半導體裝置之情形。保護膜用以防止於切割步驟以後的步驟中半導體晶片產生破裂或缺損，亦即防止所謂碎片(chipping)。 There is a case where a resin film made of an organic material is formed as a protective film on the backside of the bare semiconductor wafer, and the semiconductor wafer with the protective film obtained by forming the protective film in this way is incorporated into a semiconductor device. The protective film is used to prevent cracking or chipping of the semiconductor wafer in steps subsequent to the dicing step, that is, to prevent so-called chipping.
形成此種保護膜時，使用於支撐片上具備有保護膜形成用膜(保護膜形成層)之保護膜形成用複合片。作為前述支撐片，例如使用於樹脂製基材上積層有黏著劑層等而成之積層片。前述保護膜形成用複合片中，保護膜形成用膜具有形成保護膜之功能，並且支撐片能夠發揮作為切割片(dicing sheet)之功能，可謂為保護膜形成用膜與切割片形成為一體之保護膜形成用複合片。 When forming such a protective film, the composite sheet for protective film formation provided with the film (protective film forming layer) for protective film formation on a support sheet is used. As said support sheet, the laminated sheet which laminated|stacked the adhesive bond layer etc. on the resin base material is used, for example. In the aforementioned composite sheet for forming a protective film, the film for forming a protective film has a function of forming a protective film, and the support sheet can function as a dicing sheet, so it can be said that the film for forming a protective film and the dicing sheet are integrally formed. A composite sheet for forming a protective film.
通常，用於支撐片之加工前的前述基材的單面或雙面具有凹凸形狀。關於加工前的基材、使用該基材獲得之支撐片或保護膜形成用複合片，將這些捲取成捲筒(roll)時，若基材具有如上述之凹凸形狀之面(凹凸面)，則捲筒的接觸面彼此黏附而產生黏連(blocking)，因而使用困難。此處所謂接觸面，於基材之捲筒之情形時為基材各自的表面，於支撐片及保護膜形成用複合片之情形時為作為該支撐片及保護膜形成用複合片的最下層之基材的露出面與剝離膜等最上層的露出面。特別是，若於保護膜形成用複合片產生黏連，則會於該片產生褶皺，或者將該片自捲筒捲出時最上層(通常為剝離膜)自該片剝離。 Usually, the aforementioned base material before processing of the support sheet has a concavo-convex shape on one side or both sides. Regarding the base material before processing, the support sheet obtained by using the base material, or the composite sheet for forming a protective film, when the base material is wound into a roll, if the base material has the surface (concave-convex surface) of the above-mentioned uneven shape , the contact surfaces of the reels stick to each other to cause blocking, so it is difficult to use. The so-called contact surface here is the surface of each base material in the case of a roll of the base material, and is the lowermost layer of the support sheet and the composite sheet for protective film formation in the case of the support sheet and the composite sheet for protective film formation. The exposed surface of the base material and the exposed surface of the uppermost layer such as the release film. In particular, when blocking occurs in the composite sheet for forming a protective film, wrinkles are generated in the sheet, or the uppermost layer (usually a release film) is peeled from the sheet when the sheet is taken out from a roll.
相對於此，若捲筒的接觸面之一面為基材的凹凸面，則捲筒的接觸面的面積變小，因此黏連得到抑制。 On the other hand, when one surface of the contact surface of the reel is the uneven surface of the base material, the area of the contact surface of the reel becomes small, and thus blocking is suppressed.
另一方面，半導體裝置的製造過程中，會有對貼附於 半導體晶圓或半導體晶片之保護膜之支撐片側的面，藉由照射雷射光而進行印字(本說明書中，有時稱為「雷射印字」)之情形。此時，雷射光係自支撐片(基材)中的形成有保護膜之側的相反側經由支撐片而照射。亦即，雷射光係自基材的露出面側入射至支撐片再到達保護膜。因此，於基材的露出面為凹凸面之情形時，存在如下問題：雷射光會於該凹凸面發生漫反射導致雷射印字變得不清晰。 On the other hand, in the manufacturing process of semiconductor devices, there are The semiconductor wafer or the surface on the support sheet side of the protective film of the semiconductor chip is printed by irradiating laser light (in this specification, it may be referred to as "laser printing"). At this time, the laser beam is irradiated via the support sheet from the side opposite to the side where the protective film is formed in the support sheet (base material). That is, the laser light is incident on the support sheet from the exposed surface side of the base material, and then reaches the protective film. Therefore, when the exposed surface of the base material is a concave-convex surface, there is the following problem: the laser light will be diffusely reflected on the concave-convex surface, resulting in unclear laser printing.
另外，半導體裝置的製造過程中，會有藉由紅外線相機等經由前述片等檢測具備有保護膜形成用複合片或保護膜之半導體晶圓或半導體晶片的狀態之情形。但是，於如上述般雷射光於基材的露出面發生漫反射之情形時，亦存在無法獲取清晰的檢測影像之問題。 In addition, in the manufacturing process of a semiconductor device, the state of the semiconductor wafer or semiconductor chip provided with the composite sheet for protective film formation or the protective film may be detected by an infrared camera or the like through the aforementioned sheet or the like. However, when the laser light is diffusely reflected on the exposed surface of the substrate as described above, there is also a problem that a clear inspection image cannot be obtained.
作為可防止此種雷射光等光之漫反射之保護膜形成用複合片，例如揭示有以下的發明(切割帶一體型半導體背面保護用膜)：使用僅單面為凹凸面之基材，不將該基材的凹凸面作為露出面而是朝向保護膜形成用膜側配置(參照專利文獻1)。該保護膜形成用膜中，由基材及黏著劑層積層而成之積層片(切割帶)的霧度為45%以下。 As a composite sheet for forming a protective film capable of preventing such diffuse reflection of light such as laser light, for example, the following invention (dicing tape-integrated semiconductor backside protective film) is disclosed: a substrate having only one surface of concavo-convex surface is used, and no The concavo-convex surface of the base material is used as an exposed surface and is disposed toward the film side for forming a protective film (refer to Patent Document 1). In this film for protective film formation, the haze of the laminated sheet (dicing tape) formed by laminating the base material and the adhesive is 45% or less.
但是，專利文獻1中所揭示之保護膜形成用複合片中，由於基材的露出面為平滑面，故而存在如下問題：捲取成捲筒時，無法抑制上述黏連。
However, in the composite sheet for forming a protective film disclosed in
再者，於基材的凹凸面設置黏著劑層之情形時，存在 如下問題：必須使黏著劑層柔軟且足夠厚，以減輕該凹凸面對黏著劑層所造成之影響。若黏著劑層較硬，則會有於基材表面的凸部的根部附近的部位未填充黏著劑層而產生空隙部之情形。另外，若黏著劑層薄，則會反映基材表面的凹凸形狀，保護膜形成用膜之基材側的面(背面)成為凹凸面。如這些般，若由存在基材表面的凹凸形狀的埋入不充分之不良情況之保護膜形成用膜形成保護膜，且對該保護膜之支撐片側的面實施雷射印字時，則印字變得不清晰。另外，亦無法獲取半導體晶圓或半導體晶片的清晰的檢測影像。另一方面，於黏著劑層過厚之情形時，例如於切割步驟中切斷中的黏著劑層容易振動，因此半導體晶片或成為半導體晶片之過程之切斷中的半導體晶圓亦容易振動，並對這些半導體晶片或半導體晶圓施加多餘的力，結果容易於半導體晶片產生破裂或缺損(容易產生碎片)。 Furthermore, when the adhesive layer is provided on the uneven surface of the base material, there are The problem is as follows: the adhesive layer must be made soft and thick enough to reduce the influence of the unevenness on the adhesive layer. If the adhesive layer is hard, there are cases where the adhesive layer is not filled in the vicinity of the root of the convex portion on the surface of the base material, and a void portion may be generated. Moreover, when an adhesive layer is thin, the uneven|corrugated shape of a base material surface will be reflected, and the surface (back surface) of the base material side of the film for protective film formation will become an uneven surface. As described above, when a protective film is formed from a film for forming a protective film in which the unevenness of the surface of the substrate is insufficiently embedded, and laser printing is performed on the surface of the protective film on the support sheet side, the printing changes. not clear. In addition, clear inspection images of semiconductor wafers or semiconductor chips cannot be obtained. On the other hand, when the adhesive layer is too thick, for example, the adhesive layer during cutting in the dicing step is likely to vibrate, so the semiconductor wafer or the semiconductor wafer being cut in the process of becoming a semiconductor chip is also likely to vibrate. Excessive force is applied to these semiconductor wafers or semiconductor wafers, and as a result, the semiconductor wafers are likely to be cracked or chipped (fragmentation is likely to be generated).
[先前技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
專利文獻1：日本特開2012-033741號公報。 Patent Document 1: Japanese Patent Laid-Open No. 2012-033741.
本發明之目的在於提供一種保護膜形成用複合片以及用於製造前述保護膜形成用複合片之支撐片，前述保護膜形成用複合片能夠不產生黏著劑層對於基材表面之埋 入變得不充分、及產生碎片之不良情況，而可同時實現抑制黏連、對保護膜的清晰的雷射印字、及獲取半導體晶圓或半導體晶片的清晰的檢測影像。 An object of the present invention is to provide a composite sheet for forming a protective film and a support sheet for producing the composite sheet for forming a protective film, which can prevent the burial of the adhesive layer on the surface of the substrate. Insufficient injection and generation of debris can be achieved, while blocking inhibition, clear laser printing on protective films, and clear inspection images of semiconductor wafers or semiconductor wafers can be achieved at the same time.
本發明提供一種支撐片，係具備有基材以及積層於前述基材上的黏著劑層；前述基材中的具備有前述黏著劑層之側的表面的表面粗糙度(Ra)為0.4μm以下；前述基材中的與具備有前述黏著劑層之側為相反側的表面的表面粗糙度(Ra)大於具備有前述黏著劑層之側的表面的表面粗糙度，且為0.053μm至0.48μm。 The present invention provides a support sheet comprising a base material and an adhesive layer laminated on the base material; the surface roughness (Ra) of the surface of the base material on the side provided with the pressure-sensitive adhesive layer is 0.4 μm or less ; The surface roughness (Ra) of the surface on the opposite side to the side provided with the adhesive layer in the substrate is greater than the surface roughness of the surface on the side provided with the adhesive layer, and is 0.053 μm to 0.48 μm .
本發明之支撐片中，前述黏著劑層的厚度可為15μm以下。 In the support sheet of the present invention, the thickness of the adhesive layer may be 15 μm or less.
本發明之支撐片中，前述黏著劑層可為非能量線硬化性。 In the support sheet of the present invention, the adhesive layer may be non-energy ray curable.
另外，本發明提供一種保護膜形成用複合片，係具備有前述支撐片，且於前述支撐片中的前述黏著劑層上進一步具備有保護膜形成用膜。 Moreover, this invention provides the composite sheet for protective film formation which is provided with the said support sheet, and is further provided with the film for protective film formation on the said adhesive bond layer in the said support sheet.
藉由使用本發明之支撐片及保護膜形成用複合片，能夠不產生黏著劑層對於基材表面之埋入變得不充分、及產生碎片之不良情況，而可同時實現抑制黏連、對保護膜的 清晰的雷射印字、及獲取半導體晶圓或半導體晶片的清晰的檢測影像。 By using the support sheet and the composite sheet for forming a protective film of the present invention, it is possible to simultaneously suppress blocking and prevent the occurrence of defects such as insufficient embedding of the adhesive layer on the surface of the substrate and generation of chips. protective film Clear laser printing, and obtaining clear inspection images of semiconductor wafers or semiconductor wafers.
1‧‧‧支撐片 1‧‧‧Support
11‧‧‧基材 11‧‧‧Substrate
11a‧‧‧基材的一表面(第1面) 11a‧‧‧One surface of the substrate (Side 1)
11b‧‧‧基材的另一表面(第2面) 11b‧‧‧The other surface of the substrate (Side 2)
12‧‧‧黏著劑層 12‧‧‧Adhesive layer
12a‧‧‧黏著劑層的一表面(第1面) 12a‧‧‧One surface of the adhesive layer (Side 1)
12b‧‧‧黏著劑層的另一表面(第2面) 12b‧‧‧The other surface of the adhesive layer (Side 2)
13、23‧‧‧保護膜形成用膜 13, 23‧‧‧Protective film forming film
13a、23a‧‧‧保護膜形成用膜的一表面(第1面) 13a, 23a‧‧‧One surface (first surface) of the film for forming a protective film
14‧‧‧治具用接著劑層 14‧‧‧Adhesive layer for jig
14a‧‧‧治具用接著劑層的一表面(第1面) 14a‧‧‧One surface of the adhesive layer for the jig (the first surface)
14c‧‧‧治具用接著劑層的側面 14c‧‧‧Side surface of adhesive layer for jig
15‧‧‧剝離膜 15‧‧‧Peeling film
15a‧‧‧剝離膜的一表面(第1面) 15a‧‧‧One surface of release film (1st side)
23c‧‧‧保護膜形成用膜的側面 23c‧‧‧Side surface of protective film forming film
101、102、103‧‧‧保護膜形成用複合片 101, 102, 103‧‧‧Composite sheet for forming protective film
圖1係以示意方式表示本發明之支撐片的一實施形態之剖視圖。 FIG. 1 is a cross-sectional view schematically showing an embodiment of the support sheet of the present invention.
圖2係以示意方式表示本發明之保護膜形成用複合片的一實施形態之剖視圖。 FIG. 2 is a cross-sectional view schematically showing an embodiment of the composite sheet for forming a protective film of the present invention.
圖3係以示意方式表示本發明之保護膜形成用複合片的另一實施形態之剖視圖。 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
圖4係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖視圖。 4 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
◇支撐片、保護膜形成用複合片 ◇Support sheet, composite sheet for forming protective film
本發明之支撐片係具備有基材以及積層於前述基材上的黏著劑層；前述基材中的具備有前述黏著劑層之側的表面(以下，有時稱為「第1面」)的表面粗糙度(Ra)為0.4μm以下；前述基材中的與具備有前述黏著劑層之側為相反側的表面(以下，有時稱為「第2面」)的表面粗糙度(Ra)大於具備有前述黏著劑層之側的表面(第1面)的表面粗糙度，且為0.053μm至0.48μm。 The support sheet of the present invention includes a base material and an adhesive layer laminated on the base material; and the surface of the base material on the side provided with the pressure-sensitive adhesive layer (hereinafter, sometimes referred to as "the first surface") The surface roughness (Ra) of the base material is 0.4 μm or less; the surface roughness (Ra) of the surface (hereinafter, sometimes referred to as the “second surface”) on the opposite side of the base material to the side provided with the adhesive layer is ) is larger than the surface roughness of the surface (first surface) on the side having the aforementioned adhesive layer, and is 0.053 μm to 0.48 μm.
前述支撐片用以構成下述保護膜形成用複合片，例如可用作切割片等半導體晶圓之加工用片。 The aforementioned support sheet is used to constitute the following protective film-forming composite sheet, and can be used, for example, as a sheet for processing semiconductor wafers such as a dicing sheet.
再者，本說明書中，方便起見，有時將基材的雙面中表面粗糙度小的面(例如表面粗糙度為0.4μm以下之面，亦即第1面)稱為平滑面，將表面粗糙度大的面(例如表面粗糙度為0.053μm至0.48μm之面，亦即第2面)稱為凹凸面。亦即，基材的平滑面、凹凸面之稱呼未必表示這些面的絕對平滑度，而是表示這些面的相對平滑度的大小關係。 In this specification, for convenience, the surface with small surface roughness (for example, the surface with a surface roughness of 0.4 μm or less, that is, the first surface) on both sides of the substrate is sometimes referred to as the smooth surface, and the A surface with a large surface roughness (for example, a surface with a surface roughness of 0.053 μm to 0.48 μm, that is, the second surface) is called a concavo-convex surface. That is, the names of the smooth surface and the uneven surface of the base material do not necessarily indicate the absolute smoothness of these surfaces, but the magnitude relationship of the relative smoothness of these surfaces.
本發明之保護膜形成用複合片係具備有前述支撐片，且於前述支撐片中的前述黏著劑層上進一步具備有保護膜形成用膜。 The composite sheet for protective film formation of this invention is equipped with the said support sheet, and is equipped with the film for protective film formation further on the said adhesive bond layer in the said support sheet.
前述保護膜形成用複合片係藉由具備有第1面及第2面的表面粗糙度處於特定範圍內且第2面的表面粗糙度大於第1面的表面粗糙度之基材作為前述基材，能夠同時實現抑制黏連、對保護膜的清晰的雷射印字、及獲取半導體晶圓或半導體晶片的清晰的檢測影像。另外，前述保護膜形成用複合片係藉由基材的第1面的表面粗糙度處於特定範圍內(小值)且凹凸度低，而無需使黏著劑層柔軟且足夠厚，亦可抑制產生黏著劑層對於基材的第1面之埋入變得不充分、及產生碎片之不良情況。 The above-mentioned composite sheet for forming a protective film is provided with a substrate having a surface roughness of the first surface and the second surface within a specific range, and the surface roughness of the second surface is larger than the surface roughness of the first surface as the substrate. , which can simultaneously realize the inhibition of adhesion, the clear laser printing on the protective film, and the acquisition of a clear inspection image of the semiconductor wafer or the semiconductor wafer. In addition, in the above-mentioned composite sheet for forming a protective film, since the surface roughness of the first surface of the base material is within a specific range (small value) and the unevenness is low, it is not necessary to make the adhesive layer soft and sufficiently thick, and it is possible to suppress the occurrence of Insufficient embedding of the adhesive layer with respect to the first surface of the base material and the occurrence of chipping are inconvenient.
以下，首先，引用圖式說明本發明之支撐片及保護膜形成用複合片的整體構成。再者，以下之說明所使用之圖 中，為了易於理解本發明之特徵，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。 Hereinafter, first, the overall configuration of the support sheet and the composite sheet for forming a protective film of the present invention will be described with reference to the drawings. Furthermore, the diagrams used in the following descriptions In the above, in order to facilitate the understanding of the characteristics of the present invention, the main part may be shown enlarged for convenience, and the dimensional ratio of each component is not limited to be the same as the actual one.
圖1係以示意方式表示本發明之支撐片的一實施形態之剖視圖。 FIG. 1 is a cross-sectional view schematically showing an embodiment of the support sheet of the present invention.
此處所示之支撐片1係於基材11上具備有黏著劑層12，進一步於黏著劑層12上具備有剝離膜15。
The
於基材11的一表面(亦即基材的一表面11a，以下有時稱為第1面11a)積層有黏著劑層12，基材11的另一表面亦即基材11中的與具備有黏著劑層12之側為相反側的表面(亦即基材的另一表面11b，以下有時稱為第2面11b)係成為露出面。
The
基材11中，第1面11a的表面粗糙度為0.4μm以下，第2面11b的表面粗糙度大於第1面11a的表面粗糙度且為0.053μm至0.48μm。
In the
再者，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所求出之所謂算術平均粗糙度，有時簡稱為「Ra」。 In addition, in this specification, "surface roughness" means the so-called arithmetic mean roughness calculated|required based on JIS B0601:2001 unless otherwise specified, and may be abbreviated as "Ra" in some cases.
此處，雖然於黏著劑層12的一表面亦即黏著劑層12中的與設置有基材11之側為相反側的表面(亦即黏著劑層的一表面12a，以下有時稱為「第1面12a」)設置有剝離
膜15，然而在使用支撐片1時移除剝離膜15，且例如取而代之地積層保護膜形成用膜而構成保護膜形成用複合片。再者，符號12b意指黏著劑層12的另一表面亦即黏著劑層12中的設置有基材11之側的表面(亦即黏著劑層的另一表面12b，以下有時稱為「第2面12b」)。
Here, although one surface of the
圖2係以示意方式表示本發明之保護膜形成用複合片的一實施形態之剖視圖。再者，圖2以後之圖中，對與既已說明之圖所示相同的構成要素，標附與既已說明之圖之情形相同的符號，並省略該構成要素的詳細說明。 FIG. 2 is a cross-sectional view schematically showing an embodiment of the composite sheet for forming a protective film of the present invention. 2 and later, the same components as those shown in the previously described drawings are denoted by the same reference numerals as in the previously described drawings, and detailed descriptions of the components are omitted.
此處所示之保護膜形成用複合片101係於基材11上具備有黏著劑層12，並於黏著劑層12上具備有保護膜形成用膜13。保護膜形成用複合片101可使用支撐片1而構成，亦可謂於支撐片1中的黏著劑層12上進一步具備有保護膜形成用膜13。
The
保護膜形成用膜13積層於黏著劑層12的第1面12a的整個面。
The
另外，於保護膜形成用膜13中的與設置有黏著劑層12之側為相反側的表面(亦即保護膜形成用膜的一表面13a，以下有時稱為「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14。
In addition, the surface on the opposite side of the
並且，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14之面、及治具用接著劑層14中未與保
護膜形成用膜13接觸之面(第1面14a及側面14c)，積層有剝離膜15。此處，所謂治具用接著劑層14的第1面14a係治具用接著劑層14中的與和保護膜形成用膜13接觸之側為相反側的表面，亦存在無法明確區分治具用接著劑層14的第1面14a及側面14c之邊界之情況。另外，亦存在剝離膜15未接觸治具用接著劑層14的側面14c之情況。保護膜形成用複合片1通常如此般以具備有剝離膜15之狀態保管。再者，圖2中，符號15a表示剝離膜15中的與和保護膜形成用膜13接觸之側為相反側的表面(亦即剝離膜的一表面15a，以下有時稱為「第1面15a」)。
In addition, on the
保護膜形成用複合片101係以下述方式使用：在移除剝離膜15之狀態下，藉由保護膜形成用膜13的第1面13a貼附於半導體晶圓(省略圖示)中的與形成有電路之面(本說明書中，有時簡稱為「電路形成面」)為相反側的面(本說明書中，有時簡稱為「背面」)，並進一步將治具用接著劑層14的第1面14a貼附於環狀框等治具。
The
保護膜形成用複合片101中，基材11的第2面11b的表面粗糙度成為0.053μm至0.48μm，該表面粗糙度大於基材11的第1面11a的表面粗糙度，且具有適度的凹凸形狀。藉此，將保護膜形成用複合片101捲取成捲筒時，捲筒的接觸面彼此亦即積層之保護膜形成用複合片101中之一方的基材11的第2面11b與另一方的剝離膜
15的第1面15a之間黏附得到抑制，且黏連得到抑制。
In the
另外，半導體裝置的製造過程中，會有保護膜形成用膜13係以貼附於半導體晶圓或半導體晶片中的與電路形成面為相反側的面(背面)之狀態下藉由硬化而製成保護膜後，藉由自基材11的第2面11b側照射雷射光而進行印字(雷射印字)之情形。此時，雷射光係自基材11的第2面11b側入射至支撐片1再到達保護膜。因此，如上所述，基材11的第2面11b具有適度的凹凸形狀且凹凸度低，藉此可抑制雷射光於基材11的第2面11b發生漫反射，從而可對保護膜清晰地進行雷射印字。
In addition, in the production process of the semiconductor device, the protective
另外，半導體裝置的製造過程中，會有藉由紅外線相機等經由半導體晶圓或半導體晶片所具備的保護膜形成用複合片101或保護膜檢測具備有保護膜形成用複合片101或保護膜之半導體晶圓或半導體晶片之情形。此時，如上所述，基材11的第2面11b具有適度的凹凸形狀且凹凸度低，藉此可抑制紅外線於基材11的第2面11b發生漫反射，從而可獲取清晰的檢測影像。
In addition, in the manufacturing process of the semiconductor device, there is a case where the
另外，如以往之保護膜形成用複合片般，於基材的凹凸面設置有黏著劑層之情形時，必須使黏著劑層柔軟且足夠厚，以減輕該凹凸面對黏著劑層所造成之影響。原因在於，若黏著劑層較硬，則會有於基材表面的凸部的根部附 近的部位未填充黏著劑層而產生空隙部之情形；若黏著劑層薄，則會反映基材表面的凹凸形狀，保護膜形成用膜之基材側的面(背面)會成為凹凸面。如這些般，於黏著劑層對於基材表面的凹凸形狀之埋入不充分之情形時，若如上述般對保護膜實施雷射印字，則印字變得不清晰，亦無法獲取半導體晶圓或半導體晶片的清晰的檢測影像。但是，於黏著劑層過厚之情形時，例如於切割步驟中切斷中的黏著劑層容易振動，因此半導體晶片或成為半導體晶片之過程之切斷中的半導體晶圓亦容易振動，從而對半導體晶片施加多餘的力而容易產生破裂或缺損(容易產生碎片)。如此，於基材的凹凸面設置黏著劑層之情形時，容易產生各種不良情況。 In addition, when an adhesive layer is provided on the uneven surface of the base material as in the conventional composite sheet for forming a protective film, the adhesive layer must be soft and thick enough to reduce the impact of the uneven surface on the adhesive layer. Influence. The reason is that if the adhesive layer is hard, it will adhere to the root of the convex portion on the surface of the base material. If the adhesive layer is not filled in the near part and voids are formed; if the adhesive layer is thin, the uneven shape of the surface of the substrate will be reflected, and the surface (back) of the protective film forming film on the substrate side will be the uneven surface. As described above, when the pressure-sensitive adhesive layer is not sufficiently embedded in the unevenness of the substrate surface, if laser printing is performed on the protective film as described above, the printing becomes unclear, and semiconductor wafers or semiconductor wafers cannot be obtained. Clear inspection images of semiconductor wafers. However, when the adhesive layer is too thick, for example, the adhesive layer during cutting in the dicing step is likely to vibrate, so the semiconductor wafer or the semiconductor wafer being cut in the process of becoming a semiconductor chip is also prone to vibrate. The semiconductor wafer is prone to cracking or chipping (susceptibility to chipping) due to excessive force. In this way, when the adhesive layer is provided on the uneven surface of the base material, various inconveniences are likely to occur.
但是，本發明之保護膜形成用複合片101中，基材11中設置有黏著劑層12之第1面11a的表面粗糙度為0.4μm以下且平滑度高(凹凸度低)，因此可避免如上述之不良情況。亦即，保護膜形成用複合片101中，可藉由黏著劑層12充分地埋入基材11的第1面11a，且無需較厚地形成黏著劑層12，因此可抑制碎片。
However, in the
圖3係以示意方式表示本發明之保護膜形成用複合片的另一實施形態之剖視圖。 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
關於此處所示之保護膜形成用複合片102，除了保護膜形成用膜的形狀不同且不具備有治具用接著劑層之方面以外，與圖2所示之保護膜形成用複合片101相同。亦
即，保護膜形成用複合片102於基材11上具備有黏著劑層12，並於黏著劑層12上具備有保護膜形成用膜23，且進一步於保護膜形成用膜23上具備有剝離膜15。
The
保護膜形成用膜23積層於黏著劑層12的第1面12a的一部分，亦即積層於支撐片1的寬度方向(圖3中的左右方向)的中央側的區域。
The
另外，於黏著劑層12的第1面12a中未積層保護膜形成用膜23之面、及保護膜形成用膜23中未與黏著劑層12接觸的表面(第1面23a及側面23c)積層有剝離膜15。此處，所謂保護膜形成用膜23的第1面23a係保護膜形成用膜23中的與和黏著劑層12接觸之側為相反側的表面，亦存在無法明確區分保護膜形成用膜23的第1面23a及側面23c之邊界之情況。另外，亦存在剝離膜15未接觸於保護膜形成用膜23的側面23c之情況。保護膜形成用複合片102通常如此般以具備有剝離膜15之狀態保管。
In addition, in the
保護膜形成用複合片102係以下述方式使用：在移除剝離膜15之狀態下，藉由保護膜形成用膜23的第1面23a貼附於半導體晶圓(省略圖示)的背面，且進一步將黏著劑層12的第1面12a中未積層保護膜形成用膜23之面貼附於環狀框等治具。
The
保護膜形成用複合片102亦成為基材11的第1面11a
的表面粗糙度為0.4μm以下，第2面11b的表面粗糙度大於第1面11a的表面粗糙度且為0.053μm至0.48μm。藉此，保護膜形成用複合片102係與保護膜形成用複合片101之情形同樣地，能夠不產生黏著劑層12對於基材11的第1面11a之埋入變得不充分、及產生碎片之不良情況，而同時實現抑制黏連、對保護膜的清晰的雷射印字、及獲取半導體晶圓或半導體晶片的清晰的檢測影像。
The
圖4係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖視圖。 4 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
關於此處所示之保護膜形成用複合片103，除了於黏著劑層12的第1面12a中未積層保護膜形成用膜23之面亦即周緣部附近的區域進一步積層有治具用接著劑層14之方面以外，與圖3所示之保護膜形成用複合片102相同。
Regarding the
保護膜形成用複合片103係以下述方式使用：在移除剝離膜15之狀態下，藉由保護膜形成用膜23的第1面23a貼附於半導體晶圓(省略圖示)的背面，並進一步將治具用接著劑層14的第1面14a貼附於環狀框等治具。
The
保護膜形成用複合片103亦成為基材11的第1面11a的表面粗糙度為0.4μm以下，第2面11b的表面粗糙度大於第1面11a的表面粗糙度且為0.053μm至0.48μm。藉此，保護膜形成用複合片103係與保護膜形成用複合片
101之情形同樣地，能夠不產生黏著劑層12對於基材11的第1面11a之埋入變得不充分、及產生碎片之不良情況，而同時實現抑制黏連、對保護膜的清晰的雷射印字、及獲取半導體晶圓或半導體晶片的清晰的檢測影像。
The
本發明之保護膜形成用複合片並不限定於圖2至圖4所示的保護膜形成用複合片，在無損本發明的功效之範圍內，亦可將圖2至圖4所示之保護膜形成用複合片的一部分構成變更或刪除，或者對此前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 of the present invention is not limited to the composite sheet for forming a protective film shown in FIGS. 2 to 4 , and the protective film shown in FIGS. A part of the structure of the composite sheet for film formation is changed or deleted, or another structure is further added to the composite sheet for protective film formation described above.
其次，對本發明之支撐片及保護膜形成用複合片的各層的構成進行說明。 Next, the structure of each layer of the support sheet and the composite sheet for protective film formation of this invention is demonstrated.
◎基材 ◎Substrate
前述基材中的具備有前述黏著劑層之側的表面(第1面)的表面粗糙度為0.4μm以下，例如可設為0.37μm以下、0.3μm以下、0.2μm以下、0.1μm以下、0.09μm以下、0.08μm以下、0.07μm以下及0.06μm以下等之任一者，但這些為一例。 The surface roughness of the surface (first surface) on the side provided with the adhesive layer in the base material is 0.4 μm or less, for example, 0.37 μm or less, 0.3 μm or less, 0.2 μm or less, 0.1 μm or less, and 0.09 μm or less. Any one of μm or less, 0.08 μm or less, 0.07 μm or less, and 0.06 μm or less, but these are examples.
前述基材的第1面的表面粗糙度的下限值並無特別限定，例如可設為0.01μm等，但此為一例。 Although the lower limit value of the surface roughness of the 1st surface of the said base material is not specifically limited, For example, it can be set to 0.01 micrometer etc., but this is an example.
作為前述第1面的表面粗糙度的較佳例，可列舉：0.01μm至0.4μm、0.01μm至0.37μm、0.01μm至0.3μm、0.01μm至0.2μm、0.01μm至0.1μm、0.01μm 至0.09μm、0.01μm至0.08μm、0.01μm至0.07μm、及0.01μm至0.06μm。 Preferred examples of the surface roughness of the first surface include: 0.01 μm to 0.4 μm, 0.01 μm to 0.37 μm, 0.01 μm to 0.3 μm, 0.01 μm to 0.2 μm, 0.01 μm to 0.1 μm, 0.01 μm to 0.09 μm, 0.01 μm to 0.08 μm, 0.01 μm to 0.07 μm, and 0.01 μm to 0.06 μm.
前述基材中的與具備有前述黏著劑層之側為相反側的表面(第2面)的表面粗糙度為0.053μm至0.48μm，在該範圍內，例如可設為0.055μm以上、0.08μm以上、0.15μm以上、0.25μm以上、0.35μm以上等，且可設為0.47μm以下、0.45μm以下、0.35μm以下、0.25μm以下、0.15μm以下等，但這些為一例。 The surface roughness of the surface (second surface) on the opposite side to the side provided with the adhesive layer in the base material is 0.053 μm to 0.48 μm, and within this range, for example, it can be set to 0.055 μm or more and 0.08 μm 0.15 μm or more, 0.25 μm or more, 0.35 μm or more, etc., and can be set to 0.47 μm or less, 0.45 μm or less, 0.35 μm or less, 0.25 μm or less, 0.15 μm or less, etc., but these are examples.
作為前述第2面的表面粗糙度的較佳例，可列舉：0.053μm至0.47μm、0.053μm至0.45μm、0.053μm至0.35μm、0.053μm至0.25μm、及0.053μm至0.15μm。 Preferred examples of the surface roughness of the second surface include 0.053 μm to 0.47 μm, 0.053 μm to 0.45 μm, 0.053 μm to 0.35 μm, 0.053 μm to 0.25 μm, and 0.053 μm to 0.15 μm.
作為前述第2面的表面粗糙度的較佳的另一例，可列舉：0.055μm至0.48μm、0.08μm至0.48μm、0.15μm至0.48μm、0.25μm至0.48μm、及0.35μm至0.48μm。 As another preferable example of the surface roughness of the said 2nd surface, 0.055-0.48 micrometer, 0.08-0.48 micrometer, 0.15-0.48 micrometer, 0.25-0.48 micrometer, and 0.35-0.48 micrometer are mentioned.
但是，前述第2面的表面粗糙度大於前述第1面的表面粗糙度。 However, the surface roughness of the second surface is larger than the surface roughness of the first surface.
前述基材例如可使用成為原料之基材(以下，有時簡稱為「原料基材」)，藉由同時形成平滑面及凹凸面之方法或分別形成平滑面及凹凸面之方法而製作。 The aforementioned base material can be produced by a method of forming a smooth surface and an uneven surface at the same time or a method of separately forming a smooth surface and a uneven surface using a base material (hereinafter, sometimes abbreviated as "raw material base material") used as a raw material, for example.
作為同時形成平滑面及凹凸面之基材的製作方法，例如可列舉以下方法：於捲筒面的平滑度相互不同的一組捲 筒之間夾入原料基材，一邊使這些捲筒旋轉一邊使原料基材通過捲筒面間，藉此使得原料基材自平滑度大的捲筒面(捲筒的平滑面)形成平滑面，自平滑度小的捲筒面(捲筒的凹凸面)形成凹凸面，從而製作基材。 As a method for producing a base material that simultaneously forms a smooth surface and a concavo-convex surface, for example, the following method is mentioned: The raw substrate is sandwiched between the reels, and the raw substrate is passed between the reel surfaces while the reels are rotated, whereby the raw substrate forms a smooth surface from the reel surface (smooth surface of the reel) with high smoothness , forming a concavo-convex surface from the roll surface (the concavo-convex surface of the roll) with small smoothness to produce a base material.
另一方面，作為分別形成平滑面及凹凸面之基材的製作方法，例如可列舉以下方法：使用單面或雙面的表面粗糙度為0.4μm以下之原料基材，決定最終成為平滑面(表面粗糙度為0.4μm以下的面)之一表面，以使與該表面不同的另一表面成為表面粗糙度大於前述平滑面之凹凸面(表面粗糙度為0.053μm至0.48μm的面)之方式，進行平滑化處理或凹凸化處理，藉此製作基材。作為此時的平滑化處理或凹凸化處理的方法，例如可列舉以下所謂壓紋法：將原料基材按壓至如上述之捲筒的平滑面或凹凸面等。 On the other hand, as a method for producing a substrate having a smooth surface and a concave-convex surface, for example, there may be mentioned a method of using a raw substrate having a surface roughness of 0.4 μm or less on one side or both sides, and determining the final smooth surface ( One of the surfaces with a surface roughness of 0.4 μm or less), so that the other surface different from the surface becomes a concave and convex surface (a surface with a surface roughness of 0.053 μm to 0.48 μm) whose surface roughness is greater than that of the smooth surface. , perform smoothing treatment or concave-convex treatment to produce a base material. As a method of smoothing treatment or unevenness treatment at this time, for example, a so-called embossing method in which a raw material base material is pressed against the smooth surface or the uneven surface of the roll as described above can be mentioned.
如上述般，藉由轉印捲筒面等的形狀而使得原料基材形成平滑面或凹凸面之情形時，可藉由調節該捲筒面等的平滑面的平滑度、或者凹凸面的凹凸度，來調節基材的表面粗糙度。 As described above, when a smooth surface or a concave-convex surface is formed on the raw base material by transferring the shape of the roll surface or the like, the smoothness of the smooth surface such as the roll surface or the concave-convex surface of the concave-convex surface can be adjusted by adjusting to adjust the surface roughness of the substrate.
上述方法中，亦可視需要對原料基材中的最終成為平滑面(表面粗糙度為0.4μm以下的面)之一表面進行平滑化處理或凹凸化處理，而將該面的表面粗糙度調節為0.4μm以下之範圍內。 In the above method, one of the surfaces of the raw material substrate that will eventually become smooth surfaces (surfaces with a surface roughness of 0.4 μm or less) may be subjected to smoothing treatment or unevenness treatment, and the surface roughness of the surface may be adjusted to within the range of 0.4 μm or less.
再者，此處對利用捲筒的平滑面或凹凸面使基材的一表面的表面粗糙度成為0.053μm至0.48μm之方法進行了說明，但用於轉印平滑面或凹凸面之模具並不限定於捲筒，亦可為板、塊等其他形狀。 In addition, the method of making the surface roughness of one surface of the base material 0.053 μm to 0.48 μm using the smooth surface or the uneven surface of the roll is described here, but the mold for transferring the smooth surface or the uneven surface is not used. It is not limited to rolls, and other shapes such as plates and blocks may be used.
另外，作為原料基材的表面的凹凸化處理的方法，除了上述之壓紋法以外，例如亦可列舉噴砂處理法、溶劑處理法等。 Moreover, as a method of the unevenness|corrugation process of the surface of a raw material base material, in addition to the above-mentioned embossing method, a sandblasting method, a solvent processing method, etc. can be mentioned, for example.
上文對使用單面或雙面的表面粗糙度為0.4μm以下之原料基材製作雙面的表面粗糙度分別滿足前述條件之基材之方法進行了說明，但前述基材例如亦可利用以下之方法製作。 The method for producing a base material whose surface roughness on both sides satisfies the aforementioned conditions has been described above by using a raw material base material whose surface roughness on one side or both sides is 0.4 μm or less. However, for the aforementioned base material, for example, the following method of making.
亦即，亦可列舉以下方法：使用單面或雙面的表面粗糙度為0.053μm以上之原料基材，決定最終成為凹凸面(表面粗糙度為0.053μm至0.48μm的面)之一表面，以使與該面不同的另一表面成為表面粗糙度小於前述凹凸面之平滑面(表面粗糙度為0.4μm以下的面)之方式，進行平滑化處理或凹凸化處理，藉此製作基材。 That is, the following method can also be exemplified: using a raw material substrate having a surface roughness of 0.053 μm or more on one side or both sides, and determining one of the surfaces that will eventually become a concavo-convex surface (a surface with a surface roughness of 0.053 μm to 0.48 μm), A base material is produced by performing smoothing or concavo-convex treatment so that the other surface different from this surface becomes a smooth surface (surface with a surface roughness of 0.4 μm or less) having a surface roughness smaller than that of the concavo-convex surface.
該方法中，亦可視需要對原料基材中的最終成為凹凸面(表面粗糙度為0.053μm至0.48μm的面)的一表面進行平滑化處理或凹凸化處理，而將該面的表面粗糙度調節為0.053μm至0.48μm之範圍內。 In this method, one surface of the raw material substrate that will eventually become the uneven surface (surface with a surface roughness of 0.053 μm to 0.48 μm) may be smoothed or unevenly treated, and the surface roughness of the surface may be subjected to smoothing or uneven treatment. Adjusted to be in the range of 0.053 μm to 0.48 μm.
這些之中，作為前述基材的製作方法，較佳為使用原 料基材同時形成平滑面及凹凸面之方法。 Among these, it is preferable to use the original A method for simultaneously forming a smooth surface and a concave-convex surface on a material base.
前述基材的構成材料較佳為各種樹脂，前述樹脂可為公知的樹脂。 The constituent material of the aforementioned base material is preferably various resins, and the aforementioned resins may be known resins.
但是，基材較佳為對波長為532nm之光、及波長為1600nm之光均具有透過性。波長為532nm之光適於對保護膜進行雷射印字，波長為1600nm之光適於對半導體晶圓或半導體晶片進行紅外線檢測。 However, it is preferable that the base material is transparent to both light having a wavelength of 532 nm and light having a wavelength of 1600 nm. The light with a wavelength of 532nm is suitable for laser printing on the protective film, and the light with a wavelength of 1600nm is suitable for infrared detection of semiconductor wafers or semiconductor chips.
再者，於後述之黏著劑層為能量線硬化性之情形時，基材較佳為對紫外線區域之光具有透過性。 Furthermore, when the adhesive layer described later is energy ray curable, the base material preferably has transmittance to light in the ultraviolet region.
關於基材的具體的構成材料，於後文進行敘述。 The specific constituent material of the base material will be described later.
1層的基材的構成材料可僅為1種，亦可為2種以上；於為2種以上之情形時，這些2種以上之組合及比率可任意調節。 The constituent material of the base material of one layer 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 two or more types can be adjusted arbitrarily.
前述基材的拉伸彈性率並無特別限定，較佳為240MPa至700MPa，更佳為280MPa至650MPa，尤佳為320MPa至600MPa。 The tensile modulus of elasticity of the aforementioned substrate is not particularly limited, but is preferably 240 MPa to 700 MPa, more preferably 280 MPa to 650 MPa, and particularly preferably 320 MPa to 600 MPa.
基材可由1層(單層)構成，亦可由2層以上之複數層構成。於基材由複數層構成之情形時，這些複數層相互可相同亦可不同。亦即，可全部層相同，亦可全部層皆不同，還可僅一部分層相同。並且，於複數層相互不同之情形 時，這些複數層之組合並無特別限定。再者，本說明書中，所謂複數層相互不同並不限於基材之情形，意指各層的構成材料及厚度之至少一者相互不同。 The base material may be constituted by one layer (single layer), or may be constituted by a plurality of layers of two or more layers. When the base material is composed of plural layers, these plural layers may be the same or different from each other. That is, all the layers may be the same, all the layers may be different, or only a part of the layers may be the same. Also, when the plural layers are different from each other At the time, the combination of these plural layers is not particularly limited. In addition, in this specification, it is not limited to the case of a base material that a plurality of layers are different from each other, and it means that at least one of the constituent material and thickness of each layer is different from each other.
前述基材的厚度可根據目的適宜選擇，較佳為15μm至300μm，更佳為20μm至200μm，例如可為30μm至160μm、及40μm至120μm等之任一者。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 aforementioned substrate can be appropriately selected according to the purpose, preferably 15 μm to 300 μm, more preferably 20 μm to 200 μm, for example, any of 30 μm to 160 μm and 40 μm to 120 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 adhesion to a semiconductor wafer or a semiconductor chip are further improved.
此處，所謂「基材的厚度」意指基材整體的厚度，例如所謂由複數層構成之基材的厚度意指構成基材之全部層的合計厚度。 Here, "thickness of a base material" means the thickness of the whole base material, for example, the thickness of the base material which consists of a plurality of layers means the total thickness of all the layers which comprise a base material.
再者，基材的至少一面成為表面粗糙度為0.053μm以上且具有凹凸形狀之非平滑面，然而基材的厚度係只要於基材中的包含凸部的部位將該凸部的頂端作為一起點即可更高精度地算出。 Furthermore, at least one side of the base material is a non-smooth surface with a surface roughness of 0.053 μm or more and a concavo-convex shape, but the thickness of the base material is as long as the portion of the base material including the convex portion is taken as the tip of the convex portion. Points can be calculated with higher accuracy.
◎黏著劑層 ◎Adhesive layer
前述黏著劑層可為公知的黏著劑層，並無特別限定。例如黏著劑層可為能量線硬化性及非能量線硬化性之任一者。 The aforementioned adhesive layer may be a known adhesive layer, and is not particularly limited. For example, the adhesive layer may be either energy ray curable or non-energy ray curable.
本發明中，所謂「能量線硬化性」意指藉由照射能量線而硬化之性質。另外，將與上述相反地即便照射能量線亦不硬化之性質稱為「非能量線硬化性」。 In the present invention, the term "energy ray curability" means the property of being cured by irradiation with energy rays. In addition, contrary to the above, the property of not hardening even when irradiated with energy rays is referred to as "non-energy-beam curability".
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, the term "energy rays" means electromagnetic waves or charged particle beams having energy quanta, and examples of the energy rays include ultraviolet rays, radiation, and electron beams.
紫外線例如可藉由使用高壓水銀燈、融合(fusion)H型燈、氙氣燈、黑光燈或LED(Light Emitting Diode；發光二極體)燈等作為紫外線源進行照射。電子束可照射藉由電子束加速器等產生之電子束。 The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H-type lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode; light emitting diode) lamp or the like as an ultraviolet source. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like.
作為黏著劑層的構成材料，例如可列舉：黏著性樹脂等黏著劑、交聯劑等。 As a constituent material of the adhesive layer, for example, an adhesive such as an adhesive resin, a crosslinking agent, and the like can be mentioned.
但是，黏著劑層較佳為對波長為532nm之光、及波長為1600nm之光均具有透過性。波長為532nm之光適於對保護膜進行雷射印字，波長為1600nm之光適於對半導體晶圓或半導體晶片進行紅外線檢測。 However, it is preferable that the adhesive layer is transparent to both light with a wavelength of 532 nm and light with a wavelength of 1600 nm. The light with a wavelength of 532nm is suitable for laser printing on the protective film, and the light with a wavelength of 1600nm is suitable for infrared detection of semiconductor wafers or semiconductor chips.
前述黏著劑層較佳為能量線硬化性及非能量線硬化性之任一者，更佳為非能量線硬化性。 The aforementioned adhesive layer is preferably energy ray curable and non-energy ray curable, more preferably non-energy ray curable.
黏著劑層的儲存彈性率並無特別限定，通常較佳為0.01MPa至1000MPa，更佳為0.01MPa至500MPa，尤佳為0.01MPa至300MPa。 The storage elastic modulus of the adhesive layer is not particularly limited, but is usually preferably 0.01 MPa to 1000 MPa, more preferably 0.01 MPa to 500 MPa, and particularly preferably 0.01 MPa to 300 MPa.
黏著劑層的儲存彈性率可藉由調節黏著劑層的含有成分的種類或量而進行調節。 The storage elastic modulus of the adhesive layer can be adjusted by adjusting the types or amounts of components contained in the adhesive layer.
再者，本說明書中，所謂「黏著劑層的儲存彈性率」 只要無特別說明，則於黏著劑層為硬化性之情形時，意指「硬化前的黏著劑層的儲存彈性率」。 In addition, in this specification, the so-called "storage elastic modulus of the adhesive layer" Unless otherwise specified, when the adhesive layer is curable, it means "the storage elastic modulus of the adhesive layer before curing".
黏著劑層的儲存彈性率係藉由下述方法而求出。 The storage elastic modulus of the adhesive layer was obtained by the following method.
亦即，使黏著劑層彼此貼合，製作厚度為800μm之黏著劑層之積層體，將該積層體沖裁成直徑10mm的圓形而製成試片，使用黏彈性測定裝置等測定裝置對該試片賦予頻率1Hz之應變並測定-50℃至150℃的儲存彈性率，將23℃下的儲存彈性率之值設為上述之黏著劑層的儲存彈性率。 That is, the adhesive layers are bonded to each other to prepare a laminate of the adhesive layers having a thickness of 800 μm, the laminate is punched out into a circle with a diameter of 10 mm to prepare a test piece, and a measuring device such as a viscoelasticity measuring device is used to measure it. The test piece was given strain at a frequency of 1 Hz, and the storage elastic modulus at -50°C to 150° C. was measured, and the value of the storage elastic modulus at 23° C. was set as the storage elastic modulus of the above-mentioned adhesive layer.
黏著劑層可由1層(單層)構成，亦可由2層以上之複數層構成。於黏著劑層由複數層構成之情形時，這些複數層相互可相同亦可不同。此處，所謂「複數層相互可相同亦可不同」意指與上述之基材之情形相同。並且，於複數層相互不同之情形時，這些複數層之組合並無特別限定。 The adhesive layer may be constituted by one layer (single layer), or may be constituted by plural layers of two or more layers. When the adhesive layer is composed of plural layers, these plural layers may be the same or different from each other. Here, "a plurality of layers may be the same or different from each other" means the same as in the case of the above-mentioned base material. In addition, when the plural layers are different from each other, the combination of these plural layers is not particularly limited.
黏著劑層的厚度可根據目的適宜選擇，較佳為1μm至50μm，更佳為1μm至40μm，尤佳為1μm至30μm。藉由黏著劑層的厚度為前述下限值以上，黏著劑層對保護膜形成用膜之黏著力進一步提高。再者，埋入基材的第1面的凹凸形狀之功效變得更高，從而可進一步減小黏著劑層自該凹凸形狀所受之影響。另一方面，藉由黏著劑層的厚度為前述上限值以下，抑制碎片之功效變得更高，切割 步驟進一步穩定化。 The thickness of the adhesive layer can be appropriately selected according to the purpose, and is preferably 1 μm to 50 μm, more preferably 1 μm to 40 μm, and particularly preferably 1 μm to 30 μm. When the thickness of an adhesive bond layer is more than the said lower limit, the adhesive force of an adhesive bond layer with respect to the film for protective film formation is further improved. Furthermore, the effect of the concavo-convex shape on the first surface embedded in the base material becomes higher, and the influence of the concave-convex shape on the adhesive layer can be further reduced. On the other hand, when the thickness of the adhesive layer is equal to or less than the above-mentioned upper limit value, the effect of suppressing chipping becomes higher, and cutting Steps are further stabilized.
此處，所謂「黏著劑層的厚度」意指黏著劑層整體的厚度，例如所謂由複數層構成之黏著劑層的厚度意指構成黏著劑層之全部層的合計厚度。 Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer, for example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer.
再者，如上述般，會有前述基材的第1面的表面粗糙度為0.4μm以下，且與此種凹凸形狀相對應地黏著劑層中的設置有基材之側的表面(第2面)成為表面粗糙度為0.1μm以上等具有凹凸形狀之非平滑面之情形。該情形時，黏著劑層的厚度係只要於黏著劑層中的包含凸部之部位將該凸部的頂端作為一起點即可可更高精度地算出。 In addition, as described above, the surface roughness of the first surface of the base material is 0.4 μm or less, and the surface on the side where the base material is provided in the adhesive layer corresponding to such a concavo-convex shape (second surface). surface) is a case where the surface roughness is a non-smooth surface having a concavo-convex shape, such as a surface roughness of 0.1 μm or more. In this case, the thickness of the adhesive layer can be calculated with higher accuracy by taking the tip of the convex portion as a common point in the portion including the convex portion in the adhesive layer.
黏著劑層較佳為根據該黏著劑層的厚度調節硬度。作為用以判斷黏著劑層的硬度之指標，例如可列舉上述儲存彈性率。 The hardness of the adhesive layer is preferably adjusted according to the thickness of the adhesive layer. As an index for judging the hardness of the adhesive layer, for example, the above-mentioned storage elastic modulus can be mentioned.
例如，於黏著劑層的厚度較佳為超過15μm(厚於15μm)、更佳為18μm以上而較厚之情形時，黏著劑層的儲存彈性率較佳為30kPa以上，更佳為40kPa以上，尤佳為50kPa以上。該情形時的黏著劑層的儲存彈性率的上限值例如可設為上文列舉之通常值中的上限值。如此，若黏著劑層較硬，則即便於黏著劑層厚之情形時，例如於切割步驟中切斷中的黏著劑層亦不易振動。因此，半導體晶片或成為半導體晶片之過程之切斷中的半導體晶圓亦不 易振動，從而可抑制對這些半導體晶片或半導體晶圓施加多餘的力，結果於半導體晶片產生破裂或缺損亦即所謂碎片。 For example, when the thickness of the adhesive layer is preferably more than 15 μm (thicker than 15 μm), more preferably 18 μm or more, and thicker, the storage elastic modulus of the adhesive layer is preferably 30 kPa or more, more preferably 40 kPa or more, More preferably, it is 50 kPa or more. In this case, the upper limit of the storage elastic modulus of the adhesive layer can be, for example, the upper limit of the usual values listed above. In this way, if the adhesive layer is hard, even when the adhesive layer is thick, for example, the adhesive layer during cutting in the cutting step is not easily vibrated. Therefore, semiconductor wafers or semiconductor wafers in the process of becoming semiconductor wafers are not It is easy to vibrate, and it is possible to suppress the application of excessive force to these semiconductor wafers or semiconductor wafers, resulting in the occurrence of cracks or defects in the semiconductor wafers, that is, so-called chips.
另一方面，於黏著劑層的厚度較佳為15μm以下、更佳為10μm以下而較薄之情形時，黏著劑層的儲存彈性率並無特別限定。該情形時，即便黏著劑層柔軟，例如於切割步驟中切斷中的黏著劑層亦不易振動，因此如上述般獲得與黏著劑層較硬且厚之情形相同的功效。 On the other hand, when the thickness of the adhesive layer is preferably 15 μm or less, more preferably 10 μm or less, and is thin, the storage elastic modulus of the adhesive layer is not particularly limited. In this case, even if the adhesive layer is soft, for example, the adhesive layer being cut in the cutting step is not easily vibrated, so the same effect as the case where the adhesive layer is hard and thick is obtained as described above.
該情形(黏著劑層薄的情形)時的黏著劑層的儲存彈性率例如可設為上文列舉之通常的範圍，但此為一例。但是，抑制碎片之功效變得更高，故而該情形時，黏著劑層的儲存彈性率亦較佳為設為與上述之黏著劑層厚之情形相同的範圍。 In this case (the case where the adhesive layer is thin), the storage elastic modulus of the adhesive layer can be set to, for example, the usual range enumerated above, but this is an example. However, since the effect of suppressing the chipping becomes higher, in this case, the storage elastic modulus of the adhesive layer is preferably set in the same range as that in the case of the above-mentioned thickness of the adhesive layer.
亦即，前述支撐片中，黏著劑層的厚度較佳為15μm以下，更佳為10μm以下，藉此可不受黏著劑層的儲存彈性率的影響，而獲得抑制碎片之高功效。 That is, in the aforementioned support sheet, the thickness of the adhesive layer is preferably 15 μm or less, more preferably 10 μm or less, so that the storage elastic modulus of the adhesive layer is not affected, and a high effect of suppressing debris can be obtained.
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，藉此可於目標的部位形成黏著劑層。關於黏著劑層的更具體的形成方法，與其他層的形成方法一起，於後文進行詳細說明。黏著劑組成物中的常溫下不會 氣化的成分彼此的含量比率通常與黏著劑層中的前述成分彼此的含量比率相同。再者，本說明書中，所謂「常溫」意指不特別冷或特別熱的溫度亦即平常的溫度，例如可列舉15℃至25℃之溫度等。 The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive layer can be formed on a target site by applying an adhesive composition on the surface to be formed of the adhesive layer, and drying it if necessary. The more specific formation method of an adhesive bond layer is demonstrated in detail later together with the formation method of other layers. At room temperature in the adhesive composition, it will not The content ratio of the vaporized components is usually the same as the content ratio of the aforementioned components in the adhesive layer. In addition, in this specification, "normal temperature" means the temperature which is not particularly cold or particularly hot, that is, normal temperature, for example, the temperature of 15 degreeC - 25 degreeC etc. are mentioned.
前述黏著劑組成物藉由下述方式而獲得：將前述黏著劑、及視需要之前述黏著劑以外的成分等用以構成黏著劑組成物之成分加以調配。 The said adhesive composition is obtained by mixing the said adhesive, and the components other than the said adhesive as needed which make up an adhesive composition.
調配各成分時之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 at the time of preparing 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宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the components during the preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing method etc.
關於添加及混合各成分時的溫度及時間，只要不會使各調配成分劣化，則並無特別限定，適宜調節即可，溫度較佳為15℃至30℃。 The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.
利用公知的方法塗敷黏著劑組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、b繞線(meyer)棒式塗佈機、接觸式塗佈機等。 The adhesive composition may be applied by a known method, and examples thereof include methods using the following various coaters: air knife coater, knife coater, bar coater, gravure coater, roll coater Cloth machine, roll knife coater, curtain coater, die coater, knife coater, screen coater, b-wound (meyer) bar coater, contact coater Wait.
黏著劑組成物的乾燥條件並無特別限定，於黏著劑組成物含有後述之溶劑之情形時，較佳為進行加熱乾燥。含有溶劑之黏著劑組成物例如較佳為於70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described later, it is preferable to perform heat drying. The adhesive composition containing the solvent is preferably dried at, for example, 70° C. to 130° C. for 10 seconds to 5 minutes.
作為具備有由如上述之構成材料所構成之基材及黏著劑層之支撐片，例如可列舉：日本特許第4805549號公報中所記載之由基材膜及形成於該基材膜上之黏著劑層構成之黏著片、日本特許第4781633號公報中所記載之由基材膜及形成於該基材膜上之黏著劑層構成之黏著片、日本特許第5414953號公報中所記載之具備有基材及積層於該基材的至少一面之黏著劑層之切割片、日本特開2013-199562號公報中所記載之於基材的至少單面具有感壓接著性樹脂層(黏著劑層)之工件加工用片等。 Examples of the support sheet including the base material and the adhesive layer composed of the above-mentioned constituent materials include the base film and the adhesive formed on the base film described in Japanese Patent No. 4805549. An adhesive sheet composed of an adhesive layer, an adhesive sheet composed of a base film and an adhesive layer formed on the base film described in Japanese Patent No. 4781633, and an adhesive sheet described in Japanese Patent No. 5414953. A substrate and a dicing sheet with an adhesive layer laminated on at least one side of the substrate, having a pressure-sensitive adhesive resin layer (adhesive layer) on at least one side of the substrate as described in Japanese Patent Laid-Open No. 2013-199562 The workpiece processing sheet and so on.
作為本發明之支撐片，較佳為構成材料與這些片相同，且將第1面及第2面的表面粗糙度調節為上述之數值範圍。 As the support sheet of the present invention, it is preferable that the constituent materials are the same as those of these sheets, and the surface roughness of the first surface and the second surface is adjusted to the above-mentioned numerical range.
◎保護膜形成用膜 ◎Film for protective film formation
前述保護膜形成用膜具有硬化性，藉由硬化而形成保護膜。 The said film for protective film formation has curability, and a protective film is formed by hardening.
前述保護膜形成用膜可為熱硬化性及能量線硬化性之任一種。 The film for forming a protective film may be any of thermosetting properties and energy ray curing properties.
○熱硬化性保護膜形成用膜 ○ Thermosetting protective film forming film
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(trigger)而進行硬化(聚合)反應之成分。再者，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 a polymerization reaction of a polymerizable compound. Moreover, a thermosetting component (B) is a component which can perform a hardening (polymerization) reaction using heat as a trigger of a reaction. Furthermore, 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)構成，亦可由2層以上之複數層構成。於熱硬化性保護膜形成用膜由複數層構成之情形時，這些複數層相互可相同亦可不同。此處，所謂「複數層相互可相同亦可不同」意指與上述之基材之情形相同。並且，於複數層相互不同之情形時，這些複數層之組合並無特別限定。 The film for thermosetting protective film formation may be constituted by one layer (single layer), or may be constituted by a plurality of layers of two or more layers. When the film for thermosetting protective film formation consists of plural layers, these plural layers may be the same or different from each other. Here, "a plurality of layers may be the same or different from each other" means the same as in the case of the above-mentioned base material. In addition, when the plural layers are different from each other, the combination of these plural layers is not particularly limited.
熱硬化性保護膜形成用膜的厚度較佳為1μm至100μm，更佳為5μm至75μm，尤佳為5μm至50μm。藉由熱硬化性保護膜形成用膜的厚度為前述下限值以上，可形成保護能力更高的保護膜。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，可抑制成為過厚的厚度。 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, the protective film with higher protective ability can be formed. Moreover, since the thickness of the film for thermosetting protective film formation is below the said upper limit, it can suppress that it becomes 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，例如所謂由複數層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 the film for forming a thermosetting protective film composed of a plurality of layers means a structure heat hardening The total thickness of all layers of the film for forming a 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熱硬化性保護膜形成用膜硬化而形成保護膜時的硬化條件，只要保護膜成為充分發揮該保護膜的功能之程度的硬化度，則並無特別限定，根據熱硬化性保護膜形成用膜的種類適宜選擇即可。 Regarding the curing conditions when the film for forming a thermosetting protective film is adhered to the back surface of a semiconductor wafer, and the film for forming a thermosetting protective film is cured to form a protective film, the protective film is sufficient as long as the function of the protective film is sufficiently exhibited. The degree of hardening is not particularly limited, and may be appropriately selected according to the type of the 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℃至200℃，更佳為110℃至180℃，尤佳為120℃至170℃。並且，前述硬化時的加熱時間較佳為0.5小時至5小時，更佳為0.5小時至3小時，尤佳為1小時至2小時。 For example, 100-200 degreeC is preferable, as for the heating temperature at the time of hardening of the film for thermosetting protective film formation, 110-180 degreeC is more preferable, 120-170 degreeC is especially preferable. In addition, the heating time during the aforementioned hardening is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.
<<熱硬化性保護膜形成用組成物>> <<The composition for forming a thermosetting protective film>>
熱硬化性保護膜形成用膜可使用含有該熱硬化性保護膜形成用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，視需要使熱硬化性保護膜形成用組成物乾燥，藉此可於目標的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」如上文所說明。 The film for thermosetting protective film formation can be formed using the composition for thermosetting protective film formation containing the constituent material of the film for thermosetting protective film formation. For example, by applying the composition for forming a thermosetting protective film to the surface to be formed of the film for forming a thermosetting protective film, and drying the composition for forming a thermosetting protective film as necessary, it is possible to form a thermosetting film at the target site. A film for forming a curable protective film. The content ratio of the components which do not vaporize at normal temperature in the composition for thermosetting protective film formation is generally the same as the content ratio of the above-mentioned components in the film for thermosetting protective film formation. Here, the so-called "normal temperature" is as described above.
熱硬化性保護膜形成用組成物之塗敷例如可利用與上述黏著劑組成物之塗敷之情形相同的方法進行。 The coating of the composition for forming a thermosetting protective film can be performed by, for example, the same method as the coating of the above-mentioned adhesive composition.
熱硬化性保護膜形成用組成物之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時，較佳為進行加熱乾燥。含有溶劑之熱硬化性保護膜形成用組成物例如較佳為於70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the composition for forming a thermosetting protective film are not particularly limited, but when the composition for forming a thermosetting protective film contains a solvent described later, it is preferable to perform heat drying. The composition for forming a thermosetting protective film containing a solvent is preferably dried under the conditions of, for example, 70° C. to 130° C. and 10 seconds to 5 minutes.
<熱硬化性保護膜形成用組成物(III-1)> <The thermosetting 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，有時僅簡稱為「組成物(III-1)」)等。 As the composition for forming a thermosetting protective film, for example, the composition (III-1) for forming a thermosetting protective film containing a polymer component (A) and a thermosetting component (B) (in this specification, In some cases, it is only abbreviated as "composition (III-1)").
[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, and the like 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種以上之情形時，這些之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 two or more types; in the case of two or more types, a combination of these and the ratio can be arbitrarily selected.
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。 As the polymer component (A), for example, acrylic resins (resins having a (meth)acryloyl group), polyesters, and urethane resins (having a (meth)acryloyl group) may be mentioned. Resins with urethane bonds), urethane acrylate resins, polysiloxane resins (resins with siloxane bonds), rubber resins (resins with rubber structures), phenoxy resins, Thermosetting polyimide and the like are preferably acrylic resins.
再者，本說明書中，「(甲基)丙烯醯基」的概念係包括「丙烯醯基」及「甲基丙烯醯基」兩者。關於與(甲基)丙烯醯基類似的用語亦相同，例如，「(甲基)丙烯酸」的概念係包括「丙烯酸」及「甲基丙烯酸」兩者，「(甲基)丙烯酸酯」的概念係包括「丙烯酸酯」及「甲基丙烯酸酯」兩者。 In addition, in this specification, the concept of "(meth)acryloyl group" includes both "acryloyl group" and "methacryloyl group". The same applies to terms similar to (meth)acryloyl groups. For example, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid", and the concept of "(meth)acrylate" It includes both "acrylate" and "methacrylate".
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系聚合物。 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至2000000，更佳為100000至1500000。藉由丙烯酸系樹脂的重量平均分子量為前述下限值以上，熱硬化性保護膜形成用膜的形狀穩定性(保管時的經時穩定性)提高。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黏著體的凹凸面，可進一步抑制於被黏著體與熱硬化性保護膜形成用膜之間產生孔隙(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. The shape stability (time-dependent stability at the time of storage) of the film for thermosetting protective film formation improves by the weight average molecular weight of an acrylic resin being more than the said lower limit. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the above-mentioned upper limit value, the film for forming a thermosetting protective film can easily follow the uneven surface of the adherend, and the adherence and the thermosetting protective film can be further restrained. A void or the like is generated between the films for formation.
再者，本說明書中，所謂重量平均分子量，只要無特別說明，則為藉由凝膠滲透層析(GPC；Gel Permeation Chromatography)法所測定之聚苯乙烯換算值。 In addition, in this specification, the so-called weight average molecular weight is determined by gel permeation chromatography (GPC; Gel Permeation Chromatography) unless otherwise specified. The polystyrene conversion value measured by Chromatography) method.
丙烯酸系樹脂的玻璃轉移溫度(Tg)較佳為-60℃至70℃，更佳為-30℃至50℃。藉由丙烯酸系樹脂的Tg為前述下限值以上，可抑制保護膜與支撐片(黏著劑層)之接著力，支撐片之剝離性提高。另外，藉由丙烯酸系樹脂的Tg為前述上限值以下，熱硬化性保護膜形成用膜及保護膜與被黏著體之接著力提高。 The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -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) can be suppressed, and the peelability of a support sheet improves. Moreover, since the Tg of an acrylic resin is below the said upper limit, the adhesive force of the film for thermosetting protective film formation, a protective film, and a to-be-adhered body 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之2種以上之單體之共聚物等。 Examples of acrylic resins include polymers of one or more (meth)acrylates; polymers 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)丙烯酸環烯基酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯；(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」意指胺基之1個或2個氫原子被氫原子以外的基取代而成之基。 As said (meth)acrylate which comprises an acrylic resin, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate are mentioned, for example ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate (methyl)hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate Alkyl ester, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is a (meth)acrylate alkyl group with a chain structure of carbon number from 1 to 18 (Meth) cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate; (meth)acrylate aralkyl esters such as benzyl (meth)acrylate; ( (Meth) cycloalkenyl acrylates such as dicyclopentenyl meth)acrylate; (meth) cycloalkenyloxyalkyl acrylates such as dicyclopentenyloxyethyl (meth)acrylate; ) Acrylimide; Glycidyl (meth)acrylate and other glycidyl-containing (meth)acrylates; (meth)acrylate hydroxymethyl, (meth)acrylate 2-hydroxyethyl, (meth)acrylate ) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate (meth)acrylates containing hydroxyl groups such as esters; (meth)acrylates containing substituted amino groups such as N-methylaminoethyl (meth)acrylates, etc. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the 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合而成之樹脂。 For example, the acrylic resin may be selected from the group consisting of (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide, and the like in addition to the aforementioned (meth)acrylate. A resin obtained by copolymerizing one or two or more 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種以上之情形時，這些之組合及比率可任意選擇。 The monomer constituting the acrylic resin may be only one type, or two or more types may be used. above; in the case of two 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。丙烯酸系樹脂中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)與其他化合物直接鍵結。藉由使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的可靠性提高之傾向。 The acrylic resin may also have functional groups that can bond with other compounds, such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups. The functional group in the acrylic resin may be bonded to other compounds via the crosslinking agent (F) described later, or may be directly bonded to other compounds without the 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 making an acrylic resin couple|bond with 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，會有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黏著體的凹凸面，從而可進一步抑制於被黏著體與熱硬化性保護膜形成用膜之間產生孔隙等之情形。 In the present invention, as the polymer component (A), a thermoplastic resin other than the acrylic resin may be used alone without using the acrylic resin (hereinbelow, only abbreviated as "thermoplastic resin"), or may be used in combination with the acrylic resin. By using the above-mentioned thermoplastic resin, the peelability of the protective film from the supporting sheet is improved, or the film for forming a thermosetting protective film becomes easy to follow the uneven surface of the adherend, thereby further suppressing the adherence and thermosetting. The case where voids, etc. are generated between the films for forming a protective film.
前述熱塑性樹脂的重量平均分子量較佳為1000至100000，更佳為3000至80000。 The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.
前述熱塑性樹脂的玻璃轉移溫度(Tg)較佳為-30℃至150℃，更佳為-20℃至120℃。 The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 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, a polyurethane, a phenoxy resin, a polybutene, a polybutadiene, a 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種以上之情形時，這些之組合及比率可任意選擇。 The above-mentioned thermoplastic resin 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; in the case of two or more types, the combination and ratio of these may be Free to choose.
組成物(III-1)中，關於聚合物成分(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)，無論聚合物成分(A)的種類如何，均較佳為5質量%至85質量%，更佳為5質量%至80質量%，例如可為10質量%至70質量%、20質量%至60質量%、及30質量%至50質量%之任一者。 In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the polymer component (A) in the film for forming a thermosetting protective film) content), regardless of the type of the polymer component (A), preferably 5 to 85 mass %, more preferably 5 to 80 mass %, for example, 10 to 70 mass %, 20 mass % Any of 60 mass % and 30 mass % to 50 mass %.
會有聚合物成分(A)亦相當於熱硬化性成分(B)之情形。本發明中，於組成物(III-1)含有此種相當於聚合物成分(A)及熱硬化性成分(B)之兩者之成分之情形時，組成物(III-1)可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) can be regarded as containing A polymer component (A) and a 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之保護膜之成分。 The thermosetting component (B) is a component for forming a hard protective film by hardening the film for thermosetting protective film formation.
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種以上之情形時，這些之組合及比率可任意選擇。 Heat contained in the composition (III-1) and the film for forming a thermosetting protective film Only one type of curable component (B) may be used, or two or more types may be used; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.
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。 As the thermosetting component (B), for example, epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, polysiloxane resins, etc. may be mentioned, and preferably Epoxy 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種以上之情形時，這些之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 two or more types; in the case of two or more types, these Combinations and ratios can be arbitrarily selected.
．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。 As epoxy resin (B1), well-known epoxy resins are mentioned, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-cresol novolak epoxy resins are mentioned. 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有保護膜之半導體晶片的可靠性提高。 As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Compared with epoxy resins without unsaturated hydrocarbon groups, epoxy resins with unsaturated hydrocarbon groups Based on epoxy resin, it has high compatibility with acrylic resin. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the semiconductor wafer with a protective film obtained by using the composite sheet for protective film formation improves.
作為具有不飽和烴基之環氧樹脂，例如可列舉：多官能系環氧樹脂的一部分環氧基更換為具有不飽和烴基之基而成之化合物。此種化合物例如藉由使(甲基)丙烯酸或其衍生物與環氧基進行加成反應而獲得。 As an epoxy resin which has an unsaturated hydrocarbon group, the compound which replaced some epoxy groups of a polyfunctional epoxy resin with the group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction with an epoxy group.
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 couple|bonded directly with 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，作為該不飽和烴基之具體例，可列舉：次乙基(乙烯基)、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 ethylene (vinyl), 2-propenyl (allyl), (meth)acryloyl, A (meth)acrylamido group or the like is preferably an acrylamide 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至30000，更佳為300至10000，尤佳為300至3000。 The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30,000 in terms of the curability of the film for forming a thermosetting protective film, and the strength and heat resistance of the protective film after curing. , more preferably 300 to 10000, particularly preferably 300 to 3000.
環氧樹脂(B1)的環氧當量較佳為100g/eq至1000g/eq，更佳為150g/eq至950g/eq。 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種以上之情形時，這些之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; When using 2 or more types together, the combination and ratio of these can be selected arbitrarily.
．熱硬化劑(B2) . Thermal hardener (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 two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group formed by an anhydride, and preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride. The base formed is more preferably a phenolic hydroxyl group or an amine 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 phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol 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。 In a thermosetting agent (B2), as an amine type hardening agent which has an amine group, dicyandiamine (it may abbreviate "DICY" hereafter) etc. are mentioned, for example.
熱硬化劑(B2)亦可具有不飽和烴基。 The thermal hardener (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 with a group having an unsaturated hydrocarbon group, and 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)之情形時，就保護膜自支撐片之剝離性提高之方面而言，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 phenol-based hardener as the thermosetting agent (B2), the thermosetting agent (B2) is preferably a phenol having a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the supporting sheet. System 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至30000，更佳為400至10000，尤佳為500至3000。 In the thermosetting agent (B2), the number average molecular weight of resin components such as polyfunctional phenol resin, novolac-type phenol resin, dicyclopentadiene-type phenol resin, aralkyl-type phenol resin is preferably 300 to 30,000, more Preferably, it is 400 to 10,000, and more preferably, it is 500 to 3,000.
熱硬化劑(B2)中，例如聯苯酚、二氰二胺等非樹脂成分的分子量並無特別限定，例如較佳為60至500。 In the thermosetting agent (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited, but is preferably 60 to 500, for example.
熱硬化劑(B2)可單獨使用1種，亦可併用2種以上；於併用2種以上之情形時，這些之組合及比率可任意選擇。 A thermosetting agent (B2) may be used individually by 1 type, and may use 2 or more types together; When using 2 or more types together, the combination and ratio of these can be selected 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質量份至500質量份，更佳為1質量份至200質量份，例如可為1質量份至100質量份、1質量份至50質量份、及1質量份至25質量份之任一者。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 成用膜更易於進行硬化。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 to 500 parts by mass with respect to 100 parts by mass of the content of the epoxy resin (B1). , more preferably 1 to 200 parts by mass, for example, any of 1 to 100 parts by mass, 1 to 50 parts by mass, and 1 to 25 parts by mass. Since the said content of the thermosetting agent (B2) is more than the said lower limit value, the thermosetting protective film forms The resulting film is easier to harden. Moreover, when the said content of the thermosetting agent (B2) is below the said upper limit, the moisture absorption rate of the film for thermosetting protective film formation falls, and the reliability of the package obtained using the composite sheet for protective film formation is further improved .
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質量份至500質量份，更佳為30質量份至300質量份，尤佳為40質量份至150質量份，例如可為40質量份至125質量份、40質量份至100質量份、及40質量份至75質量份之任一者。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，支撐片的剝離性提高。 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 the material component (A) is 100 parts by mass, preferably 20 parts by mass to 500 parts by mass, more preferably 30 parts by mass to 300 parts by mass, particularly preferably 40 parts by mass to 150 parts by mass, for example, 40 parts by mass Any one of to 125 parts by mass, 40 parts by mass to 100 parts by mass, and 40 parts by mass to 75 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 improves.
[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 rate 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。 As preferable hardening accelerator (C), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. can be mentioned; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (one or more hydrogen atoms are replaced by hydrogen atoms) organic phosphine such as tributyl phosphine, diphenyl phosphine, triphenyl phosphine (phosphine in which more than 1 hydrogen atom is substituted by an organic group); tetraphenyl tetraphenyl borate Tetraphenylboron salts such as phosphonium, triphenylphosphine tetraphenylborate, 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種以上之情形時，這些之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; in the case of two or more types, the combination of these and the ratio can be arbitrarily selected.
於使用硬化促進劑(C)之情形時，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質量份至10質量份，更佳為0.1質量份至7質量份。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)所帶來之功效。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轉移而偏析之功效變高，從而使用保護膜形成用複合片所獲得之附有保護膜之半導體晶片的可靠性進一步提高。 In the case of using a curing accelerator (C), in the composition (III-1) and the film for forming a thermosetting protective film, the content of the curing accelerator (C) is 100 relative to the content of the thermosetting component (B) The mass part is preferably 0.01 to 10 mass parts, more preferably 0.1 to 7 mass parts. 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 obtained. In addition, when the content of the curing accelerator (C) is below the above-mentioned upper limit value, for example, the highly polar curing accelerator (C) is suppressed from reacting with the film for forming a thermosetting protective film under high temperature and high humidity conditions. The effect of transferring and segregating on the bonding interface side of the adhesive becomes high, and the reliability of the semiconductor wafer with a protective film obtained by using the composite sheet for forming a protective film 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。並且，藉由使該熱膨脹係數對於保護膜之形成對象物而言最適宜，使用保護膜形成用複合片所獲得之附有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). The film for forming a thermosetting protective film contains a filler (D), it is easy to adjust the thermal expansion coefficient of the protective film obtained by hardening the film for thermosetting protective film formation. And the reliability of the semiconductor wafer with a protective film obtained by using the composite sheet for protective film formation is further improved by making this thermal expansion coefficient optimal for the formation object of a protective film. 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, or heat dissipation can also be improved.
填充材料(D)可為有機填充材料及無機填充材料之任一者，較佳為無機填充材料。 The filler (D) may be any one of an organic filler and an inorganic filler, 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 fillers, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, iron dan, silicon carbide, boron nitride, etc. can be mentioned; these inorganic fillers are spherical Beads; surface modification 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.
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種以上之情形時，這些之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; in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.
於使用填充材料(D)之情形時，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%至80質量%，更佳為7質量%至60質 量%，例如可為10質量%至50質量%、15質量%至45質量%、及20質量%至40質量%之任一者。藉由填充材料(D)的含量為此種範圍，變得更容易調整上述之熱膨脹係數。 In the case of using the filler (D), the ratio of the content of the filler (D) to the total content of all components other than the solvent in the composition (III-1) (that is, for forming a thermosetting protective film) The content of the filler (D) in the film) is preferably 5 to 80% by mass, more preferably 7 to 60% by mass The amount % may be, for example, any of 10 to 50 mass %, 15 to 45 mass %, and 20 to 40 mass %. When the content of the filler (D) is in such a range, it becomes easier to adjust the above-mentioned thermal expansion coefficient.
[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黏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保護膜不損害耐熱性而耐水性提高。 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 a 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 with respect to a to-be-adhered body can be improved. Moreover, by using a coupling agent (E), the water resistance improves without impairing the heat resistance of the protective film obtained by hardening the film for thermosetting protective film formation.
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 functional groups possessed by the polymer component (A), the thermosetting component (B), and the like, and is more preferably a silane coupling agent.
作為較佳的前述矽烷偶合劑，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-(苯基胺基)丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3- 巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。 Examples of preferable silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Oxysilane, 3- mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, Vinyl triacetoxysilane, imidazosilane, 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種以上之情形時，這些之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 two or more types; in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.
於使用偶合劑(E)之情形時，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質量份至20質量份，更佳為0.05質量份至10質量份，尤佳為0.1質量份至5質量份。藉由偶合劑(E)的前述含量為前述下限值以上，可獲得更顯著的以下由使用偶合劑(E)所帶來之功效：填充材料(D)於樹脂中之分散性提高，或熱硬化性保護膜形成用膜與被黏著體之接著性提高等。另外，藉由偶合劑(E)的前述含量為前述上限值以下，可更進一步抑制產生逸氣。 When the coupling agent (E) is used, in the composition (III-1) and the film for forming a thermosetting protective film, the content of the coupling agent (E) is relative to the polymer component (A) and the thermosetting component ( The total content of B) is 100 parts by mass, preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass. By the above-mentioned content of the coupling agent (E) being more than the above-mentioned lower limit value, the following effect brought about by the use of the coupling agent (E) can be obtained more significantly: the dispersibility of the filler (D) in the resin is improved, or The adhesion between the film for forming a thermosetting protective film and the adherend is improved, etc. Moreover, when the said content of a coupling agent (E) is below the said upper limit, generation|occurrence|production of outgas can be suppressed further.
[交聯劑(F)] [Crosslinker (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)之情形時，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)。交聯劑(F)係用以使聚合物成分(A)中的前述官能基與其他化合物鍵結而進行交聯之成分，藉由如此進行交聯，可調節熱硬化性保護膜形成用膜的初期接著力及凝聚力。 In the case of using the above-mentioned acrylic resins having functional groups that can bond with other compounds, such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, isocyanate groups, etc., as the polymer component (A) When the composition (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F). The cross-linking agent (F) is a component for cross-linking by bonding the above-mentioned functional groups in the polymer component (A) with other compounds, and by cross-linking in this way, the film for forming a thermosetting protective film can be adjusted The initial adhesion and cohesion.
作為交聯劑(F)，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)、氮丙啶系交聯劑(具有氮丙啶基之交聯劑)等。 Examples of the crosslinking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate-based crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine-based 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」如上文所說明。 Examples of the organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate compounds, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers, etc. obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with a polyol compound, etc. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, which is mixed with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Reactant for low molecular active hydrogen compounds. As an example of the said adduct, the xylylene diisocyanate adduct of trimethylolpropane mentioned later, etc. are mentioned. In addition, the so-called "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；對三羥甲基丙烷等多元醇的全部或一部分羥基，加成甲苯二異氰酸酯、六亞甲基二異氰酸酯及苯二甲基二異氰酸酯的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。 As said organic polyvalent isocyanate compound, more specifically, 2, 4- toluene diisocyanate; 2, 6- toluene diisocyanate; 1, 3- xylylene diisocyanate; 1, 4- xylene diisocyanate are mentioned, for example Isocyanates; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; All or part of the hydroxyl groups of polyols such as p-trimethylolpropane, added with toluene diisocyanate, Any one or two or more compounds of hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.
作為前述有機多元亞胺化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶甲醯胺)、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、四羥甲基甲烷-三-β-氮丙啶基丙酸酯、N,N'-甲苯-2,4-雙(1-氮丙啶甲醯胺)三伸乙基三聚氰胺等。 As said organic polyvalent imine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-nitrogen Propidyl propionate, tetramethylolmethane-tri-beta-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) tris-ethyl melamine, etc.
於使用有機多元異氰酸酯化合物作為交聯劑(F)之情形時，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)具有羥基之情形時，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。 When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be easily introduced to the In the film for thermosetting protective film formation.
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種以上之情形時，這些之組合及比率可任意選擇。 Included in the composition (III-1) and the film for forming a thermosetting protective film Only one type of joint agent (F) may be used, or two or more types may be used; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.
於使用交聯劑(F)之情形時，組成物(III-1)中的交聯劑(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質量份至20質量份，更佳為0.1質量份至10質量份，尤佳為0.5質量份至5質量份。藉由交聯劑(F)的前述含量為前述下限值以上，可獲得更顯著的由使用交聯劑(F)所帶來之功效。另外，藉由交聯劑(F)的前述含量為前述上限值以下，可抑制交聯劑(F)之過量使用。 In the case of using the crosslinking agent (F), the content of the crosslinking agent (F) in the composition (III-1) is preferably 0.01 to 100 parts by mass relative to the content of the polymer component (A). 20 parts by mass, more preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass. When the said content of a crosslinking agent (F) is more than the said lower limit, the effect by using a crosslinking agent (F) is more remarkable. Moreover, since the said content of a crosslinking agent (F) is below the said upper limit, excessive use of a crosslinking agent (F) can be suppressed.
[能量線硬化性樹脂(G)] [Energy beam 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 contain the energy ray curable resin (G). Since the film for thermosetting protective film formation contains an energy ray curable resin (G), it can change a characteristic by irradiating an energy ray.
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 (hardening) 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。 As said energy-beam curable compound, the compound which has at least 1 polymerizable double bond in a molecule|numerator is mentioned, for example, Preferably it is an acrylate type compound which has a (meth)acryloyl 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；環氧改性(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。 As said acrylate type compound, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylic acid are mentioned, for example ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol dimethacrylate (Meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. (meth)acrylate containing chain aliphatic skeleton; Dicyclopentyl di(meth)acrylate, etc. (Meth)acrylate of aliphatic skeleton; Polyalkylene glycol (meth)acrylate such as polyethylene glycol di(meth)acrylate; Oligoester (meth)acrylate; (Meth)acrylic acid Urethane oligomers; Epoxy modified (meth)acrylates; Polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; Itaconic acid oligomers Wait.
前述能量線硬化性化合物的重量平均分子量較佳為100至30000，更佳為300至10000。 The weight average molecular weight of the aforementioned energy ray curable compound is preferably from 100 to 30,000, more preferably from 300 to 10,000.
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種以上之情形時，這些之組合及比率可任意選擇。 Only one type of the above-mentioned energy ray-curable compound used for polymerization may be used, or two or more types may be sufficient; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.
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種以上之情形時，這些之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 one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.
於使用能量線硬化性樹脂(G)之情形時，組成物(III-1)中的能量線硬化性樹脂(G)的含量較佳為1質量%至95質 量%，更佳為5質量%至90質量%，尤佳為10質量%至85質量%。 In the case of using the energy ray curable resin (G), the content of the energy ray curable resin (G) in the composition (III-1) is preferably 1% by mass to 95% by mass % by mass, more preferably 5% by mass to 90% by mass, particularly preferably 10% by mass to 85% by mass.
[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)之情形時，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), a photopolymerization initiator (H) may be contained in order to efficiently carry out the polymerization reaction of the energy ray-curable resin (G).
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、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫醚、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；偶氮二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, and benzoin methyl benzoate. Benzoin compounds such as esters, benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-di Acetophenone compounds such as phenylethan-1-one; bis(2,4,6-trimethylbenzyl) phenylphosphine oxide, 2,4,6-trimethylbenzyl diphenyl Acrylophosphine oxide compounds such as phosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azobisisobutyl Azo compounds such as nitriles; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; ; 2,4-Diethylthioxanthone; 1,2-Diphenylmethane; 2-Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2- Chloranthraquinone, 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種以上之情形時，這些之組合及比率可任意選擇。 The photopolymerization initiator (H) contained in the composition (III-1) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.
於使用光聚合起始劑(H)之情形時，組成物(III-1)之光聚合起始劑(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質量份至20質量份，更佳為1質量份至10質量份，尤佳為2質量份至5質量份。 In the case of using a photopolymerization initiator (H), the content of the photopolymerization initiator (H) of the composition (III-1) is preferably 100 parts by mass relative to the content of the energy ray-curable resin (G) It is 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass.
[著色劑(I)] [Colorant (I)]
組成物(III-1)及熱硬化性保護膜形成用膜亦可含有著色劑(I)。 The composition (III-1) and the film for forming a thermosetting protective film may contain a colorant (I).
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。 As a coloring agent (I), well-known coloring agents, such as an inorganic type pigment, an organic type pigment, and an organic type dye, are mentioned, for example.
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、偶氮色素、縮合偶氮色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁烷(dioxane)系色素、喹吖啶酮系色素、異吲哚啉酮系色素、喹啉黃(quinophthalone)系色素、吡咯系色素、硫代靛藍系色素、金屬錯合物系色素(金屬錯鹽染料)、二硫醇金 屬錯合物系色素、吲哚酚系色素、三烯丙基甲烷系色素、蒽醌系色素、萘酚系色素、次甲基偶氮系色素、苯并咪唑酮系色素、皮蒽酮系色素及士林(threne)系色素等。 Examples of the organic pigments and organic dyes include ammonium-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squalilium-based dyes, and azulium-based dyes. Pigments, polymethine based pigments, naphthoquinone based pigments, pyrylium based pigments, phthalocyanine based pigments, naphthalocyanine based pigments, naphthalamide based pigments, azo pigments, condensed azo pigments, indigo based pigments , Perinone dyes, perylene dyes, dioxane dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes, pyrrole dyes , thioindigo pigments, metal complex pigments (metal salt dyes), gold dithiolate It belongs to complex dyes, indoxyl dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, methine azo dyes, benzimidazolone dyes, and picanthrone dyes Pigments and threne 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, and ITO. (Indium Tin Oxide; indium tin oxide)-based dye, ATO (Antimony Tin Oxide; antimony tin oxide)-based dye, and the like.
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種以上之情形時，這些之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 two or more types; in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.
於使用著色劑(I)之情形時，熱硬化性保護膜形成用膜中的著色劑(I)的含量根據目的適宜調節即可。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，可調節對保護膜進行雷射印字之情形時的印字視認性。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，或者使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0.1質量%至10質量%，更佳 為0.1質量%至7.5質量%，尤佳為0.1質量%至5質量%。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)所帶來之功效。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), content of the coloring agent (I) in the film for thermosetting protective film formation may be adjusted 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 printing visibility when laser printing is performed on the protective film can be adjusted. In addition, by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film, the designability of the protective film can be improved, or the grinding traces on the back surface of the semiconductor wafer can be made less visible. Taking this aspect into consideration, 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 0.1% by mass to 10% by mass, more preferably It is 0.1 mass % to 7.5 mass %, and it is especially preferable that it is 0.1 mass % to 5 mass %. When the aforementioned content of the colorant (I) is more than the aforementioned lower limit value, a more significant effect by using the colorant (I) can be obtained. Moreover, when the said content of a coloring agent (I) is below the said upper limit, it can suppress that the light transmittance of the film for thermosetting protective film formation falls too much.
[通用添加劑(J)] [General Additives (J)]
組成物(III-1)及熱硬化性保護膜形成用膜中，亦可在無損本發明的功效之範圍內，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 that does not impair 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) may be a known additive, and can be arbitrarily selected according to the purpose without particular limitation. As the preferred general-purpose additive (J), for example, a plasticizer, an antistatic agent, an antioxidant, and a getter can be mentioned. (gettering agent), etc.
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種以上之情形時，這些之組合及比率可任意選擇。 The general additive (J) 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; in the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.
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，根據目的適宜選擇即可。 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)較佳為進一步含有溶劑。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 solvent-containing composition (III-1) has good handleability.
前述溶劑並無特別限定，作為較佳的前述溶劑，例如 可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(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 solvent is not particularly limited, and as the preferred aforementioned solvent, for example Examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; Ethyl ketone and other ketones; tetrahydrofuran and other ethers; dimethylformamide, N-methylpyrrolidone and other amides (compounds with amide bonds) and the like.
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種以上之情形時，這些之組合及比率可任意選擇。 The solvent contained in the composition (III-1) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.
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 from the viewpoint that the components contained in the composition (III-1) can be mixed more uniformly.
<<熱硬化性保護膜形成用組成物的製造方法>> <<The manufacturing method of the composition for thermosetting protective film formation>>
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。 The composition for thermosetting protective film formation, such as composition (III-1), is obtained by mixing each component which comprises this composition.
調配各成分時之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 at the time of preparing each component is not particularly limited, and two or more components may be added at the same time.
於使用溶劑之情形時，亦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 also be used by mixing the solvent with any preparation component other than the solvent and diluting the preparation component in advance; it can also be used in the following way: without mixing any preparation components other than the solvent. A formulating ingredient is pre-diluted and the solvent is mixed with the formulating ingredients.
調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the components during the preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing 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，適宜調節即可，溫度較佳為15℃至30℃。 The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.
○能量線硬化性保護膜形成用膜 ○Energy ray curable protective film forming 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 energy ray curable protective film formation 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」如上文所說明。 In the film for energy ray curable protective film formation, the energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and is more preferably uncured and adhesive. Here, the so-called "energy ray" and "energy ray sclerosis" 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層以上之複數層，於為複數層之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The film for forming an energy ray curable protective film may be only one layer (single layer), or may be a plurality of layers of two or more layers. In the case of a plurality of layers, these layers may be the same or different from each other. The combination is not particularly limited.
能量線硬化性保護膜形成用膜的厚度較佳為1μm至100μm，更佳為5μm至75μm，尤佳為5μm至50μm。藉由能量線硬化性保護膜形成用膜的厚度為前述下限值以上，可形成保護能力更高的保護膜。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，可抑制成為過厚的厚度。 The thickness of the film for forming an energy ray-curable protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and still more preferably 5 μm to 50 μm. By making the thickness of the film for energy ray curable protective film formation more than the said lower limit, the protective film with higher protective ability can be formed. Moreover, since the thickness of the film for energy ray curable protective film formation is below the said upper limit, it can suppress that it becomes an excessively thick thickness.
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，例如所謂由複數層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 so-called "thickness of the film for forming an energy ray-curable protective film" It means the thickness of the whole film for forming an energy ray curable protective film, for example, the thickness of the film for forming an energy ray curable protective film composed of a plurality of layers means the sum of all the layers constituting the film for forming an energy ray curable protective film. thickness.
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宜選擇即可。 Regarding the curing conditions when the film for forming an energy ray-curable protective film is attached to the back surface of a semiconductor wafer and cured to form a protective film, as long as the protective film has a degree of curing sufficient to fully exhibit the function of the protective film, the It does not specifically limit, What is necessary is just to select suitably according to the kind of the 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，能量線的照度較佳為120mW/cm2至280mW/cm2。並且，前述硬化時，能量線的光量較佳為200mW/cm2至1000mJ/cm2。 For example, in the curing of the film for forming an energy ray-curable protective film, the illuminance of the energy ray is preferably 120 mW/cm 2 to 280 mW/cm 2 . In addition, in the aforementioned curing, the light intensity of the energy beam is preferably 200 mW/cm 2 to 1000 mJ/cm 2 .
<<能量線硬化性保護膜形成用組成物>> <<The composition for forming an 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，視需要使能量線硬化性保護膜形成用組成物乾燥，藉此可於目標的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」如上文所說明。 The film for energy ray curable protective film formation can be formed using the composition for energy ray curable protective film formation containing the constituent material of the film. For example, by applying the composition for forming an energy ray curable protective film to the surface to be formed of the film for forming an energy ray curable protective film, and drying the composition for forming an energy ray curable protective film as necessary, it is possible to apply the composition for forming an energy ray curable protective film to the target surface. A film for forming an energy ray curable protective film is formed at the site. The content ratio of the components which do not vaporize at normal temperature in the composition for energy ray curable protective film formation is usually the same as the content ratio of the aforementioned components in the film for energy ray curable protective film formation. Here, the so-called "normal temperature" is as described above.
能量線硬化性保護膜形成用組成物之塗敷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進行。 The application of the composition for forming an energy ray-curable protective film can be performed by, for example, the same method as in the case of the above-mentioned application of the adhesive composition.
能量線硬化性保護膜形成用組成物之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時，較佳為進行加熱乾燥。含有溶劑之能量線硬化性保護膜形成用組成物例如較佳為於70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the composition for forming an energy ray curable protective film are not particularly limited, but when the composition for forming an energy ray curable protective film contains a solvent described later, it is preferable to perform heat drying. The composition for forming an energy ray curable protective film containing a solvent is preferably dried under the conditions of, for example, 70° C. to 130° C. for 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 energy-ray-curable protective film-forming composition include the energy-ray-curable protective film-forming composition (IV-1) (in this specification, it may be simply abbreviated as the energy ray curable component (a)), for example. "Composition (IV-1)") and the like.
[能量線硬化性成分(a)] [energy ray sclerosing component (a)]
能量線硬化性成分(a)係藉由照射能量線而硬化之成分，該成分用以對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 irradiating energy rays, 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 material 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至2000000之聚合物(a1)、及具有能量線硬化性基且分子量為100至80000之化合物(a2)。前述聚合物(a1)可該聚合物的至少一部分 藉由交聯劑進行交聯，亦可不進行交聯。 Examples of the energy ray curable component (a) include a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray curable group and a molecular weight of 100 to 80,000. (a2). The aforementioned polymer (a1) may be at least a part of the polymer The crosslinking may be performed by a crosslinking agent or not.
(具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)) (Polymer (a1) having an energy ray hardening group and 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至2000000之聚合物(a1)，例如可列舉丙烯酸系樹脂(a1-1)，該丙烯酸系樹脂(a1-1)係使丙烯酸系聚合物(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) which is an acrylic polymer (a1-1). a11) The acrylic polymer (a11) is formed by reacting with an energy ray curable compound (a12), the acrylic polymer (a11) having a functional group reactive with a group of another compound, and the energy ray curable compound (a12) has the same functional group as the above-mentioned Energy ray hardening groups such as functional groups reacting groups and energy ray hardening double bonds.
作為可與其他化合物所具有之基反應之前述官能基，例如可列舉：羥基、羧基、胺基、取代胺基(胺基的1個或2個氫原子被氫原子以外的基取代而成之基)、環氧基等。但是，就防止半導體晶圓或半導體晶片等的電路腐蝕之方面而言，前述官能基較佳為羧基以外的基。 Examples of the functional group that can react with groups contained in other compounds include a hydroxyl group, a carboxyl group, an amino group, and a substituted amino group (a group in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom). group), epoxy group, etc. However, it is preferable that the said functional group is a group other than a carboxyl group from the viewpoint of preventing circuit corrosion of a semiconductor wafer, 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 group (a11)
前述具有官能基之丙烯酸系聚合物(a11)例如可列舉：使前述具有官能基之丙烯酸系單體與前述不具有官能基之丙烯酸系單體進行共聚合而成之聚合物，亦可為除了這些單體以外，進一步使丙烯酸系單體以外的單體(非丙 烯酸系單體)進行共聚合而成之聚合物。 The acryl-based polymer (a11) having a functional group may be, for example, a polymer obtained by copolymerizing the acrylic monomer having a functional group and an acrylic monomer having no functional group. In addition to these monomers, monomers other than acrylic monomers (non-acrylic A polymer obtained by copolymerizing an alkenoic acid monomer).
另外，前述丙烯酸系聚合物(a11)可為無規共聚物，亦可為嵌段共聚物，關於聚合方法，亦可採用公知的方法。 Moreover, the said acrylic polymer (a11) may be a random copolymer or a block copolymer, and a well-known method may be employ|adopted for a polymerization method.
作為前述具有官能基之丙烯酸系單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含取代胺基之單體、含環氧基之單體等。 Examples of the functional group-containing acrylic monomer include hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, substituted amino group-containing monomers, epoxy group-containing monomers, and the like .
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, and 3-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth)acrylates such as hydroxypropyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols having no (meth)acryloyl skeleton), and the like.
作為前述含羧基之單體，例如可列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；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。 Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds) such as maleic acid and citraconic acid; anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. (methyl methacrylate) base) carboxyalkyl acrylate, 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 monomer having the aforementioned functional group is preferably a hydroxyl-containing mono body.
構成前述丙烯酸系聚合物(a11)之前述具有官能基之丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The functional group-containing acrylic monomer constituting the acrylic polymer (a11) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.
作為前述不具有官能基之丙烯酸系單體，例如，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 acrylic monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate (methyl)hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Hexaalkyl esters (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute alkyl esters The alkyl group is an alkyl (meth)acrylate having a chain structure of 1 to 18 carbon atoms.
另外，作為前述不具有官能基之丙烯酸系單體，例如亦可列舉：(甲基)丙烯酸甲氧基甲酯、(甲基)丙烯酸甲氧 基乙酯、(甲基)丙烯酸乙氧基甲酯、(甲基)丙烯酸乙氧基乙酯等含烷氧基烷基之(甲基)丙烯酸酯；包含(甲基)丙烯酸苯酯等(甲基)丙烯酸芳基酯等之具有芳香族基之(甲基)丙烯酸酯；非交聯性的(甲基)丙烯醯胺及其衍生物；(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丙酯等非交聯性的具有三級胺基之(甲基)丙烯酸酯等。 Moreover, as an acryl-type monomer which does not have the said functional group, (meth)acrylate methoxymethyl, (meth)acrylate methoxymethyl can also be mentioned, for example. (meth)acrylates containing alkoxyalkyl groups such as ethyl ethyl ester, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate; including phenyl (meth)acrylate, etc. ( (Meth)acrylates having aromatic groups such as aryl meth)acrylates; non-crosslinkable (meth)acrylamides and derivatives thereof; (meth)acrylate N,N-dimethylamine Non-crosslinkable (meth)acrylates with tertiary amine groups, such as ethyl ethyl ester and N,N-dimethylaminopropyl (meth)acrylate.
構成前述丙烯酸系聚合物(a11)之前述不具有官能基之丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The acryl-based monomer that does not have a functional group constituting the acryl-based polymer (a11) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected .
作為前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.
構成前述丙烯酸系聚合物(a11)之前述非丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The said non-acrylic-type monomer which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types; In the case of 2 or more types, the combination and ratio of these can be selected arbitrarily.
前述丙烯酸系聚合物(a11)中，由前述具有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)之結構單元的全部量之比例(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，由前述丙烯酸系聚合物(a11)與前述能量線硬化性化合物(a12)之共聚合所獲得之前述丙烯酸系樹脂(a1-1)中，能量線硬化 性基的含量能夠容易地調節為使保護膜的硬化程度較佳的範圍。 In the acrylic polymer (a11), the ratio (content) of the amount of the structural units derived from the functional group-containing acrylic monomer to the total amount of the structural units constituting the acrylic polymer (a11) is preferable It is 0.1 mass % to 50 mass %, More preferably, it is 1 mass % to 40 mass %, Especially preferably, it is 3 mass % to 30 mass %. Since the ratio is in this range, in the acrylic resin (a1-1) obtained by the copolymerization of the acrylic polymer (a11) and the energy ray curable compound (a12), the energy ray hardening The content of the property group can be 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種以上之情形時，這些之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; In the case of 2 or more types, the combination and ratio of these can be selected arbitrarily.
樹脂層形成用組成物(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%至70質量%，更佳為5質量%至60質量%，尤佳為10質量%至50質量%，例如可為15質量%至50質量%、25質量%至50質量%、及35質量%至50質量%之任一者。 In the composition (IV-1) for forming a resin layer, 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 acid in the film for forming an energy ray-curable protective film) The content of the resin (a1-1) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, particularly preferably 10 to 50% by mass, for example, 15 to 50% by mass Any of 50 mass %, 25 mass % to 50 mass %, and 35 mass % to 50 mass %.
．能量線硬化性化合物(a12) . Energy ray hardening compound (a12)
前述能量線硬化性化合物(a12)較佳為具有選自由異氰酸酯基、環氧基及羧基所組成之群組中的1種或2種以上作為可與前述丙烯酸系聚合物(a11)所具有之官能基反應之基，更佳為具有異氰酸酯基作為前述基。於前述能量線硬化性化合物(a12)例如具有異氰酸酯基作為前述基之情形時，該異氰酸酯基與前述具有羥基作為官能基之丙烯酸系聚合物(a11)的該羥基容易反應。 The aforementioned energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a compound that the aforementioned acrylic polymer (a11) has. More preferably, the functional group reacts with an isocyanate group as the aforementioned group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as a functional group.
前述能量線硬化性化合物(a12)較佳為於1分子中具有1個至5個前述能量線硬化性基，更佳為具有1個至3個。 It is preferable that the said energy ray hardening compound (a12) has 1 to 5 said energy ray hardening groups in 1 molecule, More preferably, it has 1 to 3 pieces.
作為前述能量線硬化性化合物(a12)，例如可列舉：異氰酸2-甲基丙烯醯氧基乙酯、間-異丙烯基-α,α-二甲基苄基異氰酸酯、甲基丙烯醯基異氰酸酯、異氰酸烯丙酯、異氰酸1,1-(雙丙烯醯氧基甲基)乙酯；藉由二異氰酸酯化合物或多異氰酸酯化合物與(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物；藉由二異氰酸酯化合物或多異氰酸酯化合物、多元醇化合物及(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物等。 Examples of the energy ray curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacryloyl isocyanate. diisocyanate, allyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate; by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate Acryloyl 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, it is preferable that the said energy ray curable compound (a12) is 2-methacryloyloxyethyl isocyanate.
構成前述丙烯酸系樹脂(a1-1)之前述能量線硬化性化合物(a12)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之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 two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected .
前述丙烯酸系樹脂(a1-1)中，源自前述能量線硬化性化合物(a12)之能量線硬化性基的含量相對於源自前述丙烯酸系聚合物(a11)之前述官能基的含量之比例較佳為20莫耳%至120莫耳%，更佳為35莫耳%至100莫耳%，尤 佳為50莫耳%至100莫耳%。藉由前述含量之比例為此種範圍，硬化後的保護膜的接著力進一步變大。再者，於前述能量線硬化性化合物(a12)為一官能(於1分子中具有1個前述基)化合物之情形時，前述含量之比例的上限值成為100莫耳%，但於前述能量線硬化性化合物(a12)為多官能(於1分子中具有2個以上前述基)化合物之情形時，會有前述含量之比例的上限值超過100莫耳%之情形。 In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) Preferably it is 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, especially Preferably, it is 50 mol % to 100 mol %. When the ratio of the said content is in such a range, the adhesive force of the protective film after hardening becomes further large. Furthermore, in the case where the energy ray-curable compound (a12) is a monofunctional (having one of the aforementioned groups in 1 molecule) compound, the upper limit of the ratio of the aforementioned content is 100 mol%, but in the aforementioned energy When the linear curable compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the ratio of the aforementioned content may exceed 100 mol %.
前述聚合物(a1)的重量平均分子量(Mw)較佳為100000至2000000，更佳為300000至1500000。 The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably 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」如上文所說明。 Here, the so-called "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時，前述聚合物(a1)可使不符合上述說明之構成前述丙烯酸系聚合物(a11)之任一單體且具有與交聯劑反應之基之單體進行聚合，在前述與交聯劑反應之基中進行交聯，亦可在源自前述能量線硬化性化合物(a12)之與前述官能基反應之基中進行交聯。 When at least a part of the above-mentioned polymer (a1) is cross-linked by a cross-linking agent, the above-mentioned polymer (a1) may be any monomer constituting the above-mentioned acrylic polymer (a11) which does not meet the above description and The monomer having a group reactive with the crosslinking agent is polymerized, and the crosslinking is performed in the group reactive with the crosslinking agent, or the group derived from the energy ray curable compound (a12) and the functional group reactive with the above-mentioned can also be carried out. 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種以上之情形時，這些之組合及比率可任意選擇。 The above-mentioned 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 two or more types; in the case of two or more types, these Combinations and ratios can be arbitrarily selected.
(具有能量線硬化性基且分子量為100至80000之化 合物(a2)) (with energy ray hardening group and molecular weight of 100 to 80000 Compound (a2))
作為具有能量線硬化性基且分子量為100至80000之化合物(a2)中的前述能量線硬化性基，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 in the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80,000 include groups containing an energy-ray-curable double bond, and preferable examples of the group include (methyl base) acrylyl, vinyl, etc.
若前述化合物(a2)滿足上述條件，則並無特別限定，可列舉：具有能量線硬化性基之低分子量化合物、具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂等。 The compound (a2) is not particularly limited as long as it satisfies the above-mentioned conditions, and examples thereof include a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and a phenol resin having an energy ray curable group. Wait.
前述化合物(a2)中，作為具有能量線硬化性基之低分子量化合物，例如可列舉多官能之單體或低聚物等，較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。 In the said compound (a2), as a low molecular weight compound which has an energy ray hardening group, a polyfunctional monomer, an oligomer, etc. are mentioned, for example, Preferably it is an acrylate type compound which has a (meth)acryloyl group.
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、聚丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基乙氧基)苯基]丙烷、新戊二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯、2-羥基-1,3-二(甲基)丙烯醯氧基丙烷等2官能(甲基)丙烯酸酯；異氰脲酸三(2-(甲基)丙烯醯氧基乙基)酯、ε-己內酯改性異氰脲酸三-(2-(甲基)丙烯醯氧基乙基)酯、乙氧基化甘油三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇聚(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯低聚物等多官能(甲基)丙烯酸酯低聚物等。 As said acrylate type compound, for example, 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxy bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acrylooxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(methyl) ) acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxy) ethoxy) phenyl] stilbene, 2,2-bis[4-((meth)acryloyloxypolypropoxy)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(methyl) base) acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acrylooxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, Ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acrylooxypropane and other 2-functional (meth)acrylates; tris(2-isocyanurate) (Meth)acryloyloxyethyl)ester, ε-caprolactone-modified isocyanurate tris-(2-(meth)acryloyloxyethyl)ester, ethoxylated glycerol tris(methyl) base) acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate base) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other polyfunctional (meth)acrylates; (meth)acrylate amino group Polyfunctional (meth)acrylate oligomers such as formate 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」中的段落0043等中所記載之樹脂。此種樹脂亦相當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 Laid-Open No. 2013-194102" can be used. The recorded resin. This resin also corresponds to the resin constituting the 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至30000，更佳為300至10000。 The weight average molecular weight of the aforementioned compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.
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種以上之情形時，這些之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 type or two or more types; in the case of two or more types, a combination of these may be used and the ratio can be arbitrarily selected.
[不具有能量線硬化性基之聚合物(b)] [Polymer (b) without energy ray 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)之情形時，較佳為亦進一步含有不具有能量線硬化性基之聚合物(b)。 When 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 compound (a2) which does not have energy ray curability. base 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。 At least a part of the said polymer (b) may be crosslinked by a crosslinking agent, and may not be crosslinked.
作為不具有能量線硬化性基之聚合物(b)，例如可列舉：丙烯酸系聚合物、苯氧基樹脂、胺基甲酸酯樹脂、聚酯、橡膠系樹脂、丙烯酸胺基甲酸酯樹脂等。 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, abbreviated as "acrylic polymer (b-1)" in some cases).
丙烯酸系聚合物(b-1)可為公知的聚合物，例如可為1種丙烯酸系單體的均聚物，亦可為2種以上丙烯酸系單體的共聚物，還可為1種或2種以上丙烯酸系單體與1種或2種以上除丙烯酸系單體以外的單體(非丙烯酸系單體)之共聚物。 The acrylic polymer (b-1) may be a known polymer, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a single or A copolymer of two or more acrylic monomers and one or more monomers (non-acrylic monomers) other than 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」如上文所說明。 Examples of the aforementioned acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, and (meth)acrylates having a glycidyl group. group) acrylate, hydroxyl group-containing (meth)acrylate, substituted amine group-containing (meth)acrylate, 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 alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate n-butyl meth)acrylate, isobutyl (meth)acrylate, 2nd butyl (meth)acrylate, 3rd 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, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. It is a (meth)acrylic acid alkyl ester of a chain structure with a carbon number of 1 to 18, and the like.
作為前述具有環狀骨架之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯等(甲 基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯基酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯等。 As (meth)acrylate which has the said cyclic skeleton, (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. (meth)acrylate, etc. are mentioned, for example (meth) cycloalkyl acrylate; (meth) aralkyl acrylate such as benzyl acrylate; (meth) cycloalkenyl acrylate such as dicyclopentenyl acrylate; (meth) acrylate ) Dicyclopentenyloxyethyl acrylate and the like (meth)cycloalkenyloxyalkyl acrylate and the like.
作為前述含縮水甘油基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸縮水甘油酯等。 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 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, and the like.
作為前述含取代胺基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸N-甲基胺基乙酯等。 As said substituted amino group containing (meth)acrylate, (meth)acrylate N-methylaminoethyl 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。 As said non-acrylic-type monomer which comprises an acrylic-type polymer (b-1), olefin, such as ethylene and norbornene; vinyl acetate; styrene, etc. are mentioned, for example.
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之聚合物。 Examples of the polymer (b) that is at least partially cross-linked by a cross-linking agent and does not have the above-mentioned energy ray-curable group include polymerization in which the reactive functional group in the above-mentioned polymer (b) reacts with a cross-linking agent. thing.
前述反應性官能基根據交聯劑之種類等適宜選擇即可，並無特別限定。例如，於交聯劑為多異氰酸酯化合物 之情形時，作為前述反應性官能基，可列舉羥基、羧基、胺基等，這些之中較佳為與異氰酸酯基之反應性高之羥基。另外，於交聯劑為環氧系化合物之情形時，作為前述反應性官能基，可列舉羧基、胺基、醯胺基等，這些之中，較佳為與環氧基之反應性高之羧基。但是，就防止半導體晶圓或半導體晶片的電路腐蝕之方面而言，前述反應性官能基較佳為羧基以外的基。 The reactive functional group may be appropriately selected according to the type of the crosslinking agent and the like, and is not particularly limited. For example, the crosslinking agent is a polyisocyanate compound In this case, the reactive functional group includes a hydroxyl group, a carboxyl group, an amine group, and the like, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. In addition, when the crosslinking agent is an epoxy-based compound, examples of the reactive functional group include a carboxyl group, an amino group, an amide group, and the like, and among these, the one with high reactivity with an epoxy group is preferred. carboxyl. However, the 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：至少使具有前述反應性官能基之單體進行聚合而獲得之聚合物。於丙烯酸系聚合物(b-1)之情形時，作為構成該丙烯酸系聚合物(b-1)之單體所列舉之前述丙烯酸系單體及非丙烯酸系單體的任一者或兩者，使用具有前述反應性官能基之單體即可。作為具有羥基作為反應性官能基之前述聚合物(b)，例如可列舉使含羥基之(甲基)丙烯酸酯進行聚合而獲得之聚合物，除此以外，亦可列舉使上文所列舉之前述丙烯酸系單體或非丙烯酸系單體中1個或2個以上氫原子被前述反應性官能基取代而成之單體進行聚合而獲得之聚合物。 As a polymer (b) which has the said reactive functional group and does not have an energy ray hardening group, the polymer obtained by polymerizing at least the monomer which has the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), either or both of the aforementioned acrylic monomers and non-acrylic monomers listed as the monomers constituting the acrylic polymer (b-1) , the monomer with the aforementioned reactive functional group can be used. As said polymer (b) which has a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth)acrylate can be mentioned. A polymer obtained by polymerizing a monomer in which one or more hydrogen atoms in the aforementioned acrylic monomer or non-acrylic monomer are substituted with the aforementioned reactive functional group.
具有反應性官能基之前述聚合物(b)中，由具有反應性官能基之單體衍生之結構單元的量相對於構成該聚合物(b)之結構單元的全部量之比例(含量)較佳為1質量%至20質量%，更佳為2質量%至10質量%。藉由前述比例為 此種範圍，前述聚合物(b)中，交聯程度成為更佳的範圍。 In the aforementioned polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural units constituting the polymer (b) is relatively Preferably it is 1 mass % - 20 mass %, More preferably, it is 2 mass % - 10 mass %. By the aforementioned ratio of In such a range, in the aforementioned polymer (b), the degree of crosslinking becomes 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至2000000，更佳為100000至1500000。此處，所謂「重量平均分子量」如上文所說明。 The weight average molecular weight (Mw) of the polymer (b) not having an energy ray hardening group is preferably from 10,000 to 2,000,000, more preferably 100,000, from the viewpoint that the film-forming properties of the composition (IV-1) are better. to 1500000. Here, the so-called "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種以上之情形時，這些之組合及比率可任意選擇。 The polymer (b) that does not have an energy ray curable group contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be one type or two or more types; In the above case, the combination and ratio of these can be arbitrarily selected.
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)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)之情形時，較佳為亦進一步含有不具有能量線硬化性基之聚合物(b)，該情形時，亦較佳為進一步含有前述(a1)。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)。 As the composition (IV-1), a composition containing either or both of the above-mentioned polymer (a1) and the above-mentioned compound (a2) can be mentioned. In addition, when the composition (IV-1) contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) without an energy ray curable group, and in this case, it is also preferable to further contain (a1) above. Moreover, a composition (IV-1) may not contain the said compound (a2), and may contain the said polymer (a1) and the polymer (b) which does not have an energy ray curable group together.
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)之情形時，組成物(IV-1)中，前述化合物(a2)的含量相對於前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)的總含量100質量 份，較佳為10質量份至400質量份，更佳為30質量份至350質量份。 When the composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) without an energy ray curable group, in the composition (IV-1), the compound The content of (a2) is based on 100 mass of the total content of the polymer (a1) and the polymer (b) having no energy ray curable group. parts, preferably 10 to 400 parts by mass, more preferably 30 to 350 parts by mass.
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(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)相對於溶劑以外的成分的總含量之比例較佳為5質量%至90質量%，更佳為10質量%至80質量%，尤佳為20質量%至70質量%。藉由能量線硬化性成分的含量的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 total content of the energy ray curable component (a) and the polymer (b) having no energy ray curable group (that is, the total content of the energy ray curable protective film forming film) The ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group) to the total content of components other than the solvent is preferably 5 to 90% by mass, and more 10 to 80 mass % is preferable, and 20 to 70 mass % is particularly preferable. When the said ratio of content of an energy ray curable component is such a range, the energy ray curability of the film for energy ray curable protective film formation becomes more favorable.
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黏著體之接著力提高，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。 The composition (IV-1) may contain, in addition to the above-mentioned energy ray curable components, components selected from the group consisting of thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and One or more of the group consisting of general-purpose additives. For example, by using the composition (IV-1) containing the above-mentioned energy ray curable component and thermosetting component, the formed film for energy ray curable protective film formation can be heated to improve the adhesive force to the adherend , the strength of the protective film formed from the energy ray-curable protective film-forming 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)相同之化合物。 As the aforementioned thermosetting components, fillers, coupling agents, cross-linking agents, photopolymerization initiators, colorants, and general-purpose additives in the composition (IV-1) Agents include: the thermosetting component (B), the filler (D), the coupling agent (E), the crosslinking agent (F), the photopolymerization initiator (H) in the composition (III-1), respectively. ), colorant (I) and general additive (J) are the same compounds.
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種以上之情形時，這些之組合及比率可任意選擇。 In the composition (IV-1), the aforementioned thermosetting components, fillers, coupling agents, cross-linking agents, photopolymerization initiators, colorants and general additives may be used alone or in combination of two or more; When two or more types are used together, the combination and ratio of these can be arbitrarily selected.
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宜調節即可，並無特別限定。 Contents of the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives in the composition (IV-1) may be appropriately adjusted according to the purpose, and are not particularly limited.
就藉由稀釋而使該組成物的操作性提高而言，組成物(IV-1)較佳為進一步含有溶劑。 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)中的溶劑相同之溶劑。 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 type or two or more types.
<<能量線硬化性保護膜形成用組成物的製造方法>> <<The manufacturing method of the composition for energy ray curable protective film forming>>
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。 The composition for energy ray curable protective film formation, such as the composition (IV-1), can be obtained by mixing each component which comprises the composition.
調配各成分時之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 at the time of preparing each component is not particularly limited, and two or more components may be added at the same time.
於使用溶劑之情形時，可藉由下述方式使用：將溶劑與溶劑以外的任一種調配成分混合而將該調配成分預先稀釋；亦可藉由下述方式使用：不將溶劑以外的任一種調配成分預先稀釋而將溶劑與這些調配成分混合。 In the case of using a solvent, it can be used by mixing the solvent with any preparation component other than the solvent and diluting the preparation component in advance; it can also be used in the following way: not using any preparation component other than the solvent The formulating ingredients are pre-diluted and the solvent is mixed with these formulating ingredients.
調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the components during the preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing 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，適宜調節即可，溫度較佳為15℃至30℃。 The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.
◇支撐片的製造方法、保護膜形成用複合片的製造方法 ◇Manufacturing method of support sheet, manufacturing method of composite sheet for protective film formation
前述支撐片及保護膜形成用複合片可藉由將上述各層以成為對應的位置關係之方式依序積層而製造。各層的形成方法如上文所說明。 The said support sheet and the composite sheet for protective film formation can be manufactured by laminating|stacking the said each layer sequentially so that it may become a corresponding positional relationship. The formation method of each layer is as described above.
例如，製造支撐片時，於基材上積層黏著劑層之情形時，於基材上塗敷上述之黏著劑組成物，視需要使黏著劑組成物乾燥即可。 For example, in the case of laminating an adhesive layer on a base material when manufacturing a support sheet, the above-mentioned adhesive composition is coated on the base material, and the adhesive composition may be dried as necessary.
另一方面，例如，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一步積層保護膜形成用膜之情形時，可於黏著劑層上塗敷熱硬化性保護膜形成用組 成物或能量線硬化性保護膜形成用組成物而直接形成保護膜形成用膜。如此，於使用任一組成物，形成連續之2層積層結構之情形時，可於由前述組成物形成之層上進一步塗敷組成物而新形成層。但是，較佳為使用前述組成物於另一剝離膜上預先形成這些2層中後積層之層，使該已形成之層中的與和前述剝離膜接觸之側為相反側的露出面，與既已形成之其餘層的露出面貼合，藉此形成連續之2層積層結構。此時，前述組成物較佳為塗敷於剝離膜的剝離處理面。形成積層結構後，視需要移除剝離膜即可。 On the other hand, for example, in the production of a composite sheet for forming a protective film, when a film for forming a protective film is further laminated on the adhesive layer already laminated on the base material, a thermosetting protective film can be applied on the adhesive layer. forming group The product or the composition for forming an energy ray-curable protective film is directly formed into a film for forming a protective film. In this way, when any one of the compositions is used to form a continuous two-layer laminate structure, a new layer can be formed by further coating the composition on the layer formed of the above-mentioned composition. However, it is preferable to preliminarily form a layer of these two layers after the lamination on another release film using the above-mentioned composition, so that the side of the formed layer that is in contact with the above-mentioned release film is the exposed surface on the opposite side, and The exposed surfaces of the remaining layers that have already been formed are bonded to form a continuous two-layer laminate structure. In this case, it is preferable that the said composition is apply|coated to the peeling process surface of a peeling film. After the layered structure is formed, the release film may be removed as necessary.
亦即，於製造保護膜形成用複合片之情形時，藉由下述方式而獲得保護膜形成用複合片：於基材上塗敷黏著劑組成物，視需要使黏著劑組成物乾燥，藉此於基材上預先積層黏著劑層，並另外於剝離膜上塗敷熱硬化性保護膜形成用組成物或能量線硬化性保護膜形成用組成物，視需要使熱硬化性保護膜形成用組成物或能量線硬化性保護膜形成用組成物乾燥，藉此於剝離膜上預先形成保護膜形成用膜，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，於黏著劑層上積層保護膜形成用膜。 That is, in the case of producing a composite sheet for forming a protective film, the composite sheet for forming a protective film is obtained by applying an adhesive composition on a base material, and drying the adhesive composition as necessary, thereby obtaining a composite sheet for forming a protective film. The adhesive layer is preliminarily laminated on the base material, and the composition for forming a thermosetting protective film or the composition for forming an energy ray curable protective film is separately coated on the release film. If necessary, the composition for forming a thermosetting protective film is applied. Or the composition for forming an energy ray-curable protective film is dried, whereby a film for forming a protective film is preliminarily formed on the release film, and the exposed surface of the film for forming a protective film and the adhesive layer laminated on the base material are formed. The exposed surface is bonded, and the film for protective film formation is laminated on the adhesive layer.
另一方面，於基材上積層黏著劑層之情形時，如上述般，代替於基材上塗敷黏著劑組成物之方法，亦可於剝離膜上塗敷黏著劑組成物，視需要使黏著劑組成物乾燥，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。 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 may be applied on the release film. The composition is dried, borrowed The adhesive layer is pre-formed on the release film, and the exposed surface of the adhesive layer is attached to a surface of the substrate, thereby laminating the adhesive layer on the substrate.
任一方法中，均於形成目標的積層結構後的任意時間點移除剝離膜即可。 In either method, the release film may be removed at any point in time after the formation of the target laminate structure.
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，再貼合於目標的層的表面之方法進行積層，因此視需要適宜選擇採用此種步驟之層，製造保護膜形成用複合片即可。 In this way, layers other than the base material constituting the composite sheet for protective film formation (adhesive layer, film for protective film formation) can be formed on the release film in advance and then laminated on the surface of the target layer. Therefore, the layer to be used in such a step may be appropriately selected as necessary to manufacture a composite sheet for forming a protective film.
但是，本發明中，基材中的黏著劑層的積層面的表面粗糙度亦即第1面的表面粗糙度為0.1μm至0.4μm或上述附近之值，為無法忽視該面的凹凸度之程度之情形時，較佳為藉由於基材上塗敷黏著劑組成物之方法，形成黏著劑層(形成支撐片)。原因在於，於此種凹凸面貼合預先已形成之黏著劑層之情形時，例如於該面的凸部的根部附近的部位未填充黏著劑層而產生空隙部，黏著劑層對於該面(第1面)之埋入變得不充分。如此，若第1面之埋入變得不充分，則會產生如上文說明之不良情況。 However, in the present invention, the surface roughness of the build-up layer of the adhesive layer in the base material, that is, the surface roughness of the first surface is 0.1 μm to 0.4 μm or a value in the vicinity of the above-mentioned value, so that the unevenness of the surface cannot be ignored. In the case of this degree, it is preferable to form an adhesive layer (to form a support sheet) by a method of coating the adhesive composition on the substrate. The reason is that, when such a concave-convex surface is pasted with a pre-formed adhesive layer, for example, the adhesive layer is not filled with the adhesive layer in the vicinity of the root of the convex portion of the surface, and a void portion is formed, and the adhesive layer is very important to the surface ( Embedding of the 1st side) becomes insufficient. In this way, if the embedding of the first surface becomes insufficient, the inconvenience described above will occur.
相對於此，於對基材的第1面塗敷黏著劑組成物而形成黏著劑層之情形時，具有流動性之黏著劑組成物亦充分填充至第1面的凸部的根部附近的部位，結果為黏著劑層 充分地埋入這些部位，因此可高度抑制產生如上述之不良情況。但是，例如，亦可於對基材的第1面貼合黏著劑層時，將黏著劑層加熱使之軟化，藉此抑制產生前述空隙部。因此，有時亦可應用將預先已形成之黏著劑層貼合於基材的第1面之方法。 On the other hand, when the adhesive composition is applied to the first surface of the base material to form an adhesive layer, the adhesive composition having fluidity is also sufficiently filled to the position near the root of the convex portion on the first surface. , the result is an adhesive layer Since these parts are sufficiently embedded, the occurrence of the above-mentioned inconveniences can be suppressed to a high degree. However, for example, when the adhesive layer is bonded to the first surface of the base material, the adhesive layer may be heated and softened, thereby suppressing the occurrence of the aforementioned voids. Therefore, the method of sticking the previously formed adhesive bond layer to the 1st surface of a base material may be applied.
再者，保護膜形成用複合片通常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，亦可藉由下述方式而獲得保護膜形成用複合片：於該剝離膜(較佳為該剝離膜的剝離處理面)上塗敷熱硬化性保護膜形成用組成物或能量線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，視需要使該組成物乾燥，藉此於剝離膜上預先形成構成最表層之層，於該層中的與和剝離膜接觸之側為相反側的露出面上利用上述任一種方法積層其餘各層，不移除剝離膜而保持貼合狀態不變。 In addition, the composite sheet for protective film formation is usually stored in a state where a release film is bonded to the surface of the outermost layer (eg, film for protective film formation) on the opposite side to the support sheet in the composite sheet for protective film formation. Therefore, a composite sheet for forming a protective film can also be obtained by applying a composition for forming a thermosetting protective film or an energy ray curable on the peeling film (preferably the peeling treated surface of the peeling film). A composition for forming a protective film, etc., a composition for forming a layer constituting the outermost layer, and drying the composition as necessary, whereby a layer constituting the outermost layer is formed on the release film in advance, and the layer constituting the outermost layer is formed in the layer and the release film. The exposed surface on the opposite side to the contact side is laminated with the remaining layers by any of the above methods, without removing the release film and maintaining the bonded state.
[實施例] [Example]
以下，藉由具體的實施例對本發明進行更詳細的說明。但是，本發明並不受以下所示之實施例之任何限定。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited at all by the examples shown below.
再者，以下表示下述實施例等中的保護膜形成用複合片的各層的構成。 In addition, the structure of each layer of the composite sheet for protective film formation in the following Examples etc. is shown below.
<基材> <Substrate>
以下表示構成支撐片之基材。 The base material constituting the support sheet is shown below.
基材Bm1：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.05μm，凹凸面的表面粗糙度(Ra)為0.1μm之基材。 Base material Bm1: Based on polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.05 μm, and the surface roughness (Ra) of the uneven surface is 0.1 μm. material.
基材Bm2：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.05μm，凹凸面的表面粗糙度(Ra)為0.2μm之基材。 Base material Bm2: Based on polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.05 μm, and the surface roughness (Ra) of the uneven surface is 0.2 μm. material.
基材Bm3：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.05μm，凹凸面的表面粗糙度(Ra)為0.3μm之基材。 Base material Bm3: Based on polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.05 μm, and the surface roughness (Ra) of the uneven surface is 0.3 μm. material.
基材Bm4：以聚對苯二甲酸丁二酯作為主要構成材料，厚度為80μm，拉伸彈性率為500MPa，平滑面的表面粗糙度(Ra)為0.05μm，凹凸面的表面粗糙度(Ra)為0.3μm之基材。 Base material Bm4: with polybutylene terephthalate as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 500 MPa, the surface roughness (Ra) of the smooth surface is 0.05 μm, and the surface roughness (Ra) of the uneven surface is 0.05 μm. ) is a 0.3 μm substrate.
基材Bm5：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，雙面為表面粗糙度(Ra)為0.05μm之平滑面之基材。 Base material Bm5: A base material with polypropylene as the main constituent material, a thickness of 80 μm, a tensile elastic modulus of 360 MPa, and a smooth surface with a surface roughness (Ra) of 0.05 μm on both sides.
基材Bm6：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.05μm，凹凸面的表面粗糙度(Ra)為0.5μm之基材。 Base material Bm6: Based on polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.05 μm, and the surface roughness (Ra) of the uneven surface is 0.5 μm. material.
基材Bm7：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.05μm，凹凸面的表面粗糙度(Ra)為0.055μm之基材。 Base material Bm7: Based on polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.05 μm, and the surface roughness (Ra) of the uneven surface is 0.055 μm. material.
基材Bm8：以聚丙烯作為主要構成材料，厚度為 80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.03μm，凹凸面的表面粗糙度(Ra)為0.4μm之基材。 Base material Bm8: with polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.03 μm, and the surface roughness (Ra) of the uneven surface is 0.4 μm.
基材Bm9：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.03μm，凹凸面的表面粗糙度(Ra)為0.47μm之基材。 Base material Bm9: Based on polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.03 μm, and the surface roughness (Ra) of the uneven surface is 0.47 μm. material.
基材Bm10：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.35μm，凹凸面的表面粗糙度(Ra)為0.4μm之基材。 Base material Bm10: Based on polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.35 μm, and the surface roughness (Ra) of the uneven surface is 0.4 μm. material.
基材Bm11：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.37μm，凹凸面的表面粗糙度(Ra)為0.47μm之基材。 Base material Bm11: Based on polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.37 μm, and the surface roughness (Ra) of the uneven surface is 0.47 μm. material.
基材Bm12：以聚丙烯作為主要構成材料，厚度為80μm，拉伸彈性率為360MPa，平滑面的表面粗糙度(Ra)為0.43μm，凹凸面的表面粗糙度(Ra)為0.47μm之基材。 Base material Bm12: Based on polypropylene as the main constituent material, the thickness is 80 μm, the tensile elastic modulus is 360 MPa, the surface roughness (Ra) of the smooth surface is 0.43 μm, and the surface roughness (Ra) of the uneven surface is 0.47 μm. material.
再者，前述基材的拉伸彈性率及表面粗糙度係利用以下所示之方法測定之值。 In addition, the tensile elastic modulus and the surface roughness of the said base material are the values measured by the method shown below.
(基材的拉伸彈性率之測定) (Measurement of Tensile Elastic Modulus of Substrate)
將基材裁斷而製作試片，依據JIS K7161：1994，測定23℃下的前述試片的拉伸彈性率(楊式率)。此時，將前述試片之測定時之寬度設為15mm，將夾具間距離設為100mm。 The base material was cut out to prepare a test piece, and the tensile modulus (Young's modulus) of the test piece at 23° C. was measured in accordance with JIS K7161:1994. At this time, the width of the test piece at the time of measurement was set to 15 mm, and the distance between the jigs was set to 100 mm.
(基材的表面粗糙度之測定) (Measurement of Surface Roughness of Substrate)
依據JIS B 0601：2001，使用接觸式表面形狀測定裝 置(Mitsutoyo公司製造之「SURFTEST SV-3000」)，將臨界值λ c設為0.8mm，將評價長度Ln設為10mm，測定基材的表面的表面粗糙度(Ra)。 According to JIS B 0601:2001, using a contact surface profile measuring device A set (“SURFTEST SV-3000” manufactured by Mitsutoyo Co., Ltd.) was used, the critical value λ c was set to 0.8 mm, and the evaluation length Ln was set to 10 mm, and the surface roughness (Ra) of the surface of the substrate was measured.
<黏著性樹脂> <Adhesive resin>
以下表示用於形成黏著劑層之黏著性樹脂。 The following shows the adhesive resin used to form the adhesive layer.
黏著性樹脂(i)-1：使丙烯酸正丁酯(以下，簡稱為「BA」)(85質量份)、及丙烯酸-2-羥基乙酯(以下，簡稱為「HEA」)(15質量份)進行共聚合而成之重量平均分子量600000之丙烯酸系聚合物。 Adhesive resin (i)-1: n-butyl acrylate (hereinafter abbreviated as “BA”) (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) (15 parts by mass) ) is an acrylic polymer with a weight average molecular weight of 600,000 obtained by copolymerization.
黏著性樹脂(i)-2：使丙烯酸2-乙基己酯(以下，簡稱為「2EHA」)(30質量份)、丙烯酸異冰片酯(以下，簡稱為「iBA」)(50質量份)、及HEA(20質量份)進行共聚合而成之重量平均分子量800000之丙烯酸系聚合物。 Adhesive resin (i)-2: 2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (30 parts by mass), isobornyl acrylate (hereinafter abbreviated as "iBA") (50 parts by mass) , and HEA (20 parts by mass) were copolymerized to obtain an acrylic polymer with a weight average molecular weight of 800,000.
<保護膜形成用組成物的製造原料> <Production raw material of the composition for forming a protective film>
以下表示用於製造保護膜形成用組成物之原料。 The raw materials for producing the composition for forming a protective film are shown below.
[聚合物成分(A)] [Polymer component (A)]
(A)-1：使BA(10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HEA(15質量份)進行共聚合而成之丙烯酸系樹脂(重量平均分子量800000，玻璃轉移溫度-1℃)。 (A)-1: Acrylic resin obtained by copolymerizing BA (10 parts by mass), methyl acrylate (70 parts by mass), glycidyl methacrylate (5 parts by mass), and HEA (15 parts by mass) (weight average molecular weight 800000, glass transition temperature -1°C).
[熱硬化性成分(B)] [Thermosetting component (B)]
．環氧樹脂(B1) . Epoxy resin (B1)
(B1)-1：雙酚A型環氧樹脂(三菱化學公司製造之「JER828」，環氧當量183g/eq至194g/eq，數量平均分子量370)。 (B1)-1: Bisphenol A epoxy resin (“JER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 183 g/eq to 194 g/eq, number average molecular weight 370).
(B1)-2：雙酚A型環氧樹脂(三菱化學公司製造之「JER1055」，環氧當量800g/eq至900g/eq，數量平均分子量1600)。 (B1)-2: Bisphenol A epoxy resin (“JER1055” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 800 g/eq to 900 g/eq, number average molecular weight 1600).
(B1)-3：二環戊二烯型環氧樹脂(DIC公司製造之「Epicron HP-7200HH」，環氧當量255g/eq至260g/eq)。 (B1)-3: Dicyclopentadiene-type epoxy resin (“Epicron HP-7200HH” manufactured by DIC Corporation, epoxy equivalent: 255 g/eq to 260 g/eq).
．熱硬化劑(B2) . Thermal hardener (B2)
(B2)-1：二氰二胺(熱活性潛伏性環氧樹脂硬化劑，ADEKA公司製造之「Adeka Hardener EH-3636AS」，活性氫量21g/eq)。 (B2)-1: Dicyandiamide (heat-active latent epoxy resin hardener, "Adeka Hardener EH-3636AS" manufactured by ADEKA, active hydrogen amount 21 g/eq).
[硬化促進劑(C)] [Hardening accelerator (C)]
(C)-1：2-苯基-4,5-二羥基甲基咪唑(四國化成工業公司製造之「Curezol 2PHZ」)。 (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole (“Curezol 2PHZ” manufactured by Shikoku Chemical Industry Co., Ltd.).
[填充材料(D)] [filler (D)]
(D)-1：二氧化矽填料(Admatechs公司之「SC2050MA」，利用環氧系化合物進行了表面修飾，平均粒徑0.5μm)。 (D)-1: silica filler (“SC2050MA” from Admatechs, surface-modified with epoxy compound, average particle size 0.5 μm).
[偶合劑(E)] [Coupling agent (E)]
(E)-1：3-縮水甘油氧基丙基三甲氧基矽烷(3-縮水甘油氧基丙基三甲氧基矽烷)(矽烷偶合劑，信越化學工業公司製造之「KBM403」，甲氧基當量12.7mmol/g，分子量236.3)。 (E)-1: 3-glycidyloxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane) (silane coupling agent, "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd., methoxyl Equivalent weight 12.7 mmol/g, molecular weight 236.3).
[交聯劑(F)] [Crosslinker (F)]
(F)-1：甲苯二異氰酸酯系交聯劑(Toyochem公司製造之「BHS8515」)。 (F)-1: Toluene diisocyanate-based crosslinking agent (“BHS8515” manufactured by Toyochem Corporation).
[光聚合起始劑(H)] [Photopolymerization initiator (H)]
光聚合起始劑(H)-1：1-羥基環己基苯基酮(BASF公司製造之「Irgacure(註冊商標)184」)。 Photopolymerization initiator (H)-1: 1-hydroxycyclohexyl phenyl ketone ("Irgacure (registered trademark) 184" manufactured by BASF Corporation).
[著色劑(I)] [Colorant (I)]
(I)-1：碳黑(三菱化學公司製造之「MA600B」，平均粒徑28nm) (I)-1: Carbon black (“MA600B” manufactured by Mitsubishi Chemical Corporation, average particle size: 28 nm)
[能量線硬化性成分(a)] [energy ray sclerosing component (a)]
能量線硬化性成分(a)-1：使2EHA(80質量份)及HEA(20質量份)進行共聚合而成之丙烯酸系聚合物，與異氰酸2-甲基丙烯醯氧基乙酯(以下，簡稱為「MOI」)(相對於前述丙烯酸系聚合物中的源自HEA之羥基的總莫耳數，異氰酸2-甲基丙烯醯氧基乙酯中的異氰酸酯基的總莫耳數成為0.8倍之量)反應而獲得之側鏈具有甲基丙烯醯氧基之重量平均分子量800000、玻璃轉移溫度-10℃之紫外線硬化型丙烯酸系共聚物。 Energy ray curable component (a)-1: an acrylic polymer obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass), and 2-methacryloyloxyethyl isocyanate (Hereinafter, abbreviated as "MOI") (Total molar of isocyanate groups in 2-methacryloyloxyethyl isocyanate relative to the total moles of hydroxyl groups derived from HEA in the aforementioned acrylic polymer The number of ears becomes 0.8 times the amount) to obtain a UV-curable acrylic copolymer having a weight-average molecular weight of methacryloyloxy in the side chain of 800,000 and a glass transition temperature of -10°C.
<保護膜形成用複合片之製造> <Manufacture of the composite sheet for protective film formation>
[實施例1] [Example 1]
(熱硬化性保護膜形成用組成物(III-1)之製造) (Production of Thermosetting Protective Film Forming Composition (III-1))
將聚合物成分(A)-1(40質量份)、環氧樹脂(B1)-1(5質量份)、環氧樹脂(B1)-2(4質量份)、環氧樹脂(B1)-3(10質 量份)、熱硬化劑(B2)-1(1質量份)、硬化促進劑(C)-1(1質量份)、填充材料(D)-1(36質量份)、偶合劑(E)-1(1質量份)、及著色劑(I)-1(2質量份)進行混合，進一步利用甲基乙基酮以固形物成分的濃度成為45質量%之方式進行稀釋，獲得熱硬化性保護膜形成用組成物(III-1)。再者，此處所示之甲基乙基酮以外的成分的調配量全部為固形物成分量。 Polymer component (A)-1 (40 parts by mass), epoxy resin (B1)-1 (5 parts by mass), epoxy resin (B1)-2 (4 parts by mass), epoxy resin (B1)- 3 (10 quality parts), thermosetting agent (B2)-1 (1 mass part), hardening accelerator (C)-1 (1 mass part), filler (D)-1 (36 mass parts), coupling agent (E) -1 (1 part by mass) and coloring agent (I)-1 (2 parts by mass) were mixed, and further diluted with methyl ethyl ketone so that the concentration of solid content was 45 mass % to obtain thermosetting properties Composition (III-1) for forming a protective film. In addition, the compounding quantities of the components other than methyl ethyl ketone shown here are all solid content amounts.
(保護膜形成用膜之形成) (Formation of protective film forming film)
於聚對苯二甲酸乙二酯製膜的單面藉由聚矽氧處理進行了剝離處理而成之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm)的前述剝離處理面，塗敷上述所獲得之組成物(III-1)，於100℃下乾燥3分鐘，藉此形成厚度為25μm之保護膜形成用膜Pf1。 A release film (“SP-PET381031” manufactured by Lintec, thickness 38 μm) obtained by peeling off one side of a polyethylene terephthalate film by polysiloxane treatment was applied to the peel-treated side. The above-obtained composition (III-1) was applied and dried at 100° C. for 3 minutes to form a protective film-forming film Pf1 having a thickness of 25 μm.
(黏著劑組成物之製造) (Manufacture of adhesive composition)
將黏著性樹脂(i)-1(100質量份)、及甲苯二異氰酸酯系交聯劑(Toyochem公司製造之「BHS8515」)(1質量份)進行混合，進一步利用甲基乙基酮以固形物成分的濃度成為35質量%之方式進行稀釋，獲得非能量線硬化性的黏著劑組成物(I-4)-1。再者，此處所示之甲基乙基酮以外的成分的調配量全部為固形物成分量。 Adhesive resin (i)-1 (100 parts by mass) and a toluene diisocyanate-based crosslinking agent (“BHS8515” manufactured by Toyochem) (1 part by mass) were mixed, and the solid content was further obtained by using methyl ethyl ketone. It diluted so that the density|concentration of a component might become 35 mass %, and the non-energy-beam curable adhesive composition (I-4)-1 was obtained. In addition, the compounding quantities of the components other than methyl ethyl ketone shown here are all solid content amounts.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
於上述之基材Bm1的表面粗糙度為0.05μm之平滑面，塗敷上述所獲得之黏著劑組成物(I-4)-1，於100℃下乾燥1分鐘，藉此形成厚度為5μm且為非能量線硬化性之黏著劑層Ad1，獲得支撐片Ss1。 The adhesive composition (I-4)-1 obtained above was coated on the smooth surface of the above-mentioned substrate Bm1 with a surface roughness of 0.05 μm, and dried at 100° C. for 1 minute to form a thickness of 5 μm and a A support sheet Ss1 was obtained as the non-energy ray-curable adhesive layer Ad1.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss1中的黏著劑層Ad1的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The structure shown in FIG. 2 was obtained by laminating the exposed surface of the protective film-forming film Pf1 obtained above on the side without the release film and the exposed surface of the adhesive layer Ad1 in the support sheet Ss1 The protective film forming composite sheet.
該保護膜形成用複合片係基材Bm1、黏著劑層Ad1、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm1中的具備有黏著劑層Ad1之側的面為平滑面，基材Bm1中的與具備有黏著劑層Ad1之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表1。 The composite sheet for forming a protective film is formed by laminating the base material Bm1, the adhesive layer Ad1, the film Pf1 for forming a protective film, and the release film in this order in the thickness direction, and the base material Bm1 has the adhesive layer Ad1. The side surface is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad1 in the base material Bm1 is an uneven surface. The structure of this composite sheet for protective film formation is shown in Table 1.
[實施例2] [Example 2]
形成黏著劑層時，改變黏著劑組成物(I-4)-1的塗敷量，形成厚度為20μm而非5μm且為非能量線硬化性之黏著劑層Ad2，使用所獲得之支撐片Ss2，除此方面以外，利用與實施例1相同的方法，製造保護膜形成用複合片。 When the adhesive layer was formed, the coating amount of the adhesive composition (I-4)-1 was changed to form an adhesive layer Ad2 with a thickness of 20 μm instead of 5 μm and a non-energy ray hardening property, using the obtained support sheet Ss2 , except for this point, by the same method as in Example 1, a composite sheet for forming a protective film was produced.
亦即，該保護膜形成用複合片係基材Bm1、黏著劑層Ad2、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方 向上積層而成，基材Bm1中的具備有黏著劑層Ad2之側的面為平滑面，基材Bm1中的與具備有黏著劑層Ad2之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表1。 That is, the composite sheet-based base material Bm1 for forming a protective film, the adhesive layer Ad2, the film Pf1 for forming a protective film, and the release film are in this order in the thickness direction of these. In the base material Bm1, the surface on the side with the adhesive layer Ad2 is a smooth surface, and the surface (exposed surface) on the opposite side to the side with the adhesive layer Ad2 in the base material Bm1 is a concave-convex surface. . The structure of this composite sheet for protective film formation is shown in Table 1.
[實施例3] [Example 3]
(黏著劑組成物之製造) (Manufacture of adhesive composition)
將黏著性樹脂(i)-2(100質量份)、及甲苯二異氰酸酯系交聯劑(Toyochem公司製造之「BHS8515」)(10質量份)進行混合，進一步利用甲基乙基酮以固形物成分的濃度成為35質量%之方式進行稀釋，獲得非能量線硬化性的黏著劑組成物(I-4)-2。再者，此處所示之甲基乙基酮以外的成分的調配量全部為固形物成分量。 Adhesive resin (i)-2 (100 parts by mass) and a toluene diisocyanate-based crosslinking agent (“BHS8515” manufactured by Toyochem) (10 parts by mass) were mixed, and the solid content was further prepared with methyl ethyl ketone. It diluted so that the density|concentration of a component might become 35 mass %, and the non-energy-beam curable adhesive composition (I-4)-2 was obtained. In addition, the compounding quantities of the components other than methyl ethyl ketone shown here are all solid content amounts.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
於上述之基材Bm1的表面粗糙度為0.05μm之平滑面，塗敷上述所獲得之黏著劑組成物(I-4)-2，於100℃下乾燥1分鐘，藉此形成厚度為5μm且為非能量線硬化性之黏著劑層Ad3，獲得支撐片Ss3。 The adhesive composition (I-4)-2 obtained above was coated on the smooth surface of the above-mentioned base material Bm1 with a surface roughness of 0.05 μm, and dried at 100° C. for 1 minute, thereby forming a thickness of 5 μm and a A support sheet Ss3 was obtained as the non-energy ray-curable adhesive layer Ad3.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
使用上述所獲得之支撐片Ss3代替支撐片Ss1，除此方面以外，利用與實施例1相同的方法，製造保護膜形成用複合片。 A composite sheet for forming a protective film was produced by the same method as in Example 1 except that the support sheet Ss3 obtained above was used in place of the support sheet Ss1.
亦即，該保護膜形成用複合片係基材Bm1、黏著劑層Ad3、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm1中的具備有黏著劑層Ad3之側的面為平滑面，基材Bm1中的與具備有黏著劑層Ad3之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表1。 That is, the composite sheet-based base material Bm1 for forming a protective film, the adhesive layer Ad3, the film Pf1 for forming a protective film, and the release film are laminated in this order in the thickness direction, and the base material Bm1 is provided with an adhesive. The surface on the side of the layer Ad3 is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad3 in the base material Bm1 is an uneven surface. The structure of this composite sheet for protective film formation is shown in Table 1.
[實施例4] [Example 4]
(黏著劑組成物之製造) (Manufacture of adhesive composition)
利用與實施例3相同的方法，獲得黏著劑組成物(I-4)-2。 By the same method as Example 3, the adhesive composition (I-4)-2 was obtained.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
於上述之基材Bm2的表面粗糙度為0.05μm之平滑面，塗敷上述所獲得之黏著劑組成物(I-4)-2，於100℃下乾燥1分鐘，藉此形成厚度為5μm且為非能量線硬化性之黏著劑層Ad3，獲得支撐片Ss4。 The adhesive composition (I-4)-2 obtained above was coated on the smooth surface of the above-mentioned substrate Bm2 with a surface roughness of 0.05 μm, and dried at 100° C. for 1 minute to form a thickness of 5 μm and a A support sheet Ss4 was obtained as the non-energy ray-curable adhesive layer Ad3.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
使用上述所獲得之支撐片Ss4代替支撐片Ss1，除此方面以外，利用與實施例1相同的方法，製造保護膜形成用複合片。 A composite sheet for forming a protective film was produced by the same method as in Example 1 except that the support sheet Ss4 obtained above was used in place of the support sheet Ss1.
亦即，該保護膜形成用複合片係基材Bm2、黏著劑層Ad3、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方 向上積層而成，基材Bm2中的具備有黏著劑層Ad3之側的面為平滑面，基材Bm2中的與具備有黏著劑層Ad3之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表1。 That is, the composite sheet-based base material Bm2 for forming a protective film, the adhesive layer Ad3, the film Pf1 for forming a protective film, and the release film are in this order in the thickness direction of these. The surface of the base material Bm2 on the side with the adhesive layer Ad3 is a smooth surface, and the surface (exposed surface) on the opposite side to the side with the adhesive layer Ad3 in the base material Bm2 is a concave-convex surface. . The structure of this composite sheet for protective film formation is shown in Table 1.
[實施例5] [Example 5]
(黏著劑組成物之製造) (Manufacture of adhesive composition)
利用與實施例3相同的方法，獲得黏著劑組成物(I-4)-2。 By the same method as Example 3, the adhesive composition (I-4)-2 was obtained.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
於上述之基材Bm3的表面粗糙度為0.05μm之平滑面，塗敷上述所獲得之黏著劑組成物(I-4)-2，於100℃下乾燥1分鐘，藉此形成厚度為5μm且為非能量線硬化性之黏著劑層Ad3，獲得支撐片Ss5。 The adhesive composition (I-4)-2 obtained above was coated on the smooth surface of the above-mentioned base material Bm3 with a surface roughness of 0.05 μm, and dried at 100° C. for 1 minute to form a thickness of 5 μm and a A support sheet Ss5 was obtained as the non-energy ray-curable adhesive layer Ad3.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
使用上述所獲得之支撐片Ss5代替支撐片Ss1，除此方面以外，利用與實施例1相同的方法，製造保護膜形成用複合片。 A composite sheet for forming a protective film was produced by the same method as in Example 1 except that the support sheet Ss5 obtained above was used in place of the support sheet Ss1.
亦即，該保護膜形成用複合片係基材Bm3、黏著劑層Ad3、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm3中的具備有黏著劑層Ad3之側的面為平滑面，基材Bm3中的與具備有黏著劑層Ad3之 側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表1。 That is, the composite sheet-based base material Bm3 for forming a protective film, the adhesive layer Ad3, the film Pf1 for forming a protective film, and the release film are laminated in this order in the thickness direction, and the base material Bm3 is provided with an adhesive. The surface on the side of the layer Ad3 is a smooth surface, and the surface between the base material Bm3 and the adhesive layer Ad3 is The surface on the opposite side (exposed surface) is an uneven surface. The structure of this composite sheet for protective film formation is shown in Table 1.
[實施例6] [Example 6]
(黏著劑組成物之製造) (Manufacture of adhesive composition)
利用與實施例3相同的方法，獲得黏著劑組成物(I-4)-2。 By the same method as Example 3, the adhesive composition (I-4)-2 was obtained.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
於上述之基材Bm4的表面粗糙度為0.05μm之平滑面，塗敷上述所獲得之黏著劑組成物(I-4)-2，於100℃下乾燥1分鐘，藉此形成厚度為5μm且為非能量線硬化性之黏著劑層Ad3，獲得支撐片Ss6。 The adhesive composition (I-4)-2 obtained above was coated on the smooth surface of the above-mentioned substrate Bm4 with a surface roughness of 0.05 μm, and dried at 100° C. for 1 minute to form a thickness of 5 μm and a A support sheet Ss6 was obtained as the non-energy ray-curable adhesive layer Ad3.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
使用上述所獲得之支撐片Ss6代替支撐片Ss1，除此方面以外，利用與實施例1相同的方法，製造保護膜形成用複合片。 A composite sheet for forming a protective film was produced by the same method as in Example 1 except that the support sheet Ss6 obtained above was used in place of the support sheet Ss1.
亦即，該保護膜形成用複合片係基材Bm4、黏著劑層Ad3、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm4中的具備有黏著劑層Ad3之側的面為平滑面，基材Bm4中的與具備有黏著劑層Ad3之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表1。 That is, the composite sheet-based base material Bm4 for forming a protective film, the adhesive layer Ad3, the film Pf1 for forming a protective film, and the release film are laminated in this order in the thickness direction, and the base material Bm4 is provided with an adhesive. The surface on the side of the layer Ad3 is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad3 in the base material Bm4 is an uneven surface. The structure of this composite sheet for protective film formation is shown in Table 1.
[實施例7] [Example 7]
(能量線硬化性保護膜形成用組成物(IV-1)之製造) (Production of Energy Ray Curable Protective Film Forming Composition (IV-1))
將能量線硬化性成分(a)-1(42質量份)、填充材料(D)-1(55質量份)、偶合劑(E)-1(0.3質量份)、交聯劑(F)-1(1質量份)、光聚合起始劑(H)-1(0.3質量份)、及著色劑(I)-1(1質量份)進行混合，進一步利用甲基乙基酮以固形物成分的濃度成為45質量%之方式進行稀釋，獲得能量線硬化性保護膜形成用組成物(IV-1)。再者，此處所示之甲基乙基酮以外的成分的調配量全部為固形物成分量。 Energy ray curable component (a)-1 (42 parts by mass), filler (D)-1 (55 parts by mass), coupling agent (E)-1 (0.3 parts by mass), crosslinking agent (F)- 1 (1 part by mass), the photopolymerization initiator (H)-1 (0.3 part by mass), and the coloring agent (I)-1 (1 part by mass) were mixed, and the solid content was further obtained by using methyl ethyl ketone. It diluted so that the density|concentration might become 45 mass %, and obtained the composition (IV-1) for energy ray curable protective film formation. In addition, the compounding quantities of the components other than methyl ethyl ketone shown here are all solid content amounts.
(保護膜形成用膜之形成) (Formation of protective film forming film)
於聚對苯二甲酸乙二酯製膜的單面藉由聚矽氧處理進行了剝離處理而成之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm)的前述剝離處理面，塗敷上述所獲得之組成物(IV-1)，於100℃下乾燥3分鐘，藉此形成厚度為25μm之保護膜形成用膜Pf2。 A release film (“SP-PET381031” manufactured by Lintec, thickness 38 μm) obtained by peeling off one side of a polyethylene terephthalate film by polysiloxane treatment was applied to the peel-treated side. The above-obtained composition (IV-1) was applied and dried at 100° C. for 3 minutes to form a protective film-forming film Pf2 having a thickness of 25 μm.
(黏著劑組成物之製造) (Manufacture of adhesive composition)
利用與實施例3相同的方法，獲得黏著劑組成物(I-4)-2。 By the same method as Example 3, the adhesive composition (I-4)-2 was obtained.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
利用與實施例5相同的方法，形成黏著劑層Ad3，獲 得支撐片Ss5。 Using the same method as in Example 5, the adhesive layer Ad3 was formed to obtain Get the support sheet Ss5.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜中的不具備有剝離膜之側的露出面，與支撐片Ss5中的黏著劑層Ad3的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The exposed surface of the film for forming a protective film obtained above on the side not provided with the release film was laminated with the exposed surface of the adhesive layer Ad3 in the support sheet Ss5 to obtain the structure shown in FIG. 2 . A composite sheet for forming a protective film.
該保護膜形成用複合片係基材Bm3、黏著劑層Ad3、保護膜形成用膜Pf2及剝離膜依序於這些的厚度方向上積層而成，基材Bm3中的具備有黏著劑層Ad3之側的面為平滑面，基材Bm3中的與具備有黏著劑層Ad3之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表1。 The composite sheet for forming a protective film is formed by laminating a base material Bm3, an adhesive layer Ad3, a film for forming a protective film Pf2, and a release film in this order in the thickness direction, and the base material Bm3 has an adhesive layer Ad3. The side surface is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad3 in the base material Bm3 is an uneven surface. The structure of this composite sheet for protective film formation is shown in Table 1.
[實施例8] [Example 8]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
使用上述之基材Bm7代替基材Bm1，將該基材Bm7中的表面粗糙度為0.05μm之平滑面設為黏著劑層Ad1之形成面，除此方面以外，利用與實施例1相同的方法，獲得支撐片Ss11。 The above-mentioned base material Bm7 was used in place of the base material Bm1, and the smooth surface of the base material Bm7 having a surface roughness of 0.05 μm was used as the surface for forming the adhesive layer Ad1, and the same method as in Example 1 was used except that , to obtain the support sheet Ss11.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss11中的黏著劑層Ad1的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The structure shown in FIG. 2 was obtained by laminating the exposed surface of the protective film-forming film Pf1 obtained above on the side without the release film and the exposed surface of the adhesive layer Ad1 in the support sheet Ss11 The protective film forming composite sheet.
該保護膜形成用複合片係基材Bm7、黏著劑層Ad1、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm7中的具備有黏著劑層Ad1之側的面為平滑面，基材Bm7中的與具備有黏著劑層Ad1之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表2。 The composite sheet for forming a protective film is formed by laminating the base material Bm7, the adhesive layer Ad1, the film Pf1 for forming a protective film, and the release film in this order in the thickness direction, and the base material Bm7 has the adhesive layer Ad1. The side surface is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad1 in the base material Bm7 is an uneven surface. Table 2 shows the structure of the composite sheet for forming a protective film.
[實施例9] [Example 9]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
使用上述之基材Bm8代替基材Bm1，將該基材Bm8中的表面粗糙度為0.03μm之平滑面設為黏著劑層Ad1之形成面，除此方面以外，利用與實施例1相同的方法，獲得支撐片Ss12。 The above-mentioned base material Bm8 was used in place of the base material Bm1, and the smooth surface of the base material Bm8 having a surface roughness of 0.03 μm was used as the surface for forming the adhesive layer Ad1, and the same method as in Example 1 was used except that , to obtain the support sheet Ss12.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss12中的黏著劑層Ad1的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The structure shown in FIG. 2 was obtained by laminating the exposed surface of the protective film forming film Pf1 obtained above on the side not provided with the release film and the exposed surface of the adhesive layer Ad1 in the support sheet Ss12 The protective film forming composite sheet.
該保護膜形成用複合片係基材Bm8、黏著劑層Ad1、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm8中的具備有黏著劑層Ad1之側的面為平滑面，基材Bm8中的與具備有黏著劑層Ad1之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表2。 The composite sheet for forming a protective film is formed by laminating a base material Bm8, an adhesive layer Ad1, a film for forming a protective film Pf1, and a release film in this order in the thickness direction, and the base material Bm8 has an adhesive layer Ad1. The side surface is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad1 in the base material Bm8 is an uneven surface. Table 2 shows the structure of the composite sheet for forming a protective film.
[實施例10] [Example 10]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
使用上述之基材Bm9代替基材Bm1，將該基材Bm9中的表面粗糙度為0.03μm之平滑面設為黏著劑層Ad1之形成面，除此方面以外，利用與實施例1相同的方法，獲得支撐片Ss13。 The above-mentioned base material Bm9 was used in place of the base material Bm1, and the smooth surface of the base material Bm9 having a surface roughness of 0.03 μm was used as the surface for forming the adhesive layer Ad1, and the same method as in Example 1 was used except that , to obtain the support sheet Ss13.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss13中的黏著劑層Ad1的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The structure shown in FIG. 2 is obtained by laminating the exposed surface of the protective film forming film Pf1 obtained above on the side not provided with the release film and the exposed surface of the adhesive layer Ad1 in the support sheet Ss13 The protective film forming composite sheet.
該保護膜形成用複合片係基材Bm9、黏著劑層Ad1、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm9中的具備有黏著劑層Ad1之側的面為平滑面，基材Bm9中的與具備有黏著劑層Ad1之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表2。 The composite sheet for forming a protective film is formed by laminating a base material Bm9, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, and the base material Bm9 is provided with an adhesive layer Ad1. The side surface is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad1 in the base material Bm9 is an uneven surface. Table 2 shows the structure of the composite sheet for forming a protective film.
[實施例11] [Example 11]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
使用上述之基材Bm10代替基材Bm1，將該基材Bm10中的表面粗糙度為0.35μm之平滑面設為黏著劑層Ad1之形成面，除此方面以外，利用與實施例1相同的方法，獲得支撐片Ss14。 The above-mentioned base material Bm10 was used in place of the base material Bm1, and the smooth surface of the base material Bm10 having a surface roughness of 0.35 μm was used as the surface for forming the adhesive layer Ad1, except that the same method as in Example 1 was used. , the support sheet Ss14 is obtained.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
藉由將上述所獲得之保護膜形成用膜Pf1中的不具 備有剝離膜之側的露出面，與支撐片Ss14中的黏著劑層Ad1的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 By combining the above-obtained film Pf1 for forming a protective film with a The exposed surface on the side provided with the release film was laminated with the exposed surface of the adhesive layer Ad1 in the support sheet Ss14 to obtain a composite sheet for forming a protective film having the configuration shown in FIG. 2 .
該保護膜形成用複合片係基材Bm10、黏著劑層Ad1、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm10中的具備有黏著劑層Ad1之側的面為平滑面，基材Bm10中的與具備有黏著劑層Ad1之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表2。 The composite sheet for forming a protective film is formed by laminating a base material Bm10, an adhesive layer Ad1, a film for forming a protective film Pf1, and a release film in this order in the thickness direction, and the base material Bm10 is provided with the adhesive layer Ad1. The side surface is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad1 in the base material Bm10 is an uneven surface. Table 2 shows the structure of the composite sheet for forming a protective film.
[實施例12] [Example 12]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
使用上述之基材Bm11代替基材Bm1，將該基材Bm11中的表面粗糙度為0.37μm之平滑面設為黏著劑層Ad1之形成面，除此方面以外，利用與實施例1相同的方法，獲得支撐片Ss15。 The above-mentioned base material Bm11 was used in place of the base material Bm1, and the smooth surface of the base material Bm11 having a surface roughness of 0.37 μm was used as the surface for forming the adhesive layer Ad1, and the same method as in Example 1 was used except that , to obtain the support sheet Ss15.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss15中的黏著劑層Ad1 的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The exposed surface of the protective film forming film Pf1 obtained above was not provided with the release film, and the adhesive layer Ad1 in the support sheet Ss15 was The exposed surface was laminated to obtain a composite sheet for forming a protective film having the structure shown in FIG. 2 .
該保護膜形成用複合片係基材Bm11、黏著劑層Ad1、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm11中的具備有黏著劑層Ad1之側的面為平滑面，基材Bm11中的與具備有黏著劑層Ad1之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表2。 The composite sheet for forming a protective film is formed by laminating a base material Bm11, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction. The side surface is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad1 in the base material Bm11 is an uneven surface. Table 2 shows the structure of the composite sheet for forming a protective film.
[參考例1] [Reference Example 1]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
形成黏著劑層時，改變黏著劑組成物(I-4)-2的塗敷量，形成厚度為20μm而非5μm之黏著劑層Ad4，除此方面以外，利用與實施例4相同的方法，獲得支撐片Ss7。 When the adhesive layer was formed, the coating amount of the adhesive composition (I-4)-2 was changed to form an adhesive layer Ad4 with a thickness of 20 μm instead of 5 μm, using the same method as in Example 4, except that Obtain support sheet Ss7.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss7中的黏著劑層Ad4的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The exposed surface of the protective film forming film Pf1 obtained above was laminated on the exposed surface of the adhesive layer Ad4 in the support sheet Ss7 on the side not provided with the release film, whereby the structure shown in FIG. 2 was obtained. The protective film forming composite sheet.
該保護膜形成用複合片係基材Bm2、黏著劑層Ad4、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm2中的具備有黏著劑層Ad4之側的面為平滑面，基材Bm2中的與具備有黏著劑層Ad4之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表3。 The composite sheet for forming a protective film is formed by laminating a base material Bm2, an adhesive layer Ad4, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, and the base material Bm2 has an adhesive layer Ad4. The side surface is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad4 in the base material Bm2 is an uneven surface. The structure of this composite sheet for protective film formation is shown in Table 3.
[比較例1] [Comparative Example 1]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
使用上述之基材Bm5代替基材Bm1，於該基材Bm5的一面(平滑面)形成厚度為5μm之黏著劑層Ad1，除此方面以外，利用與實施例1相同的方法，獲得支撐片Ss8。 A support sheet Ss8 was obtained by the same method as in Example 1 except that the above-mentioned base material Bm5 was used instead of the base material Bm1, and an adhesive layer Ad1 with a thickness of 5 μm was formed on one side (smooth surface) of the base material Bm5. .
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss8中的黏著劑層Ad1的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The exposed surface of the protective film forming film Pf1 obtained above was laminated on the exposed surface of the adhesive layer Ad1 in the support sheet Ss8 on the side not provided with the release film, whereby the structure shown in FIG. 2 was obtained. The protective film forming composite sheet.
該保護膜形成用複合片係基材Bm5、黏著劑層Ad1、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上 積層而成，基材Bm5中的具備有黏著劑層Ad1之側的面、及基材Bm5中的與具備有黏著劑層Ad1之側為相反側的面(露出面)均為平滑面。該保護膜形成用複合片的構成示於表3。 The composite sheet-based base material Bm5 for forming a protective film, the adhesive layer Ad1, the film Pf1 for forming a protective film, and the release film are in this order in the thickness direction of these Laminated, the surface of the base material Bm5 on the side provided with the adhesive layer Ad1 and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad1 in the base material Bm5 are smooth surfaces. The structure of this composite sheet for protective film formation is shown in Table 3.
[比較例2] [Comparative Example 2]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
使用上述之基材Bm6代替基材Bm1，於該基材Bm6中的表面粗糙度為0.5μm之凹凸面，塗敷上述所獲得之黏著劑組成物(I-4)-1，形成黏著劑層Ad2，除此方面以外，利用與實施例2相同的方法獲得支撐片Ss9。 The above-mentioned substrate Bm6 was used instead of the substrate Bm1, and the adhesive composition (I-4)-1 obtained above was coated on the uneven surface of the substrate Bm6 with a surface roughness of 0.5 μm to form an adhesive layer Ad2, except this point, the support sheet Ss9 was obtained by the same method as Example 2.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss9中的黏著劑層Ad2的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The exposed surface of the protective film forming film Pf1 obtained above was laminated on the exposed surface of the adhesive layer Ad2 in the support sheet Ss9 on the side not provided with the release film, whereby the structure shown in FIG. 2 was obtained. The protective film forming composite sheet.
該保護膜形成用複合片係基材Bm6、黏著劑層Ad2、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm6中的具備有黏著劑層Ad2之側的面 為凹凸面，基材Bm6中的與具備有黏著劑層Ad2之側為相反側之面(露出面)為平滑面。該保護膜形成用複合片的構成示於表3。 The composite sheet for forming a protective film is formed by laminating a base material Bm6, an adhesive layer Ad2, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, and the base material Bm6 has an adhesive layer Ad2. side face It is an uneven surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad2 in the base material Bm6 is a smooth surface. The structure of this composite sheet for protective film formation is shown in Table 3.
[比較例3] [Comparative Example 3]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
使用上述之基材Bm6代替基材Bm1，於該基材Bm6中的表面粗糙度為0.05μm之平滑面，塗敷上述所獲得之黏著劑組成物(I-4)-1，形成黏著劑層Ad1，除此方面以外，利用與實施例1相同的方法獲得支撐片Ss10。 The above-mentioned substrate Bm6 was used instead of the substrate Bm1, and the adhesive composition (I-4)-1 obtained above was coated on the smooth surface of the substrate Bm6 with a surface roughness of 0.05 μm to form an adhesive layer Ad1, except this point, the support sheet Ss10 was obtained by the same method as Example 1.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss10中的黏著劑層Ad1的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The structure shown in FIG. 2 is obtained by laminating the exposed surface of the protective film-forming film Pf1 obtained above on the side without the release film and the exposed surface of the adhesive layer Ad1 in the support sheet Ss10 The protective film forming composite sheet.
該保護膜形成用複合片係基材Bm6、黏著劑層Ad1、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm6中的具備有黏著劑層Ad1之側的面為平滑面，基材Bm6中的與具備有黏著劑層Ad1之側為 相反側的面(露出面)為凹凸面。該保護膜形成用複合片的構成示於表3。 The composite sheet for forming a protective film is formed by laminating a base material Bm6, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, and the base material Bm6 has an adhesive layer Ad1. The side surface is a smooth surface, and the side with the adhesive layer Ad1 in the base material Bm6 is The surface on the opposite side (exposed surface) is an uneven surface. The structure of this composite sheet for protective film formation is shown in Table 3.
[比較例4] [Comparative Example 4]
(保護膜形成用膜之形成) (Formation of protective film forming film)
利用與實施例1相同的方法，形成保護膜形成用膜Pf1。 By the same method as Example 1, the film Pf1 for protective film formation was formed.
(黏著劑層之形成、支撐片之製造) (formation of adhesive layer, manufacture of support sheet)
使用上述之基材Bm12代替基材Bm1，將該基材Bm12中的表面粗糙度為0.43μm之平滑面設為黏著劑層Ad1之形成面，除此方面以外，利用與實施例1相同的方法獲得支撐片Ss16。 The above-mentioned base material Bm12 was used in place of the base material Bm1, and the smooth surface of the base material Bm12 having a surface roughness of 0.43 μm was used as the surface for forming the adhesive layer Ad1, except that the same method as in Example 1 was used. A support sheet Ss16 is obtained.
(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)
將上述所獲得之保護膜形成用膜Pf1中的不具備有剝離膜之側的露出面，與支撐片Ss16中的黏著劑層Ad1的露出面進行層壓，藉此獲得圖2所示之構成之保護膜形成用複合片。 The structure shown in FIG. 2 is obtained by laminating the exposed surface of the protective film-forming film Pf1 obtained above on the side without the release film and the exposed surface of the adhesive layer Ad1 in the support sheet Ss16 The protective film forming composite sheet.
該保護膜形成用複合片係基材Bm12、黏著劑層Ad1、保護膜形成用膜Pf1及剝離膜依序於這些的厚度方向上積層而成，基材Bm12中的具備有黏著劑層Ad1之側的面為平滑面，基材Bm11中的與具備有黏著劑層Ad1之側為相反側的面(露出面)為凹凸面。該保護膜形成用複合 片的構成示於表3。 The composite sheet for forming a protective film is formed by laminating a base material Bm12, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, and the base material Bm12 is provided with the adhesive layer Ad1. The side surface is a smooth surface, and the surface (exposed surface) on the opposite side to the side provided with the adhesive layer Ad1 in the base material Bm11 is an uneven surface. The protective film forming composite The composition of the sheet is shown in Table 3.
<保護膜形成用複合片之評價> <Evaluation of the composite sheet for protective film formation>
針對上述所獲得之保護膜形成用複合片，藉由下述方法評價雷射印字性、紅外線檢測性、耐黏連性、黏著劑層對於基材表面之埋入性、及耐碎片性。結果示於表1至表3(表中，表示為「埋入性」)。 The composite sheet for forming a protective film obtained above was evaluated for laser printing properties, infrared detection properties, blocking resistance, embedment of the adhesive layer on the surface of the substrate, and chip resistance by the following methods. The results are shown in Tables 1 to 3 (in the tables, "embedding properties" are shown).
[雷射印字性] [Laser printability]
自保護膜形成用複合片移除剝離膜，使用貼附裝置(Lintec公司製造之「RAD-2700F/12」)，於不鏽鋼製環狀框貼附保護膜形成用複合片，並且於加熱至70℃之矽晶圓(直徑8吋，厚度100μm)的背面，貼附保護膜形成用複合片中的保護膜形成用膜。 The release film was removed from the composite sheet for protective film formation, and the composite sheet for protective film formation was adhered to the stainless steel ring frame using an attaching device (“RAD-2700F/12” manufactured by Lintec), and heated to 70 A film for forming a protective film in the composite sheet for forming a protective film is attached to the back of a silicon wafer (8 inches in diameter, 100 μm in thickness) of ℃.
繼而，於保護膜形成用膜為熱硬化性之情形時，藉由將前述膜於130℃下進行2小時加熱處理而使保護膜形成用膜硬化並形成保護膜；於保護膜形成用膜為能量線硬化性之情形時，藉由對前述膜於照度145mW/cm2、光量230mJ/cm2之條件下照射2次紫外線而使保護膜形成用膜硬化並形成保護膜。 Then, when the film for protective film formation is thermosetting, the film for protective film formation is hardened by heat-processing the said film at 130 degreeC for 2 hours, and a protective film is formed; in the film for protective film formation, In the case of energy ray curability, the film for protective film formation is cured by irradiating the film with ultraviolet rays twice under the conditions of illuminance of 145 mW/cm 2 and light amount of 230 mJ/cm 2 to form a protective film.
繼而，使用印字裝置(KEYENCE公司製造之「MD-S9910A」)，於輸出4.8W、頻率80kHz、掃描速度500mm/sec之條件下，自基材側對保護膜照射波長532nm之雷射光，按照下述之2個圖案(圖案1、圖案2)對保護
膜進行雷射印字。
Then, using a printing device ("MD-S9910A" manufactured by KEYENCE Corporation), under the conditions of output 4.8W, frequency 80kHz, and scanning speed 500mm/sec, the protective film was irradiated with laser light with a wavelength of 532nm from the substrate side, as follows The above-mentioned two patterns (
(圖案) (pattern)
圖案1：文字尺寸0.30mm×0.5mm，文字間隔0.05mm，文字數20。 Pattern 1: Character size is 0.30mm×0.5mm, character interval is 0.05mm, and the number of characters is 20.
圖案2：文字尺寸0.15mm×0.3mm，文字間隔0.05mm，文字數20。 Pattern 2: Character size is 0.15mm×0.3mm, character interval is 0.05mm, and the number of characters is 20.
繼而，針對上述之利用雷射印字形成於保護膜之文字，經由支撐片進行觀察，依據下述基準評價雷射印字性。再者，若因雷射印字而自保護膜產生之氣體於黏著劑層與保護膜之間滯留，則會導致於切割時產生碎片，因此將未產生氣體滯留之保護膜設為評價對象。 Next, the characters formed on the protective film by the above-mentioned laser printing were observed through the support sheet, and the laser printing properties were evaluated according to the following criteria. In addition, if the gas generated from the protective film due to laser printing was retained between the adhesive layer and the protective film, chips would be generated at the time of dicing, so the protective film without gas retention was set as the evaluation object.
(評價基準) (Evaluation Criteria)
A：圖案1及圖案2的全部文字可清晰地印字。
A: All characters of
B：圖案2中一部分文字存在模糊而不清晰地印字，但圖案1的全部文字可清晰地印字。
B: Part of the characters in pattern 2 were blurred and indistinctly printed, but all the characters in
C：圖案1及圖案2之任一者中，均有一部分文字不清晰地印字。
C: In any of the
[紅外線檢測性] [Infrared Detectability]
自保護膜形成用複合片移除剝離膜，使用貼附裝置(Lintec公司製造之「RAD-2700F/12」)，於不鏽鋼製環狀框貼附保護膜形成用複合片，並且於加熱至70℃之作為矽晶圓(直徑8吋，厚度100μm)的背面之#2000研削面， 貼附保護膜形成用複合片中的保護膜形成用膜。 The release film was removed from the composite sheet for protective film formation, and the composite sheet for protective film formation was adhered to the stainless steel ring frame using an attaching device (“RAD-2700F/12” manufactured by Lintec), and heated to 70 ℃ as the #2000 ground surface of the backside of a silicon wafer (8 inches in diameter, 100 μm in thickness), The film for protective film formation in the composite sheet for protective film formation is stuck.
繼而，於保護膜形成用膜為熱硬化性之情形時，藉由將前述膜於130℃下進行2小時加熱處理而使保護膜形成用膜硬化並形成保護膜；於保護膜形成用膜為能量線硬化性之情形時，藉由對前述膜於照度145mW/cm2、光量230mJ/cm2之條件下照射2次紫外線而使保護膜形成用膜硬化並形成保護膜。 Then, when the film for protective film formation is thermosetting, the film for protective film formation is hardened by heat-processing the said film at 130 degreeC for 2 hours, and a protective film is formed; in the film for protective film formation, In the case of energy ray curability, the film for protective film formation is cured by irradiating the film with ultraviolet rays twice under the conditions of illuminance of 145 mW/cm 2 and light amount of 230 mJ/cm 2 to form a protective film.
繼而，使用切割裝置(DISCO公司製造之「DFD6361」)，於給料30mm/sec、轉速30000rpm之條件下進行刀片切割，藉此分割矽晶圓，獲得2mm×2mm之大小之矽晶片。 Then, a dicing device (“DFD6361” manufactured by DISCO) was used to perform blade dicing under the conditions of feeding 30 mm/sec and rotating speed 30000 rpm, thereby dividing the silicon wafer to obtain silicon wafers with a size of 2 mm×2 mm.
針對所獲得之矽晶片，使用紅外線顯微鏡(Olympus公司製造之「BX-IR」)，經由支撐片觀察研削面(矽晶片的背面)與分割面(矽晶片的側面)，依據下述基準評價紅外線檢測性。 The obtained silicon wafer was observed with an infrared microscope ("BX-IR" manufactured by Olympus Corporation) through a support sheet to observe the ground surface (back surface of the silicon wafer) and the dividing surface (side surface of the silicon wafer), and the infrared rays were evaluated according to the following criteria detectability.
(評價基準) (Evaluation Criteria)
A：可明確確認到研削面之研削痕跡。另外，亦可明確確認到自矽晶片的分割面向矽晶片的內側形成之2μm以上且未達5μm之大小之碎片。 A: Grinding marks on the ground surface can be clearly recognized. In addition, fragments with a size of 2 μm or more and less than 5 μm formed from the dividing surface of the silicon wafer from the inner side of the silicon wafer were also clearly confirmed.
B：可明確確認到研削面之研削痕跡。另一方面，無法明確確認到自矽晶片的分割面向矽晶片的內側形成之2μm以上且未達5μm之大小之碎片。 B: Grinding marks on the ground surface can be clearly recognized. On the other hand, fragments of a size of 2 μm or more and less than 5 μm formed from the dividing surface of the silicon wafer from the inner side of the silicon wafer were not clearly confirmed.
C：完全無法確認到或者無法明確確認到研削面之研 削痕跡，無論碎片大小如何均完全無法確認到或者無法明確確認到。 C: The research on the ground surface could not be confirmed at all or could not be clearly confirmed Chipping marks, regardless of the size of the fragments, are completely unidentifiable or unequivocally unidentifiable.
[耐黏連性] [Blocking resistance]
將保護膜形成用複合片以10m之長度捲取於3吋直徑之ABS(Acrylonitrile Butadiene Styrene；丙烯腈-丁二烯-苯乙烯)樹脂製芯材，直接以該狀態於室溫下靜置3天。 The composite sheet for forming a protective film was wound on a 3-inch diameter ABS (Acrylonitrile Butadiene Styrene; acrylonitrile-butadiene-styrene) resin core material at a length of 10 m, and left to stand at room temperature in this state for 3 sky.
繼而，捲出保管後的捲筒狀的保護膜形成用複合片，移除剝離膜，使用貼附裝置(Lintec公司製造之「RAD-2700F/12」)，將所捲出之保護膜形成用複合片貼附於不鏽鋼製環狀框，並且於加熱至70℃之矽晶圓(直徑8吋，厚度100μm)的背面，貼附保護膜形成用複合片中的保護膜形成用膜，嘗試針對矽晶圓10個份連續進行。根據此時的操作性，依據下述基準評價耐黏連性。 Next, the roll-shaped composite sheet for forming a protective film after storage was rolled out, the release film was removed, and the rolled-up protective film forming sheet was rolled out using a sticking device (“RAD-2700F/12” manufactured by Lintec Corporation). The composite sheet is attached to a stainless steel ring frame, and the film for protective film formation in the composite sheet for protective film formation is attached to the back of a silicon wafer (8 inches in diameter, 100 μm in thickness) heated to 70°C. 10 copies of silicon wafers are carried out continuously. From the workability at this time, the blocking resistance was evaluated according to the following criteria.
(評價基準) (Evaluation Criteria)
A：完全未產生黏連，可無問題地進行上述操作。 A: No sticking occurred at all, and the above operation could be performed without any problem.
B：可對矽晶圓貼附保護膜形成用膜，但捲取保護膜形成用複合片而成之捲筒中，基材與剝離膜相互的接觸面一部分黏附，捲出保護膜形成用複合片時，於基材與黏著劑層之間或黏著劑層與保護膜形成用膜之間，可見一部分剝離。 B: The film for forming a protective film can be attached to a silicon wafer, but in a roll formed by winding the composite sheet for forming a protective film, a part of the contact surface between the substrate and the release film adheres to each other, and the composite sheet for forming a protective film is rolled out. At the time, a part of peeling was observed between the base material and the adhesive layer or between the adhesive layer and the film for forming a protective film.
C：捲取保護膜形成用複合片而成之捲筒中，基材與剝離膜相互的接觸面一部分黏附，明顯產生黏連，捲出保護膜形成用複合片時，於黏著劑層與保護膜形成用膜之間 一部分產生剝離，支撐片(基材及黏著劑層之積層片)轉印至剝離膜，或者根本無法進行保護膜形成用複合片之捲出。 C: In a roll formed by winding the composite sheet for forming a protective film, a part of the contact surface between the base material and the release film is adhered to each other, and the adhesion is obviously caused. When the composite sheet for forming a protective film is rolled out, the adhesive layer and the protective film between films A part of peeling occurs, and the support sheet (laminated sheet of the base material and the adhesive layer) is transferred to the release film, or the composite sheet for forming a protective film cannot be rolled out at all.
[黏著劑層對於基材表面之埋入性] [Embedding of the adhesive layer to the surface of the substrate]
使用數位顯微鏡(Keyence公司製造之「VHS-1000」)，觀察上述所獲得之支撐片，依據下述基準，評價黏著劑層對於基材表面之埋入性。 The support sheet obtained above was observed using a digital microscope ("VHS-1000" manufactured by Keyence Corporation), and the embedding property of the adhesive layer with respect to the surface of the substrate was evaluated according to the following criteria.
○：於基材與黏著劑層之間未見氣泡。 ○: No air bubbles were observed between the base material and the adhesive layer.
×：於基材與黏著劑層之間可見氣泡。 ×: Air bubbles were observed between the base material and the adhesive layer.
[耐碎片性] [fragment resistance]
針對上述之紅外線檢測性之評價中所使用之2mm×2mm之大小之矽晶片10個，使用光學顯微鏡，觀察前述矽晶片10個中的4個分割面(矽晶片的側面)，依據下述基準評價耐碎片性。 About 10 silicon wafers with a size of 2 mm × 2 mm used in the evaluation of the above-mentioned infrared detection properties, four dividing surfaces (side surfaces of the silicon wafer) of the 10 silicon wafers were observed using an optical microscope, and the following criteria were used. Fragment resistance was evaluated.
○：自矽晶片的分割面向矽晶片的內側形成之30μm以上之大小之碎片部位的數量每1個矽晶片平均未達1個部位。 ○: The number of chip sites with a size of 30 μm or more formed from the dividing surface of the silicon wafer from the inner side of the silicon wafer is less than one site per silicon wafer on average.
×：自矽晶片的分割面向矽晶片的內側形成之30μm以上之大小之碎片部位的數量每1個矽晶片平均為1個部位以上。 ×: The number of chip sites with a size of 30 μm or more formed from the dividing surface of the silicon wafer from the inner side of the silicon wafer is 1 site or more on average per one silicon wafer.
[表1]
[表2]
[表3]
根據上述結果可明確，實施例1至實施例12之保護膜形成用複合片中，基材的第1面的表面粗糙度為0.37μm以下，基材的第2面的表面粗糙度大於前述第1面的表面粗糙度且為0.055μm至0.47μm，藉此耐黏連性、雷射印字性及紅外線檢測性均優異。再者，任一實施例中，耐碎片性及埋入性亦均優異。其中，實施例1至實
施例3及實施例8之保護膜形成用複合片中，基材的第2面的表面粗糙度較小，藉此雷射印字性及紅外線檢測性尤其優異。相對於此，實施例5至實施例7及實施例9至實施例12之保護膜形成用複合片中，基材的第2面的表面粗糙度較大，藉此耐黏連性尤其優異。並且，實施例4之保護膜形成用複合片中，基材的第2面的表面粗糙度為中等程度，藉此耐黏連性、雷射印字性及紅外線檢測性均尤其優異。
From the above results, it is clear that in the composite sheets for forming a protective film of Examples 1 to 12, the surface roughness of the first surface of the base material is 0.37 μm or less, and the surface roughness of the second surface of the base material is larger than the above-mentioned second surface roughness. The surface roughness of one side is 0.055 μm to 0.47 μm, and thereby blocking resistance, laser printing properties, and infrared detection properties are all excellent. Furthermore, in any of the Examples, chip resistance and embedment properties were also excellent. Wherein,
相對於此，比較例1之保護膜形成用複合片中，由於基材的第2面的表面粗糙度過小，故而耐黏連性差。 On the other hand, in the composite sheet for protective film formation of the comparative example 1, since the surface roughness of the 2nd surface of a base material was too small, blocking resistance was inferior.
另外，比較例2之保護膜形成用複合片中，由於基材的第1面的表面粗糙度過大，基材的第2面的表面粗糙度過小，故而耐黏連性、雷射印字性及紅外線檢測性均差。另外，比較例2之保護膜形成用複合片中，由於基材的第1面的表面粗糙度過大，故而埋入性亦差。 In addition, in the composite sheet for forming a protective film of Comparative Example 2, since the surface roughness of the first surface of the base material was too large and the surface roughness of the second surface of the base material was too small, the blocking resistance, laser printing properties and Infrared detection is poor. Moreover, in the composite sheet for protective film formation of the comparative example 2, since the surface roughness of the 1st surface of a base material was too large, embedment property was also inferior.
另外，比較例3之保護膜形成用複合片中，由於基材的第2面的表面粗糙度過大，故而雷射印字性及紅外線檢測性差。 Moreover, in the composite sheet for protective film formation of the comparative example 3, since the surface roughness of the 2nd surface of a base material was too large, the laser printing property and infrared detection property were inferior.
另外，比較例4之保護膜形成用複合片中，由於基材的第1面的表面粗糙度過大，故而雷射印字性、紅外線檢測性及埋入性差。 Moreover, in the composite sheet for protective film formation of the comparative example 4, since the surface roughness of the 1st surface of a base material was too large, the laser printing property, infrared detection property, and embedding property were inferior.
參考例1之保護膜形成用複合片中，藉由滿足基材的 第1面的表面粗糙度為0.4μm以下，基材的第2面的表面粗糙度為0.053μm至0.48μm之條件，耐黏連性、雷射印字性及紅外線檢測性均優異。但是，由於黏著劑層過厚，故而耐碎片性差。 In the composite sheet for forming a protective film of Reference Example 1, by satisfying the Under the condition that the surface roughness of the first surface is 0.4 μm or less, and the surface roughness of the second surface of the base material is 0.053 μm to 0.48 μm, the blocking resistance, laser printing properties and infrared detection properties are excellent. However, since the adhesive layer is too thick, the chip resistance is poor.
(產業可利用性) (Industrial Availability)
本發明可用於製造半導體裝置。 The present invention can be used to manufacture semiconductor devices.
1‧‧‧支撐片 1‧‧‧Support
11‧‧‧基材 11‧‧‧Substrate
11a‧‧‧基材的一表面(第1面) 11a‧‧‧One surface of the substrate (Side 1)
11b‧‧‧基材的另一表面(第2面) 11b‧‧‧The other surface of the substrate (Side 2)
12‧‧‧黏著劑層 12‧‧‧Adhesive layer
12a‧‧‧黏著劑層的一表面(第1面) 12a‧‧‧One surface of the adhesive layer (Side 1)
12b‧‧‧黏著劑層的另一表面(第2面) 12b‧‧‧The other surface of the adhesive layer (Side 2)
13‧‧‧保護膜形成用膜 13‧‧‧Film for forming protective film
13a‧‧‧保護膜形成用膜的一表面(第1面) 13a‧‧‧One surface (first surface) of the film for forming a protective film
14‧‧‧治具用接著劑層 14‧‧‧Adhesive layer for jig
14a‧‧‧治具用接著劑層的一表面(第1面) 14a‧‧‧One surface of the adhesive layer for the jig (the first surface)
14c‧‧‧治具用接著劑層的側面 14c‧‧‧Side surface of adhesive layer for jig
15‧‧‧剝離膜 15‧‧‧Peeling film
15a‧‧‧剝離膜的一表面(第1面) 15a‧‧‧One surface of release film (1st side)
101‧‧‧保護膜形成用複合片 101‧‧‧Composite sheet for forming protective film
Claims (5)
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| JP2016-060577 | 2016-03-24 | ||
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| JP (1) | JP6893500B2 (en) |
| KR (1) | KR102313074B1 (en) |
| CN (1) | CN108966671B (en) |
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| JP7059553B2 (en) * | 2017-10-04 | 2022-04-26 | 昭和電工マテリアルズ株式会社 | Adhesive tape for stealth dicing, dicing die bonding integrated tape, and method for manufacturing semiconductor devices |
| CN111279468B (en) * | 2017-10-27 | 2023-10-20 | 琳得科株式会社 | Film for forming protective film, composite sheet for forming protective film, and method for manufacturing semiconductor chip |
| JP6677939B2 (en) * | 2017-10-31 | 2020-04-08 | 東レフィルム加工株式会社 | Laminated film |
| JP7138448B2 (en) * | 2018-02-22 | 2022-09-16 | リンテック株式会社 | Adhesive sheet roll |
| WO2019172438A1 (en) * | 2018-03-09 | 2019-09-12 | リンテック株式会社 | Composite sheet for forming protective film and method for producing semiconductor chip with protective film |
| KR102524205B1 (en) * | 2018-03-30 | 2023-04-20 | 린텍 가부시키가이샤 | Composite sheet for forming protective film and manufacturing method thereof |
| JP7182610B2 (en) * | 2018-03-30 | 2022-12-02 | リンテック株式会社 | Composite sheet for forming protective film and method for manufacturing semiconductor device with protective film |
| JP7182611B2 (en) * | 2018-03-30 | 2022-12-02 | リンテック株式会社 | COMPOSITE SHEET FOR PROTECTIVE FILM FORMATION AND METHOD FOR MANUFACTURING SAME |
| WO2019187014A1 (en) * | 2018-03-30 | 2019-10-03 | リンテック株式会社 | Support sheet and composite sheet for protective film formation |
| JP7119070B2 (en) * | 2018-03-30 | 2022-08-16 | リンテック株式会社 | Method for manufacturing composite sheet for forming protective film, method for manufacturing semiconductor chip with protective film, and method for manufacturing semiconductor device |
| CN111630631B (en) * | 2018-03-30 | 2023-07-14 | 琳得科株式会社 | Support sheet and composite sheet for forming protective film |
| CN113692352A (en) * | 2019-04-26 | 2021-11-23 | 琳得科株式会社 | Method for producing third laminate, method for producing fourth laminate, method for producing semiconductor device with back surface protective film, and third laminate |
| JP7478524B2 (en) | 2019-09-05 | 2024-05-07 | リンテック株式会社 | Film for forming protective film, composite sheet for forming protective film, and method for manufacturing workpiece with protective film |
| JP7387510B2 (en) | 2020-03-26 | 2023-11-28 | リンテック株式会社 | Protective film-forming film, protective film-forming composite sheet, and method for transporting workpieces with protective film-forming film |
| TWI811636B (en) * | 2020-03-31 | 2023-08-11 | 日商東洋紡股份有限公司 | Inorganic substrate/engineering plastic film laminate with protective film, stacking of laminates, storage method of laminates, and transportation method of laminates |
| CN111777961B (en) * | 2020-07-15 | 2022-05-17 | 宁波东旭成新材料科技有限公司 | Preparation method of UV (ultraviolet) anti-adhesion protective film |
| JP2022143454A (en) | 2021-03-17 | 2022-10-03 | リンテック株式会社 | Support sheet, composite sheet for protective film formation, and method for manufacturing apparatus |
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| JP2011243613A (en) * | 2010-05-14 | 2011-12-01 | Mitsui Chemicals Inc | Semiconductor wafer protective adhesive film and semiconductor wafer protective adhesive film roll |
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| SG11201807645SA (en) | 2018-10-30 |
| CN108966671B (en) | 2023-09-26 |
| CN108966671A (en) | 2018-12-07 |
| JP6893500B2 (en) | 2021-06-23 |
| KR20180124868A (en) | 2018-11-21 |
| TW201739078A (en) | 2017-11-01 |
| KR102313074B1 (en) | 2021-10-14 |
| WO2017163971A1 (en) | 2017-09-28 |
| JPWO2017163971A1 (en) | 2019-01-31 |
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