TWI803605B - Adhesive composition and adhesive tape - Google Patents

Abstract

本發明之課題，是在被使用作為背面研磨帶、切割膠帶等的黏著膠帶，消除在半導體晶片、晶圓等工件產生的糊劑殘渣及端部外觀不良。 本發明之解決手段，提供一種黏著性組合物，其特徵在於，在23℃的儲存模數G’(23)為1.0×10⁵ Pa以上，在50℃之儲存模數G’(50)為2.5×10⁵ Pa以下，在60℃之動態黏彈性的tanδ為0.5以上，而且包括丙烯酸系聚合物作為主成分。The subject of the present invention is to eliminate paste residues and end appearance defects on workpieces such as semiconductor wafers and wafers in adhesive tapes used as back grinding tapes and dicing tapes. The solution of the present invention is to provide an adhesive composition, characterized in that the storage modulus G'(23) at 23°C is above 1.0×10 ⁵ Pa, and the storage modulus G'(50) at 50°C is 2.5×10 ⁵ Pa or less, tan δ of dynamic viscoelasticity at 60°C is 0.5 or more, and contains an acrylic polymer as a main component.

Description

黏著性組合物及黏著膠帶Adhesive composition and adhesive tape

本發明有關於一種暫時保護半導體晶圓等被加工物(以下有記載為「工件」之情形)表面，在進行研磨、切割等加工時能夠適合使用作為貼附、保持該工件的工件加工用膠帶之黏著膠帶。又，本發明有關於一種能夠適合使用在該黏著膠帶之黏著性組合物。The present invention relates to a tape for workpiece processing that temporarily protects the surface of a workpiece (hereinafter referred to as "workpiece") such as a semiconductor wafer, and can be suitably used as an adhesive tape for attaching and holding the workpiece during grinding, dicing, etc. Adhesive tape. Also, the present invention relates to an adhesive composition that can be suitably used for the adhesive tape.

矽、鎵砷等的半導體晶圓能夠在大直徑的狀態下進行製造。半導體晶圓在表面形成電路之後，藉由背面磨削而磨削至預定厚度為止，在切斷分離(切割)成為元件小片(半導體晶片)之後，被移送至下一個步驟之接合步驟。在該等一系列步驟，使用各種黏著膠帶。Semiconductor wafers such as silicon, gallium arsenide, etc. can be manufactured in a large diameter state. After the circuit is formed on the surface of the semiconductor wafer, it is ground to a predetermined thickness by back grinding, cut and separated (diced) into small element pieces (semiconductor wafers), and then transferred to the next step of bonding. In these series of steps, various adhesive tapes are used.

在背面磨削步驟，使用被稱為背面研磨帶的黏著膠帶，以在磨削中保持晶圓，且保護電路表面避免受到磨削屑等的污染。又，在背面磨削步驟後，亦有在磨削面進行電路形成等之情形，此時亦使用黏著膠帶保護及固定晶圓而進行加工。背面研磨帶等背面加工時的表面保護膠帶由基材、及具有感壓接著性的黏著劑層所構成。為了確實地保護電路面，有使用較軟質且應力緩和性較高的黏著劑之黏著膠帶之情形。In the back grinding step, an adhesive tape called a back grinding tape is used to hold the wafer during grinding and protect the circuit surface from contamination such as grinding debris. In addition, after the back grinding step, there are cases where circuit formation and the like are performed on the ground surface, and at this time, the wafer is also protected and fixed with an adhesive tape for processing. The surface protection tape for back surface processing such as back grinding tape consists of a base material and an adhesive layer with pressure-sensitive adhesive properties. In order to securely protect the circuit surface, an adhesive tape with a relatively soft adhesive with high stress relaxation properties may be used.

又，使用在切割步驟之黏著膠帶亦被稱為切割膠帶，且由基材及具有感壓接著性的黏著劑層所構成，用以在切割半導體晶圓等的工件時將該工件固定，且在切割後保持晶片切割後，為了使分離晶片間隔之擴展變得容易，有使用具有較軟質的基材之黏著膠帶之情形。In addition, the adhesive tape used in the dicing process is also called a dicing tape, and is composed of a base material and an adhesive layer having pressure-sensitive adhesive properties, and is used to fix a workpiece such as a semiconductor wafer when dicing the workpiece, and To maintain wafers after dicing, an adhesive tape having a softer base material may be used in order to facilitate the expansion of the interval for separating wafers after dicing.

近年來，不限定於形成有電路之具有二維圖案的半導體晶片，亦逐漸地能夠看到突起物作為立體結構之半導體晶片。例如，在半導體裝置的製造，將藉由切割而個片化的晶片設置在基板時能夠使用無線接合(wireless bonding)之手法。該手法不使用金屬細線亦能夠進行晶片與基板的電連接，作為一個例子，藉由使設置在晶片電路面之被稱為凸塊的突起狀電極、與基板上的電極接觸，而能夠確保電連接。該封裝方法被稱為倒裝(face down)封裝或覆晶(flip Chip)封裝，且有助於元件的小型化。In recent years, not limited to semiconductor wafers having a two-dimensional pattern on which circuits are formed, semiconductor wafers having protrusions as three-dimensional structures have gradually been seen. For example, in the manufacture of a semiconductor device, a wireless bonding technique can be used when placing a wafer that has been singulated by dicing on a substrate. This method can also perform electrical connection between the chip and the substrate without using thin metal wires. As an example, by making the protruding electrodes called bumps provided on the circuit surface of the chip contact the electrodes on the substrate, the electrical connection can be ensured. connect. This packaging method is called face down packaging or flip chip packaging, and contributes to miniaturization of components.

在製造形成有此種突起物之晶片之方法的一個例子中，在半導體晶圓表面形成電路且在電路面形成突起物之後，將背面研磨帶貼附在表面，且將背面進行磨削加工而調整厚度。隨後，將半導體晶圓保持在切割膠帶上，且將半導體晶圓進行切割而個片化成為晶片。In one example of a method of manufacturing a wafer having such protrusions formed thereon, after forming a circuit on the surface of a semiconductor wafer and forming protrusions on the circuit surface, a back grinding tape is attached to the surface, and the back side is ground and processed. Adjust the thickness. Subsequently, the semiconductor wafer is held on the dicing tape, and the semiconductor wafer is diced and singulated into wafers.

在半導體晶圓表面，由於突起物而產生5~100μm左右的微細凹凸差。背面研磨帶被要求對該凹凸面具有追隨性且能夠確實地保護電路面。背面研磨帶的追隨性不充分時，在背面的磨削中有磨削屑等侵入電路面且將電路污染或破損之情形。因而，背面研磨帶被要求對微細凹凸面之埋入性。On the surface of the semiconductor wafer, there is a fine unevenness of about 5 to 100 μm due to the protrusions. The back grinding tape is required to follow the uneven surface and protect the circuit surface reliably. When the followability of the back grinding tape is insufficient, grinding debris and the like may intrude into the circuit surface during back grinding, contaminating or damaging the circuit. Therefore, the back grinding tape is required to embed the fine uneven surface.

作為對此種具有高低差的半導體晶圓之背面研磨帶，已知一種由基材、中間層及黏著劑層所構成之黏著膠帶(專利文獻1、2)。在該黏著膠帶，藉由中間層而吸收晶圓表面的高低差且追隨電路面。但是，在前述文獻之中間層，多半是由聚烯烴系聚合物所構成，而且，黏著劑層多半是由丙烯酸系聚合物所構成。聚烯烴系聚合物與丙烯酸系聚合物通常親和性較低。因此，在將背面研磨帶從半導體晶圓的電路面剝離時，有在中間層與黏著劑層之間產生剝離且引起黏著劑殘留附著在半導體晶圓的電路面之問題。As a back grinding tape for such a semiconductor wafer having a level difference, an adhesive tape comprising a base material, an intermediate layer, and an adhesive layer is known (Patent Documents 1 and 2). In this adhesive tape, the level difference on the wafer surface is absorbed by the intermediate layer and follows the circuit surface. However, in the aforementioned documents, the intermediate layer is mostly composed of polyolefin polymers, and the adhesive layer is mostly composed of acrylic polymers. Polyolefin-based polymers generally have low affinity with acrylic-based polymers. Therefore, when the back grinding tape is peeled off from the circuit surface of the semiconductor wafer, there is a problem that peeling occurs between the intermediate layer and the adhesive layer and the adhesive remains on the circuit surface of the semiconductor wafer.

又，作為背面研磨帶，亦已知由基材及黏著劑層所構成之二層結構的黏著膠帶。在如此的黏著膠帶，為了追隨半導體晶圓表面的凹凸，已研討將黏著劑層增厚、或使黏著劑層較軟質。但是，在如此的黏著膠帶，有引起外觀不良、黏著劑殘留附著在半導體晶圓的電路面的問題之情形。Moreover, the adhesive tape of the two-layer structure which consists of a base material and an adhesive agent layer is also known as a back grinding tape. In such an adhesive tape, thickening of the adhesive layer or making the adhesive layer soft has been considered in order to follow the unevenness of the surface of the semiconductor wafer. However, such adhesive tapes may cause problems such as poor appearance and adhesive residue adhering to the circuit surface of the semiconductor wafer.

黏著膠帶通常被捲取成為捲物狀而保管、搬運。此時，對黏著膠帶施加捲撓壓力(winding pressure)，致使黏著劑層和中間層的一部分漏出至捲物端面。特別是在夏季保管、在海上搬運時，有被暴露在40℃左右的環境下之情形，致使樹脂成分的漏出變的顯著。漏出至捲物端面之樹脂成分，成為端部外觀不良的主要原因，而且塵埃等附著亦成為污染半導體晶圓的主要原因。又，使黏著劑層較軟質時，對半導體晶圓表面的凹凸之追隨性提升。但是，若將黏著膠帶從半導體晶圓表面剝離，則剝離時黏著劑層伸長、斷裂，而且黏著劑的一部分殘留附著在晶圓電路面(糊劑殘渣)，且有污染電路面之情形。 [先前技術文獻] [專利文獻]The adhesive tape is usually wound up into a roll and stored and transported. At this time, a winding pressure is applied to the adhesive tape, so that a part of the adhesive layer and the intermediate layer leaks to the end surface of the roll. Especially during summer storage and transportation at sea, it may be exposed to an environment of about 40°C, resulting in significant leakage of resin components. The resin component leaked to the end surface of the roll becomes the main cause of poor appearance of the end, and the adhesion of dust and the like also becomes the main cause of contamination of the semiconductor wafer. Also, when the adhesive layer is made softer, the followability to the unevenness of the surface of the semiconductor wafer is improved. However, when the adhesive tape is peeled from the surface of the semiconductor wafer, the adhesive layer is stretched and broken during peeling, and a part of the adhesive remains on the wafer circuit surface (paste residue), which may contaminate the circuit surface. [Prior Art Literature] [Patent Document]

[專利文獻1]日本特許第3773358號 [專利文獻2]日本特許第4918181號[Patent Document 1] Japanese Patent No. 3773358 [Patent Document 2] Japanese Patent No. 4918181

[發明欲解決之課題][Problem to be solved by the invention]

本發明之目的，是在被使用作為背面研磨帶、切割膠帶等的黏著膠帶，消除在工件產生的糊劑殘渣及端部外觀不良。 [用以解決課題之手段]The purpose of the present invention is to eliminate paste residues and edge appearance defects on workpieces in adhesive tapes used as back grinding tapes, dicing tapes, and the like. [Means to solve the problem]

通常將黏著膠帶貼附在凹凸面時，是將黏著膠帶加溫至40~60℃左右，且在使黏著劑層(或中間層)的流動性、埋入性提升之後進行貼附。另一方面，端部外觀不良的主要原因之保管時黏著劑(或中間層)的漏出，是起因於黏著劑(或中間層)在常溫~40℃左右產生流動。因此，本發明者等詳細地研討構成黏著劑層(或中間層)之黏著性組合物的黏彈性行為。該結果，發現若能夠實現在室溫~40℃左右時具有能夠抑制流動性的程度之彈性，且在加溫下具有適當的流動性及形狀維持性之丙烯酸系聚合物時，則能夠消除上述課題，而完成了本發明。本發明之目的是解決此種課題，其要旨如以下。Usually, when attaching the adhesive tape to the concave-convex surface, the adhesive tape is heated to about 40~60°C, and the fluidity and embedding of the adhesive layer (or intermediate layer) are improved before attaching. On the other hand, leakage of the adhesive (or intermediate layer) during storage, which is the main cause of poor appearance at the end, is caused by the flow of the adhesive (or intermediate layer) at room temperature ~ 40°C. Therefore, the inventors of the present invention studied in detail the viscoelastic behavior of the adhesive composition constituting the adhesive layer (or intermediate layer). As a result, it was found that if an acrylic polymer having elasticity to the extent that fluidity can be suppressed at room temperature to about 40°C and having appropriate fluidity and shape retention under heating can be realized, the above-mentioned problems can be eliminated. subject, and completed the present invention. The object of this invention is to solve such a subject, and the summary is as follows.

(1)一種黏著性組合物，在23℃的儲存模數G’(23)為1.0×10⁵ Pa以上，在50℃之儲存模數G’(50)為2.5×10⁵ Pa以下，在60℃之動態黏彈性的tanδ為0.5以上，而且包括丙烯酸系聚合物作為主成分。 (2)如(1)所述之黏著性組合物，其在60℃的儲存模數G’(60)相對於在23℃的儲存模數G’(23)之比，亦即，G’(60)/G’(23)為0.1~0.7。 (3)一種黏著膠帶，包包括基材及黏著劑層，其中該黏著劑層包括如(1)或(2)所述之黏著性組合物。 (4)一種黏著膠帶，包括基材、黏著劑層、以及基材與黏著劑層之間之中間層，其中該中間層包括如(1)或(2)所述之黏著性組合物。 [發明效果](1) An adhesive composition having a storage modulus G'(23) at 23°C of not less than 1.0×10 ⁵ Pa and a storage modulus G'(50) at 50°C of not more than 2.5×10 ⁵ Pa. The tan δ of dynamic viscoelasticity at 60°C is 0.5 or more, and contains an acrylic polymer as a main component. (2) The adhesive composition as described in (1), which is the ratio of the storage modulus G'(60) at 60°C to the storage modulus G'(23) at 23°C, that is, G'(60)/G'(23) is 0.1~0.7. (3) An adhesive tape comprising a substrate and an adhesive layer, wherein the adhesive layer includes the adhesive composition as described in (1) or (2). (4) An adhesive tape comprising a substrate, an adhesive layer, and an intermediate layer between the substrate and the adhesive layer, wherein the intermediate layer comprises the adhesive composition as described in (1) or (2). [Invention effect]

在黏著劑等所使用的丙烯酸系聚合物，通常能夠在-50~0℃左右的低溫區域確認tanδ的尖峰值，且隨著溫度上升而tanδ降低。又，彈性模數隨著溫度上升而降低。本發明者等針對作為黏著性組合物的主成分之丙烯酸系聚合物的黏彈性進行各種研討，且成功設計一種在室溫~40℃左右時具有能夠抑制流動性的程度之彈性，而且在加溫下具有適當的流動性及形狀維持性之丙烯酸系聚合物。藉由使用此種丙烯酸聚合物作為黏著性組合物的主成分，能夠提供一種黏著膠帶，其在貼附時及保管時容易控制黏著劑層(或中間層)的流動性，且在貼附時追隨工件的凹凸面，而且在保管時黏著性組合物的漏出較少。For acrylic polymers used in adhesives, etc., a sharp peak of tan δ can usually be observed in a low temperature range of about -50 to 0°C, and tan δ decreases as the temperature rises. Also, the modulus of elasticity decreases as the temperature rises. The inventors of the present invention conducted various studies on the viscoelasticity of the acrylic polymer, which is the main component of the adhesive composition, and succeeded in designing one that has elasticity to the extent that fluidity can be suppressed at room temperature to about 40°C. Acrylic polymer with proper fluidity and shape retention at low temperature. By using such an acrylic polymer as the main component of the adhesive composition, it is possible to provide an adhesive tape that is easy to control the fluidity of the adhesive layer (or intermediate layer) at the time of attachment and storage, and that is easy to control during attachment. It follows the uneven surface of the workpiece, and there is less leakage of the adhesive composition during storage.

[用以實施發明之形態][Mode for Carrying Out the Invention]

以下，具體地說明本發明之黏著膠帶。首先，說明在本說明書所使用的主要用語。 在本說明書，例如所謂「(甲基)丙烯酸酯」，是使用作為表示「丙烯酸酯」及「甲基丙烯酸酯」的雙方之用語，針對其它類似用語亦同樣。Hereinafter, the adhesive tape of this invention is demonstrated concretely. First, main terms used in this specification will be described. In this specification, for example, "(meth)acrylate" is used as a term representing both "acrylate" and "methacrylate", and the same applies to other similar terms.

所謂黏著膠帶，意指包含基材、及黏著劑層之積層體，而且包含該等以外的其它構成層亦無妨。例如，亦可為在基材與黏著劑層之間具有中間層之構成；為了提升基材表面與黏著劑層界面、或基材表面與中間層界面的密著性，且防止低分子量成分移行等目的，亦可在黏著劑層側的基材表面形成底漆(primer)層；在黏著劑層表面亦可層積用以保護黏著劑層至使用時為止之剝離膜。又，基材可為單層，亦可為具備緩衝層等的功能層之多層。以下說明之本發明的黏著性組合物，能夠適合使用在黏著膠帶的黏著劑層或中間層。The adhesive tape means a laminate including a base material and an adhesive layer, and may include other constituent layers than these. For example, there may be an intermediate layer between the base material and the adhesive layer; in order to improve the adhesion of the interface between the base material surface and the adhesive layer, or the interface between the base material surface and the intermediate layer, and prevent low molecular weight components from migrating For other purposes, a primer layer can also be formed on the surface of the substrate on the side of the adhesive layer; a release film can also be laminated on the surface of the adhesive layer to protect the adhesive layer until it is used. In addition, the substrate may be a single layer or a multilayer having functional layers such as a buffer layer. The adhesive composition of this invention demonstrated below can be suitably used for the adhesive agent layer or intermediate|middle layer of an adhesive tape.

所謂背面研磨帶，是指在半導體晶圓的背面磨削時為了保護晶圓電路面而使用的黏著膠帶。所謂切割膠帶，是指將晶圓連電路一起個片化成為晶片時，為了保持晶圓及晶片而使用之黏著膠帶。 所謂半導體晶圓的「表面」，是指形成有電路之面，所謂「背面」，是指未形成有電路之面。The so-called back grinding tape refers to an adhesive tape used to protect the circuit surface of the wafer when grinding the back of the semiconductor wafer. The so-called dicing tape refers to the adhesive tape used to hold the wafer and the chip when the wafer-connected circuit is sliced into chips. The "surface" of the semiconductor wafer refers to the surface on which circuits are formed, and the so-called "back surface" refers to the surface on which no circuits are formed.

(黏著性組合物) 本發明的黏著性組合物，包括丙烯酸系聚合物，且滿足以下的黏彈性行為。又，黏著性組合物的黏彈性是基於固體成分之黏彈性，黏著性組合物為溶液形態時，意指將溶液乾燥而得到的黏著性物質之黏彈性。又，黏著性組合物僅由丙烯酸系聚合物所構成時，意指丙烯酸系聚合物本身的性質。又，黏著性組合物為能量線硬化性時，下述物性是指藉由能量線照射使黏著性組合物硬化之前的物性。(adhesive composition) The adhesive composition of the present invention includes an acrylic polymer and satisfies the following viscoelastic behavior. Moreover, the viscoelasticity of an adhesive composition is based on the viscoelasticity of a solid content, and when an adhesive composition is a solution form, it means the viscoelasticity of the adhesive material obtained by drying a solution. Moreover, when an adhesive composition consists only of an acrylic polymer, it means the property of an acrylic polymer itself. In addition, when the adhesive composition is energy ray curable, the following physical properties refer to physical properties before the adhesive composition is cured by energy ray irradiation.

黏著性組合物在23℃的儲存模數G’(23)，較佳為1.0×10⁵ pa以上，更佳為1.2×10⁵ pa以上，較佳為1.3×10⁵ ~8.0×10⁵ pa，特佳為1.7×10⁵ ~7.0×10⁵ pa。The storage modulus G'(23) of the adhesive composition at 23°C is preferably at least 1.0×10 ⁵ Pa, more preferably at least 1.2×10 ⁵ Pa, more preferably 1.3×10 ⁵ ~8.0×10 ⁵ Pa , especially 1.7×10 ⁵ ~7.0×10 ⁵ pa.

黏著性組合物的儲存模數G’(23)為上述範圍時，能夠抑制在常溫~40℃左右的流動性。該結果，即便將黏著膠帶以捲物狀的形態保管、搬運，黏著性組合物亦不會從捲物端面漏出，而能夠良好地維持捲物端部的外觀。When the storage modulus G'(23) of the adhesive composition is in the above-mentioned range, the fluidity at room temperature to about 40°C can be suppressed. As a result, even if the adhesive tape is stored and conveyed in the form of a roll, the adhesive composition does not leak from the end surface of the roll, and the appearance of the end of the roll can be maintained favorably.

黏著性組合物在50℃的儲存模數G’(50)，較佳為2.5×10⁵ pa以下，更佳為2.4×10⁵ pa以下，較佳為7.0×10⁴ ~2.3×10⁵ pa，特佳為8.0×10⁴ ~2.2×10⁵ pa。The storage modulus G'(50) of the adhesive composition at 50°C is preferably less than 2.5×10 ⁵ Pa, more preferably less than 2.4×10 ⁵ Pa, more preferably 7.0×10 ⁴ ~2.3×10 ⁵ Pa , especially 8.0×10 ⁴ ~2.2×10 ⁵ pa.

黏著性組合物的儲存模數G’(50)為上述範圍時，將黏著膠帶加溫至40~60℃左右而進行貼附時，能夠得到適當的流動性，且對半導體晶圓表面的凹凸之埋入性提升。When the storage modulus G'(50) of the adhesive composition is in the above range, when the adhesive tape is heated to about 40-60°C and attached, appropriate fluidity can be obtained, and the unevenness of the surface of the semiconductor wafer can be obtained. Embedding enhancement.

在黏著性組合物60℃之動態黏彈性的tanδ (以下有記載為「tanδ(60)」之情形)，較佳為0.5以上，更佳為0.51以上，較佳為0.52~0.8，特佳為0.53~0.75。The tanδ of the dynamic viscoelasticity of the adhesive composition at 60°C (hereinafter referred to as "tanδ(60)") is preferably 0.5 or higher, more preferably 0.51 or higher, preferably 0.52 to 0.8, particularly preferably 0.53~0.75.

黏著性組合物的tanδ可如下所述而得到。亦即，能夠從黏著性組合物得到預定形狀的試料，對該試料施加頻率1Hz的應變，且在各測定溫度測定儲存模數G’及損失模數G’’，而且從該等值算出在60℃之損失正切tanδ(G’’/G’)而得到tanδ(60)。The tan δ of the adhesive composition can be obtained as follows. That is, it is possible to obtain a sample of a predetermined shape from the adhesive composition, apply a strain at a frequency of 1 Hz to the sample, and measure the storage modulus G' and the loss modulus G'' at each measurement temperature, and calculate the The loss tangent at 60°C is tan δ(G''/G') to obtain tan δ(60).

藉由tanδ(60)在上述範圍，一旦變形的黏著劑層或中間層維持變形後的形狀之傾向變高。該結果，因為被埋入至半導體晶圓表面的凹凸之黏著劑層或中間層維持其形狀，所以能夠阻止切削水浸入至晶圓表面，且能夠減低電路的污染、破損。When tan δ(60) is in the above-mentioned range, the adhesive layer or the intermediate layer once deformed tends to maintain the deformed shape high. As a result, since the uneven adhesive layer or intermediate layer buried in the surface of the semiconductor wafer maintains its shape, it is possible to prevent cutting water from penetrating the wafer surface, and to reduce contamination and damage of circuits.

又，本發明的黏著性組合物較佳為滿足以下的黏彈性。 黏著性組合物之在60℃的儲存模數G’(60)相對於在23℃的儲存模數G’(23)之比，G’(60)/G’(23)良好為0.1~0.7，更佳為0.2~0.6，較佳為0.21~0.45，特佳為0.23~0.41。Moreover, it is preferable that the adhesive composition of this invention satisfies the following viscoelasticity. The ratio of the storage modulus G'(60) at 60°C to the storage modulus G'(23) at 23°C of the adhesive composition, G'(60)/G'(23) is preferably 0.1~0.7 , more preferably 0.2-0.6, more preferably 0.21-0.45, particularly preferably 0.23-0.41.

G’(60)/G’(23)為上述範圍時，即便將黏著劑層或中間層加溫亦不會過度地流動化，所以黏著性組合物不侵入至電路面的微細構造。因此，即便在預定步驟結束後將黏著膠帶剝離，黏著性組合物亦不會殘留附著在電路面的微細構造。When G'(60)/G'(23) is in the above range, the adhesive layer or the intermediate layer does not fluidize excessively even when heated, and therefore the adhesive composition does not intrude into the fine structure of the circuit surface. Therefore, even if the adhesive tape is peeled off after the predetermined step is completed, the adhesive composition does not leave a fine structure adhering to the circuit surface.

又，黏著性組合物具有複數個動態黏彈性的tanδ之極大值，較佳為二個。在使用下述含兩性離子的丙烯酸系聚合物作為黏著性組合物的主成分之丙烯酸系聚合物的情況，在該聚合物中，相當於通常的黏著性聚合物之部位與源自含兩性離子單元之部位共存。認為因為兩者的黏彈性行為是不同的，所以tanδ之極大值出現複數個。 在較佳態樣中，低溫側的tanδ之極大值出現在-50~0℃的範圍，而高溫側的tanδ之極大值出現在10~60℃的範圍。Also, the adhesive composition has a plurality of maximum values of tanδ of dynamic viscoelasticity, preferably two. In the case of using the following zwitterion-containing acrylic polymer as the main component of the acrylic polymer of the adhesive composition, in this polymer, the part corresponding to the usual adhesive polymer and the part derived from the zwitterion-containing The parts of the unit coexist. It is considered that because the viscoelastic behaviors of the two are different, there are plural maximum values of tan δ. In a preferred embodiment, the maximum value of tanδ on the low temperature side appears in the range of -50°C to 0°C, and the maximum value of tanδ on the high temperature side appears in the range of 10°C to 60°C.

因為在低溫側具有tanδ之極大值，所以常溫時具有優異的黏著力特別是初期黏著力。又，因為高溫側具有tanδ之極大值，所以將黏著膠帶加溫至40~60℃左右且將黏著劑埋入半導體晶圓表面的凹凸之後，黏著劑層的變形能夠維持，且能夠減低因切削水引起之電路面的污染、破損。Since it has the maximum value of tanδ at the low temperature side, it has excellent adhesive force, especially initial adhesive force at room temperature. Also, since the high temperature side has the maximum value of tanδ, after heating the adhesive tape to about 40~60°C and embedding the adhesive into the unevenness on the surface of the semiconductor wafer, the deformation of the adhesive layer can be maintained and the damage caused by chipping can be reduced. Pollution and damage to the circuit surface caused by water.

本發明之黏著性組合物包括丙烯酸系聚合物作為主成分。所謂丙烯酸系聚合物，是將源自(甲基)丙烯酸或其衍生物的酯類之重複單元作為主要構成要素之聚合物，且亦可為改性聚合物。上述黏著性組合物的各種物性主要是起因於丙烯酸系聚合物。因而，藉由選擇具有適當的黏彈性之丙烯酸系聚合物，能夠得到本發明的黏著性組合物。以下，說明能夠適合使用的丙烯酸系聚合物，但是該等為非限定的例示，本發明的丙烯酸系聚合物不被下述之物限定。藉由基於以下的說明及技術常識而適當地調節聚合物的構造，能夠得到在本發明能夠使用的其它丙烯酸系聚合物。The adhesive composition of the present invention includes an acrylic polymer as a main component. The acrylic polymer is a polymer having a repeating unit derived from esters of (meth)acrylic acid or its derivatives as a main constituent, and may be a modified polymer. The various physical properties of the above-mentioned adhesive composition are mainly attributable to the acrylic polymer. Therefore, the adhesive composition of the present invention can be obtained by selecting an acrylic polymer having appropriate viscoelasticity. Hereinafter, acrylic polymers that can be suitably used will be described, but these are non-limiting examples, and the acrylic polymer of the present invention is not limited to the following. Other acrylic polymers usable in the present invention can be obtained by appropriately adjusting the structure of the polymer based on the following description and common technical knowledge.

本發明之黏著性組合物，較佳是包括具有含兩性離子結構的重複單元及源自(甲基)丙烯酸系單體的重複單元之丙烯酸系聚合物作為丙烯酸系聚合物作為。以下，有將含兩性離子結構的重複單元稱為「含兩性離子單元」，將源自(甲基)丙烯酸系單體的重複單元稱為「(甲基)丙烯酸((meth)acrylic)單元」且將含有該等重複單元之聚合物稱為「含兩性離子的丙烯酸系聚合物」之情形。The adhesive composition of the present invention preferably includes, as the acrylic polymer, an acrylic polymer having a repeating unit containing a zwitterionic structure and a repeating unit derived from a (meth)acrylic monomer. Hereinafter, a repeating unit containing a zwitterionic structure is referred to as a "zwitterionic-containing unit", and a repeating unit derived from a (meth)acrylic monomer is referred to as a "(meth)acrylic unit". And the polymer containing these repeating units is called "zwitterion-containing acrylic polymer".

(含兩性離子的丙烯酸系聚合物) 含兩性離子的丙烯酸系聚合物包括含有兩性離子結構的重複單元。在此，所謂兩性離子結構，是指包括正電荷及負電荷之分極結構。含兩性離子的丙烯酸系聚合物，較佳是在聚合物的側鏈具有兩性離子結構。兩性離子結構只要具有分極結構，就沒有特別限定，就製造上的方便性而言，正電荷較佳是源自四級銨、含氮的雜環或四級鏻之正電荷，負電荷是源自磺內酯(sultone)之磺基殘基(SO₃ ^- )。聚合物的主鏈結構沒有特別限定，較佳是由碳骨架所構成。因而，較佳的含兩性離子單元如下述式(1)所表示。又，以下，將正電荷是源自四級銨時作為例子而進行說明，但是正電荷亦可為源自含氮的雜環或四級鏻之物。(Zwitterion-Containing Acrylic Polymer) The zwitterion-containing acrylic polymer includes a repeating unit having a zwitterion structure. Here, the so-called zwitterionic structure refers to a polarized structure including positive charges and negative charges. The zwitterion-containing acrylic polymer preferably has a zwitterion structure in the side chain of the polymer. The zwitterionic structure is not particularly limited as long as it has a polarized structure. In terms of manufacturing convenience, the positive charge is preferably derived from quaternary ammonium, nitrogen-containing heterocycle or quaternary phosphonium. The sulfo residue (SO ₃ ^- ) from sultone (sultone). The main chain structure of the polymer is not particularly limited, but is preferably composed of a carbon skeleton. Therefore, a preferable zwitterion-containing unit is represented by the following formula (1). In addition, in the following, the case where the positive charge is derived from quaternary ammonium will be described as an example, but the positive charge may be derived from a nitrogen-containing heterocycle or quaternary phosphonium.

式(1)中，R¹ 表示氫原子或甲基，R² 、R³ 各自獨立地表示氫原子、具有或不具有醚鍵之碳數1~10的烷基、具有或不具有醚鍵之碳數2~11的氰烷基(cyanoalkyl)、具有或不具有醚鍵之碳數2~10的烯基、或具有或不具有取代基之碳數6~20的芳基。R² 及R³ 亦可互相鍵結而形成環。m為2~5的整數，以3或4為佳。In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbons with or without an ether bond, an alkyl group with or without an ether bond Cyanoalkyl with 2 to 11 carbons, alkenyl with 2 to 10 carbons with or without an ether bond, or aryl with 6 to 20 carbons with or without substituents. R ² and R ³ may also be bonded to each other to form a ring. m is an integer of 2 to 5, preferably 3 or 4.

R² 、R³ 之具有或不具有醚鍵之碳數1~10的烷基，該碳數1~10的烷基之碳數，以1~8為佳，以1~5為較佳。作為不具有醚鍵之烷基，可舉出甲基、乙基、正丙基、正丁基、正戊基、正己基等。作為具有醚鍵之烷基，可舉出下述式(2)或(3)表示之基等。The alkyl group having 1-10 carbon atoms of R ² and R ³ may or may not have an ether bond, the alkyl group having 1-10 carbon atoms preferably has 1-8 carbon atoms, more preferably 1-5 carbon atoms. A methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group etc. are mentioned as an alkyl group which does not have an ether bond. As an alkyl group which has an ether bond, the group represented by following formula (2) or (3), etc. are mentioned.

式(2)中，R⁴ 表示碳數1~8的烷基，Z¹ 表示碳數2~9的伸烷基，R⁴ 與Z¹ 的碳數之合計為3~10。 *表示連結鍵。 式(3)中，R⁵ 表示碳數1~6的烷基、Z² 表示碳數2~7的伸烷基，Z³ 表示碳數2~7的伸烷基，R⁵ 、Z² 、Z³ 的碳數之合計為5~10。*表示連結鍵。In formula (2), R ⁴ represents an alkyl group having 1 to 8 carbons, Z ¹ represents an alkylene group having 2 to 9 carbons, and the total number of carbons of R ⁴ and Z ¹ is 3 to 10. * Indicates a link key. In formula (3), R ⁵ represents an alkyl group with 1 to 6 carbons, Z ² represents an alkylene group with 2 to 7 carbons, Z ³ represents an alkylene group with 2 to 7 carbons, R ⁵ , Z ² , The sum of the carbon numbers of Z ³ is 5-10. * Indicates a link key.

R² 、R³ 之具有或不具有醚鍵之碳數2~11的氰烷基，該碳數2~11的氰烷基之碳數，以2~9為佳，以2~6為較佳。作為不具有醚鍵之氰烷基，可舉出氰甲基、2-氰乙基、3-氰丙基、4-氰丁基、6-氰己基等。作為具有醚鍵之氰烷基，可舉出下述式(4)或(5)表示之基等。R ² and R ³ are cyanoalkyl groups with or without ether linkages and carbon numbers of 2 to 11. The carbon number of the cyanoalkyl groups with 2 to 11 carbon numbers is preferably 2 to 9, and more preferably 2 to 6. good. Examples of the cyanoalkyl group not having an ether bond include cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, 6-cyanohexyl and the like. Examples of the cyanoalkyl group having an ether bond include groups represented by the following formula (4) or (5).

式(4)中，R⁶ 表示碳數2~9的氰烷基，Z⁴ 表示碳數2~9的伸烷基，R⁶ 與Z⁴ 的碳數之合計為4~11。*表示連結鍵。 式(5)中，R⁷ 表示碳數2~7的氰烷基，Z⁵ 表示碳數2~7的伸烷基，Z⁶ 表示碳數2~7的伸烷基，R⁷ 、Z⁵ 、Z⁶ 的碳數之合計為6~11。*表示連結鍵。In formula (4), R ⁶ represents a cyanoalkyl group with 2 to 9 carbons, Z ⁴ represents an alkylene group with 2 to 9 carbons, and the total carbon number of R ⁶ and Z ⁴ is 4 to 11. * Indicates a link key. In formula (5), R ⁷ represents a cyanoalkyl group with 2 to 7 carbons, Z ⁵ represents an alkylene group with 2 to 7 carbons, Z ⁶ represents an alkylene group with 2 to 7 carbons, R ⁷ , Z ⁵ , The sum of the carbon numbers of Z ⁶ is 6~11. * Indicates a link key.

R² 、R³ 之具有或不具有醚鍵之碳數2~10的烯基，該碳數2~10的烯基之碳數，以2~9為佳，以2~6為較佳。作為不具有醚鍵之烯基，可舉出乙烯基、烯丙基、1-丁烯基、2-丁烯基、1-戊烯基等。 作為具有醚鍵之烯基，可舉出下述式(6)或(7)表示之基等。The alkenyl group having 2-10 carbon atoms of R ² and R ³ may or may not have an ether bond, the alkenyl group having 2-10 carbon atoms preferably has 2-9 carbon atoms, more preferably 2-6 carbon atoms. As an alkenyl group which does not have an ether bond, a vinyl group, an allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group etc. are mentioned. As an alkenyl group which has an ether bond, the group represented by following formula (6) or (7), etc. are mentioned.

式(6)中，R⁸ 表示碳數2~8的烯基，Z⁷ 表示碳數2~8的伸烷基，R⁸ 與Z⁷ 的碳數之合計為4~10。*表示連結鍵。 式(7)中，R⁹ 表示碳數2~6的烯基，Z⁸ 表示碳數2~6的伸烷基，Z⁹ 表示碳數2~6的伸烷基，R⁹ 、Z⁸ 、Z⁹ 的碳數之合計為6~10。*表示連結鍵。In formula (6), R ⁸ represents an alkenyl group with 2 to 8 carbons, Z ⁷ represents an alkylene group with 2 to 8 carbons, and the total number of carbons of R ⁸ and Z ⁷ is 4 to 10. * Indicates a link key. In formula (7), R ⁹ represents an alkenyl group with 2 to 6 carbons, Z ⁸ represents an alkylene group with 2 to 6 carbons, Z ⁹ represents an alkylene group with 2 to 6 carbons, R ⁹ , Z ⁸ , The sum of the carbon numbers of Z ⁹ is 6-10. * Indicates a link key.

R² 、R³ 之具有或不具有取代基之碳數6~20的芳基，該碳數6~20的芳基之碳數，以6~10為佳。作為未取代的芳基，可舉出苯基、1-萘基、2-萘基等。作為具有取代基之芳基的取代基，可舉出甲基、乙基等的碳數1~6的烷基；甲氧基、乙氧基等的碳數1~6的烷氧基；氟原子、氯原子等的鹵素原子等。R ² and R ³ are aryl groups with or without substituents having 6-20 carbon atoms, preferably 6-10 aryl groups with 6-20 carbon atoms. Examples of the unsubstituted aryl group include phenyl, 1-naphthyl, 2-naphthyl and the like. Examples of substituents for aryl groups having substituents include alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups; fluorine atoms, halogen atoms such as chlorine atoms, etc.

作為R² 與R³ 鍵結而形成的環，可舉出吡咯啶(pyrrolidine)環、哌啶(piperidine)環、嗎啉(morpholine)環等。 式(1)中，A¹ 表示下述式(8)~(10)的任一者表示之二價基。Examples of the ring formed by bonding R ² and R ³ include a pyrrolidine ring, a piperidine ring, and a morpholine ring. In formula (1), A ¹ represents a divalent group represented by any one of the following formulas (8) to (10).

式(8)~(10)中，A² 及A³ 各自獨立地表示碳數1~10的伸烷基，n表示1~10的整數。*1表示與碳原子之連結鍵，*2表示與氮原子之連結鍵。In formulas (8) to (10), A ² and A ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10. *1 represents a bond with a carbon atom, and *2 represents a bond with a nitrogen atom.

A² 、A³ 之碳數1~10的伸烷基之碳數，以1~8為佳，以1~6為較佳。作為碳數1~10的伸烷基，可舉出亞甲基、伸乙基、三亞甲基、四亞甲基、五亞甲基等的直鏈狀伸烷基；丙烷-1,2-二基、丁烷-1,3-二基等的支鏈狀伸烷基。n為1~10的整數，以1~5的整數為佳。The carbon number of the alkylene group having 1-10 carbons in A ² and A ³ is preferably 1-8, more preferably 1-6. Examples of the alkylene group having 1 to 10 carbon atoms include straight-chain alkylene groups such as methylene, ethylidene, trimethylene, tetramethylene, and pentamethylene; propane-1,2- Branched chain alkylene such as diyl and butane-1,3-diyl. n is an integer of 1-10, preferably an integer of 1-5.

又，在兩性離子結構的正電荷是源自含氮的雜環或四級鏻的情況中，可舉出將在前述式(1)的含兩性離子單元之四級銨部位(N⁺ R² R³ )取代成為下述式(11)~(14)的構造之含兩性離子單元。Also, in the case where the positive charge of the zwitterionic structure is derived from a nitrogen-containing heterocycle or a quaternary phosphonium, the quaternary ammonium site (N ⁺ R ² R ³ ) is substituted into a zwitterion-containing unit having a structure of the following formulas (11) to (14).

(式中，R¹⁰ 表示具有或不具有醚鍵之碳數1~10的烷基、具有或不具有醚鍵之碳數2~11的氰烷基、或是具有或不具有醚鍵之碳數2~10的烯基，R¹¹ 表示氫原子、或是具有或不具有醚鍵之碳數1~10的烷基。但是R¹⁰ 或R¹¹ 的任一方不存在原子或基而為自由基狀態且表示對前述A¹ 的連結鍵。*表示對(CH₂ )_m 的連結鍵)。(wherein, R ¹⁰ represents an alkyl group with or without ether linkages having 1 to 10 carbon atoms, a cyanoalkyl group with or without ether linkages having 2 to 11 carbon atoms, or a carbon atom with or without ether linkages An alkenyl group with a number of 2 to 10, R ¹¹ represents a hydrogen atom, or an alkyl group with or without an ether bond with a carbon number of 1 to 10. However, either R ¹⁰ or R ¹¹ does not have an atom or a group and is a free radical state and represents the bond to the aforementioned A ^1. * represents the bond to (CH ₂ ) _m ).

(式中，R¹² ~R¹⁶ 各自獨立地表示氫原子、或是具有或不具有醚鍵之碳數1~10的烷基。但是R¹² ~R¹⁶ 之其中的一個不存在原子或基而為自由基狀態且表示對前述A¹ 的連結鍵。*表示對(CH₂ )_m 的連結鍵)。(In the formula, R ¹² to R ¹⁶ each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms with or without an ether bond. However, one of R ¹² to R ¹⁶ does not have an atom or group but is in a radical state and represents a bond to the aforementioned A ^1. * represents a bond to (CH ₂ ) _m ).

(式中，R¹⁷ ~R²¹ 各自獨立地表示氫原子、或是具有或不具有醚鍵之碳數1~10的烷基。但是R¹⁷ ~R²¹ 之其中的一個不存在原子或基而為自由基狀態且表示對前述A¹ 的連結鍵。*表示對(CH₂ )_m 的連結鍵)。(In the formula, R ¹⁷ to R ²¹ each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms with or without an ether bond. However, one of R ¹⁷ to R ²¹ does not have an atom or group but is in a radical state and represents a bond to the aforementioned A ^1. * represents a bond to (CH ₂ ) _m ).

(式中，R²² 表示具有或不具有醚鍵之碳數1~10的烷基、具有或不具有醚鍵之碳數2~11的氰烷基、具有或不具有醚鍵之碳數2~10的烯基、或是取代或未取代之碳數6~20的芳基。R²³ 、R²⁴ 各自獨立地表示氫原子、具有或不具有醚鍵之碳數1~10的烷基、具有或不具有醚鍵之碳數2~11的氰烷基、具有或不具有醚鍵之碳數2~10的烯基、或是取代或未取代之碳數6~20的芳基。但是R²² ~R²⁴ 之其中的一個不存在原子或基而為自由基狀態且表示對前述A¹ 的連結鍵。*表示對(CH₂ )_m 的連結鍵)。(wherein, ^R22 represents an alkyl group with or without ether linkages with 1 to 10 carbon atoms, a cyanoalkyl group with or without ether linkages with carbon number 2 to 11, or a carbon number with or without ether linkages with 2 ~10 alkenyl groups, or substituted or unsubstituted aryl groups with 6 to 20 carbon atoms. R ²³ and R ²⁴ each independently represent a hydrogen atom, an alkyl group with or without an ether bond with 1 to 10 carbon atoms, A cyanoalkyl group with or without ether linkages having 2 to 11 carbons, an alkenyl group with or without ether linkages having 2 to 10 carbons, or a substituted or unsubstituted aryl group with 6 to 20 carbons. But One of R ²² to R ²⁴ does not have an atom or a group but is in a free radical state and represents a bond to the aforementioned A ^1. * represents a bond to (CH ₂ ) _m ).

含兩性離子的丙烯酸系聚合物包括上述含兩性離子單元及(甲基)丙烯酸單元。 含兩性離子的丙烯酸系聚合物中之含兩性離子單元的比例，將含兩性離子的丙烯酸系聚合物的總量設為基準，為小於100質量%，較佳為30質量%以下，更佳為15質量%以下，特佳為0.1~10質量%，最佳為0.5~5.0質量%。含兩性離子的丙烯酸系聚合物中之含兩性離子單元的比例太少時，則在黏著性組合物的特性，不容易顯現源自含兩性離子單元之特性，且對凹凸面之埋入性低落，而且有端部外觀不良之情形。又，含兩性離子單元的比例太多時，比率有無法得到充分的黏著性之情形。The zwitterion-containing acrylic polymer includes the aforementioned zwitterion-containing units and (meth)acrylic acid units. The ratio of the zwitterion-containing unit in the zwitterion-containing acrylic polymer is less than 100% by mass, preferably 30% by mass or less, more preferably 15% by mass or less, preferably 0.1-10% by mass, most preferably 0.5-5.0% by mass. When the ratio of the zwitterion-containing unit in the zwitterion-containing acrylic polymer is too small, the characteristics of the adhesive composition are not easy to show the characteristics derived from the zwitterion-containing unit, and the embedding property to the concave-convex surface is low. , and there are cases where the appearance of the end is poor. Also, when the ratio of the zwitterion-containing unit is too large, sufficient adhesiveness may not be obtained in the ratio.

作為(甲基)丙烯酸單元，可舉出源自(甲基)丙烯酸酯的重複單元、源自(甲基)丙烯酸的重複單元、源自(甲基)丙烯醯胺的重複單元等。(甲基)丙烯酸單元的比例，將含兩性離子的丙烯酸系聚合物的總量設為基準，為大於0質量%，較佳為70質量%以上，更佳為85質量%以上，特佳為90~99.9質量%，最佳為95~99.5質量%。As a (meth)acrylic acid unit, the repeating unit derived from (meth)acrylate, the repeating unit derived from (meth)acrylic acid, the repeating unit derived from (meth)acrylamide, etc. are mentioned. The ratio of (meth)acrylic acid units is greater than 0% by mass, preferably at least 70% by mass, more preferably at least 85% by mass, particularly preferably at least 85% by mass, based on the total amount of the zwitterion-containing acrylic polymer. 90~99.9% by mass, preferably 95~99.5% by mass.

作為(甲基)丙烯酸酯，以(甲基)丙烯酸烷酯為佳。作為(甲基)丙烯酸烷酯，可舉出烷基的碳數為1~20之物，烷基可為直鏈，亦可為支鏈。作為(甲基)丙烯酸烷酯的具體例，可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一酯、(甲基)丙烯酸十二酯等。(甲基)丙烯酸烷酯可單獨或組合2種以上而使用。As (meth)acrylate, alkyl (meth)acrylate is preferable. Examples of the alkyl (meth)acrylate include those having 1 to 20 carbon atoms in the alkyl group, and the alkyl group may be straight or branched. Specific examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, ( n-butyl methacrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, (meth) Decyl acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, etc. Alkyl (meth)acrylate can be used individually or in combination of 2 or more types.

又，從使黏著性組合物的黏著力提升之觀點而言，以包括源自烷基的碳數為4以上之(甲基)丙烯酸烷酯的重複單元為佳。作為該(甲基)丙烯酸烷酯的碳數，較佳為4~12，更佳為4~6。又，烷基的碳數為4以上之(甲基)丙烯酸烷酯以丙烯酸烷酯為佳。Moreover, from a viewpoint of improving the adhesive force of an adhesive composition, it is preferable to contain the repeating unit derived from the C4 or more alkyl (meth)acrylate of an alkyl group. As carbon number of this alkyl (meth)acrylate, Preferably it is 4-12, More preferably, it is 4-6. Also, the alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms is preferably an alkyl acrylate.

在含兩性離子的丙烯酸系聚合物中，源自烷基的碳數為4以上之(甲基)丙烯酸烷酯的重複單元的比例，將含兩性離子的丙烯酸系聚合物的總量設為基準，良好為40~98質量%，較佳為45~95質量%，更佳為50~90質量%。In the zwitterion-containing acrylic polymer, the proportion of the repeating unit derived from the alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms is based on the total amount of the zwitterion-containing acrylic polymer , preferably 40-98% by mass, preferably 45-95% by mass, more preferably 50-90% by mass.

含兩性離子的丙烯酸系聚合物，除了源自烷基的碳數為4以上之(甲基)丙烯酸烷酯之重複單元以外，為了調整黏著性組合物的彈性模數、黏著特性等，亦可為包括源自烷基的碳數為1~3之(甲基)丙烯酸烷酯的重複單元之共聚物。又，該(甲基)丙烯酸烷酯以碳數1或2的(甲基)丙烯酸烷酯為佳，以(甲基)丙烯酸甲酯為較佳，以甲基丙烯酸甲酯為最佳。在含兩性離子的丙烯酸系聚合物中，源自烷基的碳數為1~3之(甲基)丙烯酸烷酯的重複單元的比例，將含兩性離子的丙烯酸系聚合物的總量設為基準，良好為0~30質量%，較佳為0~26質量%，更佳為0~22質量%。The zwitterion-containing acrylic polymer, in addition to repeating units derived from alkyl (meth)acrylates with a carbon number of 4 or more, can also be used to adjust the elastic modulus and adhesive properties of the adhesive composition. It is a copolymer comprising repeating units of alkyl (meth)acrylates with 1 to 3 carbon atoms derived from an alkyl group. In addition, the alkyl (meth)acrylate is preferably an alkyl (meth)acrylate having 1 or 2 carbon atoms, more preferably methyl (meth)acrylate, most preferably methyl methacrylate. In the zwitterion-containing acrylic polymer, the ratio of the repeating unit of the (meth)acrylic acid alkyl ester having 1 to 3 carbon atoms derived from the alkyl group, the total amount of the zwitterion-containing acrylic polymer is given as The standard is preferably 0 to 30% by mass, preferably 0 to 26% by mass, more preferably 0 to 22% by mass.

含兩性離子的丙烯酸系聚合物，能夠藉由使含兩性離子的聚合性單體與(甲基)丙烯酸系單體共聚合而得到。又，亦能夠使具有能夠導入兩性離子結構的結構之聚合性單體與(甲基)丙烯酸系單體共聚合，且使磺內酯化合物等對所得到的共聚合物起作用，而得到含兩性離子的丙烯酸系聚合物。又，在合成該等聚合物時，除了含兩性離子的聚合性單體或具有能夠導入兩性離子結構的結構之聚合性單體及(甲基)丙烯酸系單體以外，亦可使能夠與該等共聚合的其它單體共聚合。The zwitterion-containing acrylic polymer can be obtained by copolymerizing a zwitterion-containing polymerizable monomer and a (meth)acrylic monomer. In addition, it is also possible to copolymerize a polymerizable monomer having a structure capable of introducing a zwitterionic structure and a (meth)acrylic monomer, and make a sultone compound or the like act on the obtained copolymer to obtain a Zwitterionic acrylic polymer. Also, when synthesizing these polymers, in addition to polymerizable monomers containing zwitterions or polymerizable monomers having a structure capable of introducing zwitterionic structures and (meth)acrylic monomers, it is also possible to make Copolymerization of other monomers such as copolymerization.

首先，說明使前者之含兩性離子的聚合性單體與(甲基)丙烯酸系單體共聚合而得到含兩性離子的丙烯酸系聚合物之情況。在含兩性離子的丙烯酸系聚合物的合成所使用之含兩性離子的聚合性單體，是指在分子內具有聚合性碳-碳雙鍵及前述分極結構之化合物。作為(甲基)丙烯酸系單體，可舉出前述(甲基)丙烯酸酯、(甲基)丙烯酸、(甲基)丙烯醯胺等。First, the case where a zwitterion-containing acrylic polymer is obtained by copolymerizing the former zwitterion-containing polymerizable monomer and a (meth)acrylic monomer will be described. The zwitterion-containing polymerizable monomer used in the synthesis of the zwitterion-containing acrylic polymer refers to a compound having a polymerizable carbon-carbon double bond and the aforementioned polarized structure in the molecule. As a (meth)acrylic-type monomer, the said (meth)acrylate, (meth)acrylic acid, (meth)acrylamide etc. are mentioned.

在本發明，含兩性離子的聚合性單體能夠配合目標含兩性離子的丙烯酸系聚合物而適當地決定。例如，具有上述式(1)表示的重複單元之含兩性離子的丙烯酸系聚合物，能夠使用下述式(1a)表示之含兩性離子的聚合性單體而合成。又，亦能夠使用將在下述式(1a)之含兩性離子的聚合性單體之四級銨部位(N⁺ R² R³ )取代成為前述式(11)~(14)的構造之含兩性離子的聚合性單體。In the present invention, the zwitterion-containing polymerizable monomer can be appropriately determined according to the target zwitterion-containing acrylic polymer. For example, a zwitterion-containing acrylic polymer having a repeating unit represented by the above formula (1) can be synthesized using a zwitterion-containing polymerizable monomer represented by the following formula (1a). In addition, it is also possible to use amphoteric amphoteric monomers that substitute the quaternary ammonium site (N ⁺ R ² R ³ ) of the zwitterion-containing polymerizable monomer of the following formula (1a) into the structure of the aforementioned formulas (11) to (14). Ionic polymerizable monomer.

式(1a)中，R¹ 、R² 、R³ 、A¹ 、及m各自表示與前述相同的意思。 式(1a)表示之兩性離子含有聚合性單體沒有特別的限定。例如，如下述式所顯示，含式(1a)的聚合性單體能夠藉由使對應之胺化合物(1b)與磺內酯化合物(1c)反應而得到。In the formula (1a), R ¹ , R ² , R ³ , A ¹ , and m each represent the same meaning as above. The zwitterion-containing polymerizable monomer represented by formula (1a) is not particularly limited. For example, as shown in the following formula, the polymerizable monomer containing the formula (1a) can be obtained by reacting the corresponding amine compound (1b) with the sultone compound (1c).

(上述式中，R¹ ~R³ 、A¹ 表示與前述相同意思，p為(m-2))。 胺化合物(1b)能夠使用習知的方法而製造、取得。 又，在上述胺化合物(1b)中，亦能夠使用將胺部位(NR² R³ )取代成為下述式(15)~(18)表示之能夠導入兩性離子的構造之化合物。(In the above formula, R ¹ to R ³ and A ¹ have the same meaning as above, and p is (m-2)). The amine compound (1b) can be produced and obtained by a known method. In addition, among the above-mentioned amine compounds (1b), compounds in which the amine moieties (NR ² R ³ ) are substituted into structures capable of introducing zwitterions represented by the following formulas (15) to (18) can also be used.

(式中，R¹⁰ ~R²⁴ 表示與前述相同意思。但是R¹⁰ 或R¹¹ 之其中的一個不存在原子或基而為自由基狀態且表示對前述A¹ 的連結鍵。R¹² ~R¹⁶ 之其中的一個不存在原子或基而為自由基狀態且表示對前述A¹ 的連結鍵。R¹⁷ ~R²¹ 之其中的一個不存在原子或基而為自由基狀態且表示對前述A¹ 的連結鍵。R²² ~R²⁴ 之其中的一個不存在原子或基而為自由基狀態且表示對前述A¹ 的連結鍵)。(In the formula, R ¹⁰ to R ²⁴ represent the same meaning as above. However, one of R ¹⁰ or R ¹¹ does not have an atom or a group, but is in a free radical state and represents a bond to the aforementioned A ^1. R ¹² to R ¹⁶ One of them does not have an atom or a radical but is in a free radical state and represents a bond to the aforementioned A ^1. One of R ¹⁷ ~ R ²¹ does not have an atom or a radical but is in a free radical state and represents a bond to the aforementioned A ¹ A bond. One of R ²² to R ²⁴ does not have an atom or a group but is in a free radical state and represents a bond to the aforementioned A ¹ ).

作為前述磺內酯化合物(1c)，可舉出1,2-乙烷磺內酯、1,3-丙烷磺內酯、1,4-丁烷磺內酯、2,4-丁烷磺內酯、1.5-戊烷磺內酯。該等為習知化合物，能夠使用習知的方法而製造、取得，亦能夠使用市售品。Examples of the aforementioned sultone compound (1c) include 1,2-ethane sultone, 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, Esters, 1.5-pentane sultone. These are known compounds and can be produced and obtained using known methods, and commercially available products can also be used.

在胺化合物(1b)與磺內酯化合物(1c)之反應，磺內酯化合物(1c)的使用量，相對於胺化合物(1b)，良好為0.8~1.2當量，較佳為0.9~1.1當量。藉由使磺內酯化合物(1c)的使用量在上述範圍，能夠省略將未反應物除去之步驟，或是縮短除去所花費的時間。In the reaction between the amine compound (1b) and the sultone compound (1c), the amount of the sultone compound (1c) is preferably 0.8-1.2 equivalents, preferably 0.9-1.1 equivalents, relative to the amine compound (1b). . By making the usage-amount of sultone compound (1c) into the said range, the process of removing an unreacted substance can be omitted, or the time taken for removal can be shortened.

胺化合物(1b)與磺內酯化合物(1c)之反應可無溶劑而進行，亦可在惰性溶劑的存在下進行。作為所使用的惰性溶劑，可舉出四氫呋喃、二甘醇二甲醚(diglyme)等的醚系溶劑；乙腈、丙腈等的丙腈系溶劑；丙酮、甲基乙基酮等的酮系溶劑；甲苯、二甲苯等的芳香族烴系溶劑；氯仿等的鹵化烴系溶劑等。The reaction of the amine compound (1b) and the sultone compound (1c) may be performed without a solvent or in the presence of an inert solvent. Examples of the inert solvent used include ether-based solvents such as tetrahydrofuran and diglyme; propionitrile-based solvents such as acetonitrile and propionitrile; and ketone-based solvents such as acetone and methyl ethyl ketone. ; Aromatic hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as chloroform, etc.

使用惰性溶劑時，其使用量沒有特別限制，相對於胺化合物(1b)1質量份，通常為1~100質量份。反應溫度沒有特別限定，通常為0~200℃，良好為10~100℃，較佳為20~60℃的範圍。又，可在常壓(大氣壓)下實施反應，亦可在加壓條件下實施反應。When using an inert solvent, the usage-amount is not specifically limited, Usually, it is 1-100 mass parts with respect to 1 mass part of amine compound (1b). The reaction temperature is not particularly limited, but is usually in the range of 0 to 200°C, preferably in the range of 10 to 100°C, more preferably in the range of 20 to 60°C. In addition, the reaction may be carried out under normal pressure (atmospheric pressure), or may be carried out under pressurized conditions.

反應時間沒有特別限定，通常為12~332小時，較佳為24~168小時。從能夠防止因氧氣引起氧化、因空氣中的水分引起磺內酯化合物(1c)產生水解致使產率低落的觀點而言，反應以在氮氣、氬氣體等的惰性氣體環境下進行為佳。能夠使用氣體層析法、高效液體層析法、薄層層析法、NMR、IR等通常的分析手段而確認反應的進行。The reaction time is not particularly limited, and is usually 12 to 332 hours, preferably 24 to 168 hours. From the viewpoint of preventing oxidation due to oxygen and hydrolysis of the sultone compound (1c) due to moisture in the air, resulting in a decrease in yield, it is preferable to carry out the reaction under an inert gas atmosphere such as nitrogen or argon. The progress of the reaction can be confirmed using common analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR, and IR.

反應結束後，進行在有機合成化學之通常的後處理操作，亦能夠按照需要而使用再結晶、管柱層析法等習知的精製方法進行精製且將目標含兩性離子的聚合性單體離析。又，在本發明，亦可使用市售品作為含兩性離子的聚合性單體。又，針對將前述胺化合物(1b)的胺取代成為式(15)~(18)之能夠導入兩性離子結構的結構之化合物，亦能夠與使用上述胺化合物(1b)時同樣地進行，藉由使其與磺內酯化合物(1c)反應而得到含兩性離子的聚合性單體。After the reaction is completed, the usual post-processing operations in organic synthetic chemistry can also be used to refine and isolate the target zwitterion-containing polymerizable monomer as required by using known purification methods such as recrystallization and column chromatography. . Moreover, in this invention, a commercial item can also be used as a zwitterion-containing polymerizable monomer. In addition, it is also possible to substitute the amine of the above-mentioned amine compound (1b) into a compound having a structure capable of introducing a zwitterionic structure of the formulas (15) to (18) in the same manner as when using the above-mentioned amine compound (1b), by This is reacted with the sultone compound (1c) to obtain a zwitterion-containing polymerizable monomer.

含兩性離子的丙烯酸系聚合物的合成方法沒有特別限定。例如，能夠藉由在自由基聚合起始劑的存在下，使包括含兩性離子的聚合性單體、(甲基)丙烯酸系單體、及視需要之能夠與含兩性離子的聚合性單體共聚合的單體之單體混合物進行聚合反應，以合成含兩性離子的丙烯酸系聚合物。The synthesis method of the zwitterion-containing acrylic polymer is not particularly limited. For example, it can be obtained by including a zwitterion-containing polymerizable monomer, a (meth)acrylic monomer, and optionally a zwitterion-containing polymerizable monomer in the presence of a radical polymerization initiator. A monomer mixture of copolymerized monomers is polymerized to synthesize a zwitterion-containing acrylic polymer.

作為自由基聚合起始劑，可舉出有機過氧化物、偶氮系化合物等。作為有機過氧化物，可舉出過氧化月桂醯、過氧化苯甲醯等的二醯基過氧化物(diacyl peroxide)類；1,1-雙(三級丁基過氧化)環己烷、1,1-雙(三級丁基過氧化)3,3,5-三甲基環己烷等的過氧化縮酮(peroxyketal)類；過氧化二碳酸二異丙酯、過氧化二碳酸二-2-乙基己酯等的過氧化二碳酸酯(peroxydicarbonate)類；過氧化2-乙基己酸三級丁酯、過氧化異丁酸三級丁酯等的過氧化酯(peroxyester)類等。As a radical polymerization initiator, an organic peroxide, an azo compound, etc. are mentioned. Examples of organic peroxides include diacyl peroxides such as lauryl peroxide and benzoyl peroxide; 1,1-bis(tertiary butylperoxy)cyclohexane, Peroxyketals such as 1,1-bis(tertiary butyl peroxide) 3,3,5-trimethylcyclohexane; diisopropyl peroxydicarbonate, diisopropyl peroxydicarbonate - peroxydicarbonate such as 2-ethylhexyl ester; peroxyester such as tertiary butyl peroxy 2-ethylhexanoate and tertiary butyl peroxyisobutyrate wait.

作為偶氮系化合物，可舉出2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷-1-腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基2,2’-偶氮雙(2-甲基丙酸酯)、4,4’-偶氮雙(4-氰戊酸)、2,2’-偶氮雙(2-羥甲基丙腈)、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷] (2,2′-azobis[2-(2-imidazolin-2-yl) propane)等。該等能夠1種單獨、或組合2種以上而使用。Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane -1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile ), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2- hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (2,2'-azobis[2-(2-imidazolin-2-yl) propane )wait. These can be used individually by 1 type or in combination of 2 or more types.

自由基聚合起始劑的使用量，相對於在聚合反應所使用的單體1莫耳(但是，在共聚物的情況中，則為單體合計莫耳)，通常為0.0001~0.1000莫耳，較佳為0.0005~0.0050莫耳。The amount of the radical polymerization initiator used is usually 0.0001 to 0.1000 moles relative to 1 mole of monomers used in the polymerization reaction (however, in the case of a copolymer, it is the total moles of monomers), Preferably it is 0.0005~0.0050 mole.

自由基聚合反應的條件，只要目標聚合反應進行，就沒有特別限定。加熱溫度通常為40~150℃，反應時間能夠適當地設定為1分鐘~24小時的範圍。 所得到的反應液，可直接使用在其黏著性組合物的調製，亦可依照常用的方法而將含兩性離子的丙烯酸系聚合物進行離析、精製。The conditions of the radical polymerization reaction are not particularly limited as long as the intended polymerization reaction proceeds. The heating temperature is usually 40 to 150° C., and the reaction time can be appropriately set within a range of 1 minute to 24 hours. The obtained reaction liquid can be directly used in the preparation of the adhesive composition, and the zwitterion-containing acrylic polymer can also be isolated and purified according to a common method.

又，如前述，含兩性離子的丙烯酸系聚合物，亦能夠使具有能夠導入兩性離子結構的結構之聚合性單體與(甲基)丙烯酸系單體共聚合，且使磺內酯化合物等對所得到的聚合物起作用而得到。In addition, as mentioned above, the zwitterion-containing acrylic polymer can also copolymerize a polymerizable monomer having a structure capable of introducing a zwitterion structure and a (meth)acrylic monomer, and allow the sultone compound, etc. The resulting polymer works to obtain.

作為能夠導入兩性離子結構的結構，可舉出，例如，胺基、含氮的雜環、膦(phosphine)等。作為具有能夠導入兩性離子結構的結構之聚合性單體，能夠適合使用前述的胺化合物(1b)。胺化合物(1b)與(甲基)丙烯酸系單體的共聚合，能夠在和前述含兩性離子的聚合性單體與(甲基)丙烯酸系單體的共聚合同樣的條件下進行，且共聚合時視需要使包括能夠與胺化合物(1b)及(甲基)丙烯酸系單體共聚合的單體之單體混合物進行聚合反應，藉以合成具有能夠導入兩性離子結構的結構之聚合物。Examples of structures capable of introducing a zwitterionic structure include amine groups, nitrogen-containing heterocycles, phosphine, and the like. As the polymerizable monomer having a structure capable of introducing a zwitterionic structure, the aforementioned amine compound (1b) can be suitably used. The copolymerization of the amine compound (1b) and the (meth)acrylic monomer can be carried out under the same conditions as the aforementioned copolymerization of the zwitterion-containing polymerizable monomer and the (meth)acrylic monomer, and the copolymerization During the polymerization, a monomer mixture including a monomer copolymerizable with the amine compound (1b) and a (meth)acrylic monomer is optionally polymerized to synthesize a polymer having a structure capable of introducing a zwitterionic structure.

其次，藉由使前述磺內酯化合物(1c)對所得到的丙烯酸系聚合物之能夠導入兩性離子結構的結構進行反應，以得到含兩性離子的丙烯酸系聚合物。胺基等的官能基與磺內酯化合物之反應，能夠在和前述胺化合物(1b)與磺內酯化合物(1c)的反應同樣的條件下進行。亦能夠使用將該胺化合物(1b)的胺部位(NR² R³ )取代成為前述式(15)~(18)之能夠導入兩性離子結構的結構之化合物，以代替上述胺化合物(1b)。Next, a zwitterion-containing acrylic polymer is obtained by reacting the aforementioned sultone compound (1c) with a structure capable of introducing a zwitterion structure in the obtained acrylic polymer. The reaction of a functional group such as an amine group with the sultone compound can be carried out under the same conditions as the reaction of the aforementioned amine compound (1b) with the sultone compound (1c). Instead of the amine compound (1b), it is also possible to use a compound in which the amine portion (NR ² R ³ ) of the amine compound (1b) is substituted into a structure capable of introducing a zwitterionic structure of the aforementioned formulas (15) to (18).

含兩性離子的丙烯酸系聚合物，除了上述的重複單元以外，亦可具有源自含官能基單體的重複單元。作為含官能基單體的官能基，可舉出羥基、羧基、胺基、環氧基等。含官能基單體與後述的交聯劑反應且成為交聯起點，或與含不飽和基的化合物反應，而能夠將不飽和基導入至含兩性離子的丙烯酸系聚合物的側鏈。The zwitterion-containing acrylic polymer may have a repeating unit derived from a functional group-containing monomer in addition to the above-mentioned repeating unit. As a functional group of a functional group containing monomer, a hydroxyl group, a carboxyl group, an amino group, an epoxy group etc. are mentioned. The functional group-containing monomer reacts with a crosslinking agent described later to become a crosslinking origin, or reacts with an unsaturated group-containing compound to introduce an unsaturated group into the side chain of the zwitterion-containing acrylic polymer.

作為含官能基單體，可舉出含羥基單體、含羧基單體、含胺基單體、含環氧基單體等。該等單體可單獨或組合2種以上而使用。該等之中，以含羥基單體、含羧基單體為佳，以含羥基單體為較佳。Examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, and the like. These monomers can be used individually or in combination of 2 or more types. Among these, hydroxyl-containing monomers and carboxyl-containing monomers are preferred, and hydroxyl-containing monomers are more preferred.

作為含羥基單體，可舉出，例如，(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸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-羥基丁酯等的(甲基)丙烯酸羥基烷酯；乙烯醇、烯丙醇類等的不飽和醇類等。Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol class etc.

作為含羧基單體，可舉出，例如，巴豆酸等的乙烯性不飽和單羧酸；反丁烯二酸、伊康酸、檸康酸等的乙烯性不飽和二羧酸及其酸酐、甲基丙烯酸2-羧基乙酯等。As the carboxyl group-containing monomer, for example, ethylenically unsaturated monocarboxylic acids such as crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, citraconic acid and their anhydrides, 2-carboxyethyl methacrylate, etc.

源自含官能基單體的重複單元的比例，將含兩性離子的丙烯酸系聚合物的總量設為基準，為70質量%以下，較佳為50質量%以下。The ratio of the repeating unit derived from the functional group-containing monomer is 70% by mass or less, preferably 50% by mass or less, based on the total amount of the zwitterion-containing acrylic polymer.

又，除了上述以外，含兩性離子的丙烯酸系聚合物亦可含有源自苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲酸乙烯酯、乙酸乙烯酯、丙烯腈、丙烯醯胺等之能夠與上述的丙烯酸系單體共聚合的單體之重複單元。In addition, the zwitterion-containing acrylic polymer may contain compounds derived from styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, etc. A repeating unit of a monomer copolymerized with the above-mentioned acrylic monomer.

所得到之含兩性離子的丙烯酸系聚合物的玻璃轉移溫度(Tg)，較佳為-60~-20℃，更佳為-50~-22℃。含兩性離子的丙烯酸系聚合物的Tg，是指由含兩性離子的丙烯酸系聚合物所構成的試料在頻率1Hz的動態黏彈性測定中，在-60~50℃的區域之損失正切(tanδ)顯示最大值之溫度。含兩性離子的丙烯酸系聚合物的Tg太低時，容易產生糊劑殘渣。又，Tg太高時，對電路面的凹凸之埋入性有低落之情形。The glass transition temperature (Tg) of the obtained zwitterion-containing acrylic polymer is preferably -60~-20°C, more preferably -50~-22°C. The Tg of the zwitterion-containing acrylic polymer refers to the loss tangent (tanδ) in the region of -60 to 50°C in the dynamic viscoelasticity measurement of a sample composed of the zwitterion-containing acrylic polymer at a frequency of 1 Hz Displays the maximum temperature. When the Tg of the zwitterion-containing acrylic polymer is too low, paste residues tend to be generated. Also, when Tg is too high, the embedding property to the unevenness of the circuit surface may be reduced.

含兩性離子的丙烯酸系聚合物的玻璃轉移溫度，例如，將源自烷基的碳數為4以上之(甲基)丙烯酸烷酯的重複單元的比例增大時，有低落之傾向。The glass transition temperature of the zwitterion-containing acrylic polymer tends to decrease when, for example, the proportion of repeating units derived from an alkyl group having 4 or more carbon atoms is increased.

又，含兩性離子的丙烯酸系聚合物的質量平均分子量(Mw)，較佳為1萬~30萬，更佳為2萬~20萬。又，在本說明書，所謂質量平均分子量，是使用凝膠滲透層析法而測定之標準聚苯乙烯換算之值。含兩性離子的丙烯酸系聚合物的Mw太低時，容易產生糊劑殘渣。又，Mw太高時，對電路面的凹凸之埋入性有低落之情形。Moreover, the mass average molecular weight (Mw) of the zwitterion-containing acrylic polymer is preferably from 10,000 to 300,000, more preferably from 20,000 to 200,000. In addition, in this specification, a mass average molecular weight is the value of standard polystyrene conversion measured using the gel permeation chromatography. When the Mw of the zwitterion-containing acrylic polymer is too low, paste residues tend to be generated. Also, when Mw is too high, the embedding property to the unevenness of the circuit surface may be reduced.

例如，在製造含兩性離子的丙烯酸系聚合物時若增大所使用的自由基聚合起始劑，則含兩性離子的丙烯酸系聚合物的質量平均分子量有降低之傾向。又，增長聚合反應時間時，質量平均分子量有增大之傾向。使聚合反應溫度上升時，質量平均分子量有降低之傾向。For example, when the radical polymerization initiator used in the production of the zwitterion-containing acrylic polymer is increased, the mass average molecular weight of the zwitterion-containing acrylic polymer tends to decrease. Also, when the polymerization reaction time is prolonged, the mass average molecular weight tends to increase. When the polymerization reaction temperature is increased, the mass average molecular weight tends to decrease.

又，含兩性離子的丙烯酸系聚合物的分子量分佈(Mw/Mn、Mn為數量平均分子量)，較佳為15以下，更佳為2~11。含兩性離子的丙烯酸系聚合物的分子量分佈太廣闊時，容易產生糊劑殘渣。Moreover, the molecular weight distribution (Mw/Mn, Mn is a number average molecular weight) of the zwitterion-containing acrylic polymer is preferably 15 or less, more preferably 2-11. When the molecular weight distribution of the zwitterion-containing acrylic polymer is too wide, paste residues are likely to be generated.

分佈例如，可使用活性自由基法調製含兩性離子的丙烯酸系聚合物，藉此，含兩性離子的丙烯酸系聚合物的分子量亦能夠狹窄化。在活性自由基法中，例如，使用含碲化合物作為自由基聚合起始劑。又，使用原子轉移自由基聚合(Atom Transfer Radical Polymerization：ATRP)、可逆性加成‧斷裂鏈轉移聚合(Reversible Addition/Fragmentation Chain Transfer Polymerization：RAFT)等的聚合法，亦能夠使分子量分佈狹窄化。Distribution For example, the zwitterion-containing acrylic polymer can be prepared by using an active radical method, whereby the molecular weight of the zwitterion-containing acrylic polymer can also be narrowed. In the living radical method, for example, a tellurium-containing compound is used as a radical polymerization initiator. In addition, the molecular weight distribution can also be narrowed by using polymerization methods such as atom transfer radical polymerization (ATRP) and reversible addition/fragmentation chain transfer polymerization (RAFT).

(黏著性組合物的成分) 本發明的黏著性組合物包括丙烯酸系聚合物，較佳為包括含兩性離子的丙烯酸系聚合物。使用含兩性離子的丙烯酸系聚合物時，可單獨使用1種，亦可組合2種以上而使用。黏著性組合物可僅由含兩性離子的丙烯酸系聚合物所形成，亦可包括含兩性離子的丙烯酸系聚合物以外的成分。在本發明的黏著性組合物中之含兩性離子的丙烯酸系聚合物的比例，將黏著性組合物的總量作為基準，良好為80質量%以上，較佳為85質量%以上，更佳為90質量%以上。(ingredients of adhesive composition) The adhesive composition of the present invention comprises an acrylic polymer, preferably a zwitterion-containing acrylic polymer. When using a zwitterion-containing acrylic polymer, it may use individually by 1 type, and may use it in combination of 2 or more types. The adhesive composition may consist only of the zwitterion-containing acrylic polymer, or may include components other than the zwitterion-containing acrylic polymer. The ratio of the zwitterion-containing acrylic polymer in the adhesive composition of the present invention is preferably at least 80% by mass, preferably at least 85% by mass, more preferably at least 85% by mass, based on the total amount of the adhesive composition. More than 90% by mass.

除了含兩性離子的丙烯酸系聚合物以外，本發明的黏著性組合物亦可包括，例如，能量線硬化性化合物、交聯劑、光聚合起始劑、含兩性離子的丙烯酸系聚合物以外的黏著性聚合物、及其它添加劑。In addition to the zwitterion-containing acrylic polymer, the adhesive composition of the present invention may also include, for example, energy ray-curing compounds, crosslinking agents, photopolymerization initiators, zwitterion-containing acrylic polymers other than Adhesive polymers, and other additives.

(能量線硬化性化合物) 作為能量線硬化性化合物，以在分子內具有不飽和基且能夠藉由照射能量線而聚合硬化的單體或寡聚物為佳。作為此種能量線硬化性化合物，可舉出，例如，三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯等的多價(甲基)丙烯酸酯單體、胺甲酸乙酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等的寡聚物。(energy ray hardening compound) The energy ray curable compound is preferably a monomer or oligomer having an unsaturated group in the molecule and capable of being polymerized and cured by irradiation of energy ray. As such an energy ray-curing compound, for example, trimethylolpropane tri(meth)acrylate, neopentylthritol (meth)acrylate, neopentylthritol tetra(meth)acrylate Polyvalent (meth) Acrylate monomers, oligomers of urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, epoxy (meth)acrylate, etc.

該等之中，從分子量較高、不容易使黏著劑層的彈性模數低落的的觀點而言，以胺甲酸乙酯(甲基)丙烯酸酯寡聚物為佳。能量線硬化性化合物的分子量(在寡聚物的情況中，則為質量平均分子量)，良好為100~12000，較佳為200~10000，更佳為400~8000，特佳為600~6000。Among them, the urethane (meth)acrylate oligomer is preferable from the viewpoint that the molecular weight is relatively high and the modulus of elasticity of the adhesive layer is not easily reduced. The molecular weight of the energy ray-curable compound (mass average molecular weight in the case of an oligomer) is preferably 100-12000, preferably 200-10000, more preferably 400-8000, and most preferably 600-6000.

將能量線硬化性化合物使用在黏著性組合物時，其調配比例，將黏著性組合物的總量作為基準，良好為1~99質量%，較佳為10~85質量%，更佳為20~80質量%。When the energy ray-curing compound is used in the adhesive composition, the blending ratio is preferably 1 to 99% by mass, preferably 10 to 85% by mass, more preferably 20% based on the total amount of the adhesive composition. ~80% by mass.

(交聯劑) 黏著性組合物亦可進一步含有交聯劑。交聯劑是，例如，對源自丙烯酸系聚合物所具有的含官能基單體之官能基進行反應而使丙烯酸系聚合物彼此交聯之物。作為交聯劑，可舉出，例如，甲苯二異氰酸酯、六亞甲基二異氰酸酯等、及該等的加成物等的異氰酸酯系交聯劑；乙二醇環氧丙基醚、1,3-雙(N,N’-二環氧丙基胺甲基)環己烷等的環氧系交聯劑；六[1-(2-甲基)-氮丙啶基]三磷雜三嗪(hexa[1-(2-methyl)-aziridinyl]triphosphatriazine)等的氮丙啶系交聯劑；鋁螯合物等的螯合物系交聯劑等。該等交聯劑可單獨或組合2種以上而使用。(crosslinking agent) The adhesive composition may further contain a crosslinking agent. The crosslinking agent is, for example, reacting a functional group derived from a functional group-containing monomer contained in an acrylic polymer to crosslink acrylic polymers. Examples of the crosslinking agent include isocyanate crosslinking agents such as toluene diisocyanate, hexamethylene diisocyanate, and their adducts; ethylene glycol glycidyl ether, 1,3 - Epoxy-based crosslinking agents such as bis(N,N'-diecidylaminomethyl)cyclohexane; hexa[1-(2-methyl)-aziridinyl]triphosphatriazine Aziridine-based crosslinking agents such as (hexa[1-(2-methyl)-aziridinyl]triphosphatriazine); chelate-based crosslinking agents such as aluminum chelates; These crosslinking agents can be used individually or in combination of 2 or more types.

該等之中，從提高凝聚力而使黏著力提升之觀點、及取得容易性等的觀點而言，以異氰酸酯系交聯劑為佳。將交聯劑使用在黏著性組合物時，從促進交聯反應的觀點而言，其調配比例，將黏著性組合物的總量作為基準，良好為0.01~20質量%，較佳為0.05~15質量%，更佳為0.1~10質量%。Among them, an isocyanate-based crosslinking agent is preferable from the viewpoint of enhancing the cohesive force to enhance the adhesive force, and the ease of acquisition. When the crosslinking agent is used in the adhesive composition, from the viewpoint of accelerating the crosslinking reaction, the blending ratio is preferably 0.01 to 20% by mass, preferably 0.05 to 20% by mass, based on the total amount of the adhesive composition. 15% by mass, more preferably 0.1 to 10% by mass.

(光聚合起始劑) 又，黏著性組合物為能量線硬化性時，黏著性組合物以進一步含有光聚合起始劑為佳。藉由含有光聚合起始劑，即便紫外線等較低能量的能量線亦能夠使黏著性組合物的硬化反應充分地進行。(photopolymerization initiator) Also, when the adhesive composition is energy ray curable, it is preferable that the adhesive composition further contains a photopolymerization initiator. By containing a photoinitiator, even the energy rays of low energy, such as an ultraviolet-ray, can fully progress the hardening reaction of an adhesive composition.

作為光聚合起始劑，可舉出，例如，苯偶姻(benzoin)化合物、苯乙酮(acetophenone)化合物、醯基氧化膦(acylphosphine oxide)化合物、二茂鈦(titanocene)化合物、9-氧硫

(thioxanthone)化合物、過氧化化合物、以及胺、苯醌(quinone)等的光敏化劑等，更具體而言，可舉出，例如，1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、苯偶姻、苯偶姻甲醚、苯偶姻***、苯偶姻異丙醚、苄基苯基硫醚(benzyl phenyl sulfide)、一硫化四甲基秋蘭姆(tetramethylthiuram monosulfide)、偶氮雙異丁腈(azobisisobutyronitrile)、聯苄(dibenzyl)、聯乙醯、8-氯蒽醌(8-chloroanthraquinone)、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦(bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide)等。Examples of photopolymerization initiators include benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, 9-oxo sulfur

Photosensitizers such as (thioxanthone) compounds, peroxide compounds, amines, and quinones (quinone), etc., more specifically, include, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl phenyl sulfide, monosulfide Tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, 8-chloroanthraquinone, bis(2,4,6- Trimethylbenzoyl) phenylphosphine oxide (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide), etc.

該等光聚合起始劑可單獨或組合2種以上而使用。使用光聚合起始劑時，其調配比例將能量線硬化性成分的總量作為基準，良好為0.1~10質量%，較佳為0.3~8.0質量%，更佳為0.5~5質量%。These photopolymerization initiators can be used individually or in combination of 2 or more types. When a photopolymerization initiator is used, the blending ratio is preferably 0.1 to 10% by mass, preferably 0.3 to 8.0% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the energy ray-curable component.

(其它黏著性聚合物) 除了含兩性離子的丙烯酸系聚合物以外，黏著性組合物亦可調配含兩性離子的丙烯酸系聚合物以外的黏著性聚合物。作為此種黏著性聚合物，可舉出被泛用作為黏著劑的主材料之不具有兩性離子結構的丙烯酸系黏著性聚合物、胺甲酸乙酯系黏著性聚合物、橡膠系黏著性聚合物、矽酮(silicone)系黏著性聚合物等。特別是，從相溶性、親和性的觀點而言，以丙烯酸系黏著劑為佳。該等黏著性聚合物可單獨或組合2種以上而使用。(other adhesive polymers) In addition to the zwitterion-containing acrylic polymer, the adhesive composition may also contain an adhesive polymer other than the zwitterion-containing acrylic polymer. Examples of such adhesive polymers include acrylic adhesive polymers that do not have a zwitterionic structure, urethane adhesive polymers, and rubber adhesive polymers that are widely used as the main material of adhesives. , Silicone-based adhesive polymers, etc. In particular, an acrylic adhesive is preferable from the viewpoint of compatibility and affinity. These adhesive polymers can be used individually or in combination of 2 or more types.

(其它添加劑) 在不損害本發明的效果之範圍，黏著性組合物亦可含有其它添加劑。作為其它添加劑，可舉出，例如，抗靜電劑、抗氧化劑、黏著賦予劑、軟化劑(可塑劑)、填充劑、防鏽劑、顏料、染料等。(other additives) The adhesive composition may contain other additives in the range which does not impair the effect of this invention. Examples of other additives include antistatic agents, antioxidants, tackifiers, softeners (plasticizers), fillers, antirust agents, pigments, and dyes.

又，從提升對基材、剝離膜等的塗佈性之觀點，黏著性組合物亦可為進一步使用有機溶劑稀釋而成為黏著劑組合物的溶液形態。作為有機溶劑，可舉出，例如，甲基乙基酮、丙酮、乙酸乙酯、四氫呋喃、二㗁烷(dioxane)、環己烷、正己烷、甲苯、二甲苯、正丙醇、異丙醇等。Moreover, from a viewpoint of improving applicability to a base material, a peeling film, etc., an adhesive composition may be in the form of the solution which diluted with an organic solvent further and became an adhesive composition. Examples of organic solvents include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol wait.

而且，該等有機溶劑可直接使用黏著性樹脂的合成時所使用的有機溶劑，亦能夠以使該黏著劑組合物的溶液能夠均勻地塗佈之方式，添加合成時所使用的有機溶劑以外之1種以上的有機溶劑。In addition, the organic solvent used in the synthesis of the adhesive resin may be used as it is, or the organic solvent used in the synthesis may be added so that the solution of the adhesive composition can be uniformly coated. 1 or more organic solvents.

(黏著性組合物的黏彈性的控制) 黏著性組合物的儲存模數G’(23)，能夠藉由，例如，含兩性離子的丙烯酸系聚合物之單體組成而控制。源自烷基的碳數為4以上之(甲基)丙烯酸烷酯的重複單元的含量增加時，儲存模數G’(23)有降低之傾向。又，認為含兩性離子單元的含量增加時，藉由在23℃附近兩性離子結構彼此的締合而能夠形成較硬質的結構。認為這是因為在兩性離子結構的負電荷部位與其它兩性離子結構的正電荷部位之間生成離子鍵。該結果，儲存模數G’(23)有增加之傾向。(Control of Viscoelasticity of Adhesive Composition) The storage modulus G'(23) of the adhesive composition can be controlled by, for example, the monomer composition of the zwitterion-containing acrylic polymer. The storage modulus G'(23) tends to decrease as the content of the repeating unit derived from an alkyl group having 4 or more carbon atoms (meth)acrylate increases. In addition, it is considered that when the content of the zwitterion-containing unit increases, a harder structure can be formed by association of the zwitterion structures at around 23°C. This is considered to be because ionic bonds are generated between negatively charged sites of zwitterionic structures and positively charged sites of other zwitterionic structures. As a result, the storage modulus G'(23) tends to increase.

黏著性組合物的儲存模數G’(50)，能夠藉由，例如，含兩性離子的丙烯酸系聚合物的單體組成而控制。源自烷基的碳數為4以上之(甲基)丙烯酸烷酯的重複單元的含量增加時，儲存模數G’(50)有降低之傾向。又，認為含兩性離子單元的含量增加時，藉由在50℃附近兩性離子結構彼此的締合而能夠形成較硬質的結構。認為這是因為在兩性離子結構的負電荷部位與其它兩性離子結構的正電荷部位之間生成離子鍵。該結果，儲存模數G’(50)有增加之傾向。The storage modulus G'(50) of the adhesive composition can be controlled by, for example, the monomer composition of the zwitterion-containing acrylic polymer. The storage modulus G'(50) tends to decrease as the content of the repeating unit derived from an alkyl group having 4 or more carbon atoms (meth)acrylate increases. In addition, it is considered that when the content of the zwitterion-containing unit increases, a harder structure can be formed by association of the zwitterion structures at around 50°C. This is considered to be because ionic bonds are generated between negatively charged sites of zwitterionic structures and positively charged sites of other zwitterionic structures. As a result, the storage modulus G'(50) tends to increase.

tanδ(60)能夠藉由，例如，含兩性離子的丙烯酸系聚合物的單體組成而控制。認為含兩性離子單元的含量增加時，因為在60℃附近，能量被消耗在兩性離子結構的締合部位之開裂且損失模數G’’增大。該結果，黏著膠帶的加溫時，黏著劑層或中間層的變形能夠維持，且能夠減低因切削水引起之電路面的污染、破損。tan δ(60) can be controlled by, for example, the monomer composition of the zwitterion-containing acrylic polymer. It is considered that when the content of the zwitterion-containing unit increases, because around 60°C, energy is consumed in the cracking of the association site of the zwitterion structure and the loss modulus G'' increases. As a result, when the adhesive tape is heated, the deformation of the adhesive layer or the intermediate layer can be maintained, and contamination and damage of the circuit surface due to cutting water can be reduced.

黏著性組合物的G’(60)/G’(23)，能夠藉由，例如，含兩性離子的丙烯酸系聚合物的單體組成而控制。源自烷基的碳數為4以上之(甲基)丙烯酸烷酯的重複單元的含量增加時，儲存模數G’(23)有降低之傾向。又，含兩性離子單元的含量增加時，儲存模數G’(23)有增加之傾向。G'(60)/G'(23) of the adhesive composition can be controlled by, for example, the monomer composition of the zwitterion-containing acrylic polymer. The storage modulus G'(23) tends to decrease as the content of the repeating unit derived from an alkyl group having 4 or more carbon atoms (meth)acrylate increases. Also, when the content of zwitterion-containing units increases, the storage modulus G'(23) tends to increase.

源自烷基的碳數為4以上之(甲基)丙烯酸烷酯的重複單元的含量增加時，儲存模數G’(60)有降低之傾向。含兩性離子單元的含量對儲存模數G’(60)之影響不大，因為即便在60℃附近，兩性離子結構彼此的締合部位為部分地殘留，所以能夠抑制儲存模數G’(60)過度降低。The storage modulus G'(60) tends to decrease as the content of repeating units derived from alkyl (meth)acrylates having 4 or more carbon atoms increases. The content of the zwitterionic unit has little effect on the storage modulus G'(60), because even at around 60°C, the association sites of the zwitterionic structures remain partially, so the storage modulus G'(60) can be suppressed. ) is excessively reduced.

tanδ之極大值顯現的溫度，能夠藉由，例如，含兩性離子的丙烯酸系聚合物的單體組成而控制。含兩性離子單元的含量增加時，tanδ之極大值顯現的溫度呈現低溫側尖峰、高溫側尖峰同時往高溫側位移的趨勢。因而，藉由控制含兩性離子的丙烯酸系聚合物的單體組成，而能夠達成在所需要的貼附溫度之良好的埋入性、形狀維持性。The temperature at which the maximum value of tan δ appears can be controlled by, for example, the monomer composition of the zwitterion-containing acrylic polymer. When the content of zwitterion-containing units increases, the maximum temperature of tanδ presents a trend of a peak at the low temperature side and a peak at the high temperature side shifting to the high temperature side at the same time. Therefore, by controlling the monomer composition of the zwitterion-containing acrylic polymer, it is possible to achieve good embedding properties and shape retention properties at a desired attachment temperature.

(黏著膠帶) 本發明之黏著膠帶具有包括上述黏著性組合物之黏著劑層或中間層。黏著膠帶的用途沒有特別限定，例如，能夠使用作為背面研磨帶、切割膠帶、用以將拾取後的晶片轉移之膠帶等。又，黏著膠帶亦可配合被貼附的對象之形狀而預先切割。例如，使用在半導體晶圓的背面磨削時，亦可切斷成為半導體晶圓的形狀。又，使用作為切割膠帶時，亦可配合環狀框的形狀而切割。以下，主要將針對使用作為背面研磨帶(半導體晶圓表面保護膠帶)或切割膠帶的情況而進行說明。 以下，將具有包括上述黏著性組合物的黏著劑層之黏著膠帶設為第1形態，而且將具有包括上述黏著性組合物的中間層之黏著膠帶設為第2形態而進行說明。(adhesive tape) The adhesive tape of the present invention has an adhesive layer or an intermediate layer comprising the above-mentioned adhesive composition. The use of the adhesive tape is not particularly limited, and for example, it can be used as a back grinding tape, a dicing tape, a tape for transferring a picked-up wafer, and the like. In addition, the adhesive tape can also be pre-cut according to the shape of the object to be attached. For example, when used for back grinding of semiconductor wafers, it can also be cut into the shape of semiconductor wafers. Moreover, when using it as a dicing tape, it can also be cut|disconnected according to the shape of a ring frame. Hereinafter, the case where it is used as a back grinding tape (semiconductor wafer surface protection tape) or a dicing tape will be mainly demonstrated. Hereinafter, the adhesive tape which has the adhesive layer which consists of the said adhesive composition as a 1st form, and the adhesive tape which has an intermediate|middle layer which consists of the said adhesive composition are demonstrated as a 2nd form.

(第1形態之黏著膠帶) 第1形態之黏著膠帶包括基材及黏著劑層，其特徵在於，黏著劑層包括上述黏著性組合物。(The first form of adhesive tape) The adhesive tape of the first aspect includes a base material and an adhesive layer, and is characterized in that the adhesive layer includes the above-mentioned adhesive composition.

(基材) 第1形態之黏著膠帶的基材，只要黏著膠帶在切割步驟、背面研磨步驟等所需要的步驟能夠適當地達成功能，其構成材料就沒有特別限定，通常由將樹脂系的材料作為主材料之薄膜所構成。作為該薄膜的具體例，可舉出乙烯-乙酸乙烯酯共聚物膜、乙烯-(甲基)丙烯酸共聚物膜、乙烯-(甲基)丙烯酸酯共聚物膜等的乙烯系共聚物膜；低密度聚乙烯(LDPE)膜、直鏈低密度聚乙烯(LLDPE)膜、高密度聚乙烯(HDPE)膜等的聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、乙烯-降莰烯共聚物膜、降莰烯樹脂膜等的聚烯烴系薄膜；聚氯乙烯膜、氯乙烯共聚物膜等的聚氯乙烯系薄膜；聚對苯二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜等的聚酯系薄膜；聚氨酯膜；聚醯亞胺膜；聚苯乙烯膜；聚碳酸酯膜；氟樹脂膜等。而且亦能夠使用如該等的交聯膜、離子聚合物膜之改性薄膜。上述基材可由該等的1種所構成之薄膜，而且亦可為將該等組合2種類以上而成之積層膜。(Substrate) The base material of the adhesive tape of the first form is not particularly limited as long as the adhesive tape can properly perform functions in the steps required for the dicing step, back grinding step, etc. composed of thin films. Specific examples of the film include ethylene-based copolymer films such as ethylene-vinyl acetate copolymer films, ethylene-(meth)acrylic acid copolymer films, and ethylene-(meth)acrylate copolymer films; Polyethylene films such as high-density polyethylene (LDPE) films, linear low-density polyethylene (LLDPE) films, and high-density polyethylene (HDPE) films, polypropylene films, polybutene films, polybutadiene films, polyformaldehyde Polyolefin-based films such as amylpentene films, ethylene-norcamphene copolymer films, and norbornene resin films; polyvinyl chloride-based films such as polyvinyl chloride films and vinyl chloride copolymer films; polyethylene terephthalate Polyester films such as diester films and polybutylene terephthalate films; polyurethane films; polyimide films; polystyrene films; polycarbonate films; fluororesin films, etc. Furthermore, modified thin films such as cross-linked membranes and ionomer membranes such as these can also be used. The above-mentioned base material may be a thin film composed of one of these types, or may be a laminated film obtained by combining two or more types of these types.

構成基材之薄膜，以具備乙烯系共聚物膜及聚烯烴系薄膜的至少一種為佳。乙烯系共聚物膜能夠藉由改變共聚合比等而容易在廣泛的範圍控制其機械特性。因此，具備乙烯系共聚物膜之基材，容易滿足作為本實施形態之黏著膠帶的基材被要求的機械特性。又，因為乙烯系共聚物膜對黏著劑層之密著性較高，所以在使用作為黏著膠帶時不容易在基材與黏著劑層之界面產生剝離。The film constituting the substrate preferably has at least one of an ethylene-based copolymer film and a polyolefin-based film. The ethylene-based copolymer film can easily control its mechanical properties in a wide range by changing the copolymerization ratio and the like. Therefore, the base material provided with the ethylene-based copolymer film can easily satisfy the mechanical properties required as the base material of the adhesive tape of this embodiment. In addition, since the ethylene-based copolymer film has high adhesion to the adhesive layer, it is difficult to cause peeling at the interface between the base material and the adhesive layer when used as an adhesive tape.

在此，在聚氯乙烯系薄膜等的一部分的薄膜中，包括較多對黏著膠帶的特性造成不良影響之成分。例如，在聚氯乙烯系薄膜等，在該薄膜中所含有的可塑劑從基材移行至黏著劑層，而且分佈在黏著劑層之與基材相向側為相反側的面，且有使黏著劑層的對工件(半導體晶圓、晶片等)之黏著性低落之情形。但是，因為乙烯系共聚物膜及聚烯烴系薄膜中對黏著膠帶的特性造成不良影響之成分的含量較少，所以不容易產生黏著劑層的對工件之黏著性低落等的問題。亦即，乙烯系共聚物膜及聚烯烴系薄膜具有優異的化學安定性。Here, some films such as polyvinyl chloride-based films contain many components that adversely affect the properties of the adhesive tape. For example, in a polyvinyl chloride-based film, etc., the plasticizer contained in the film migrates from the base material to the adhesive layer, and is distributed on the side of the adhesive layer opposite to the base material, and has the effect of making the adhesive When the adhesiveness of the agent layer to the workpiece (semiconductor wafer, chip, etc.) is low. However, since the ethylene-based copolymer film and the polyolefin-based film contain less components that adversely affect the properties of the adhesive tape, problems such as decreased adhesion to workpieces of the adhesive layer are less likely to occur. That is, ethylene-based copolymer films and polyolefin-based films have excellent chemical stability.

基材亦可在將上述樹脂系材料作為主材料之薄膜內，含有顏料等的著色劑、阻燃劑、可塑劑、抗靜電劑、滑劑、填料等的各種添加劑。作為顏料，可舉出，例如，二氧化鈦、碳黑等。又，作為填料，可例示如三聚氰胺樹脂的有機系材料、如氣相法氧化矽(fumed silica)的無機系材料及如鎳粒子的金屬系材料。此種添加劑的含量沒有特別限定，但是應該限於在基材可發揮所需要的功能且不喪失平滑性和柔軟性的範圍。The base material may also contain various additives such as coloring agents such as pigments, flame retardants, plasticizers, antistatic agents, lubricants, fillers, etc. in a film mainly made of the above-mentioned resin-based materials. As a pigment, titanium dioxide, carbon black, etc. are mentioned, for example. Further, examples of fillers include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles. The content of such additives is not particularly limited, but should be limited to a range in which the base material can perform the required functions without losing smoothness and softness.

黏著劑層為能量線硬化性時，基材以對紫外線、電子射線等預定的能量線具有透射性為佳。When the adhesive layer is energy ray curable, the base material is preferably transparent to predetermined energy rays such as ultraviolet rays and electron rays.

又，為了提升與黏著劑層的密著性，在基材之黏著劑層側的面(以下亦稱為「基材被黏著面」)，亦可經施行電暈處理或設置有底漆(primer)層。又，在基材之與基材被黏著面相反側的面亦可設置有各種塗膜。In addition, in order to improve the adhesion with the adhesive layer, the surface of the substrate on the side of the adhesive layer (hereinafter also referred to as "the surface to be adhered to the substrate") may also be treated with corona treatment or provided with a primer ( primer) layer. In addition, various coating films may be provided on the surface of the substrate opposite to the surface to be adhered.

基材的厚度只要黏著膠帶在所需要的步驟能夠適當地發揮功能，就沒有限定。良好為20~450μm，較佳為25~400μm，特佳為50~350μm的範圍。The thickness of the base material is not limited as long as the adhesive tape can properly function in the required steps. It is preferably in the range of 20 to 450 μm, preferably in the range of 25 to 400 μm, and particularly preferably in the range of 50 to 350 μm.

(黏著劑層) 在基材的一面形成包括前述黏著性組合物之黏著劑層。將黏著膠帶使用作為切割膠帶時，黏著劑層的厚度，以5~50μm為佳，以1~40μm為特佳，進而以10~20μm為佳。黏著劑層的厚度小於5μm時，黏著劑層有產生黏著性偏差變大的問題之可能性。(adhesive layer) An adhesive layer comprising the aforementioned adhesive composition is formed on one side of the substrate. When the adhesive tape is used as a dicing tape, the thickness of the adhesive layer is preferably 5-50 μm, particularly preferably 1-40 μm, and more preferably 10-20 μm. When the thickness of the adhesive layer is less than 5 μm, there is a possibility that the adhesive layer may cause a problem of large variation in adhesiveness.

將黏著膠帶使用作為背面研磨帶時，黏著劑層具有能夠埋入半導體晶圓表面的凹凸之厚度即可。因而，黏著膠帶被貼附在設置有凸塊之半導體晶圓表面時，黏著劑層的厚度比凸塊高度更大即可。具體而言，黏著劑層的厚度，以凸塊高度的1.0倍以上為佳，以1.2~3倍為較佳，以1.4~2倍為更佳。又，在此所謂凸塊高度，是指設置在半導體晶圓之凸塊高度的最大值。又，此時的黏著劑層厚度，具體而言，以20~300μm為佳，以30~200μm為較佳，以40~150μm為更佳。When an adhesive tape is used as a back grinding tape, the adhesive layer should just have the thickness which can bury the uneven|corrugated surface of a semiconductor wafer. Therefore, when the adhesive tape is attached to the surface of the semiconductor wafer provided with bumps, the thickness of the adhesive layer should be greater than the height of the bumps. Specifically, the thickness of the adhesive layer is preferably at least 1.0 times the bump height, more preferably 1.2-3 times, more preferably 1.4-2 times. In addition, the term "bump height" here refers to the maximum value of the height of the bumps provided on the semiconductor wafer. In addition, the thickness of the adhesive layer at this time is, specifically, preferably 20 to 300 μm, more preferably 30 to 200 μm, and more preferably 40 to 150 μm.

(其它) 在上述基材與黏著劑層之間，亦可設置有由各種軟質聚合物所構成之中間層。在第1形態之中間層的構成為任意且未必需要設置。例如，使用含兩性離子的丙烯酸系聚合物作為黏著性組合物的主成分時，以使用丙烯酸系軟質聚合物構成中間層為佳。藉由設置此種中間層，黏著劑層與中間層之間的密著性能夠提升，且能夠防止層間剝離。設置中間層時，黏著劑層的厚度亦可比凸塊高度更小。亦即，能夠藉由中間層與黏著劑層之二層埋入半導體晶圓表面的凹凸即可。此時之中間層的厚度以30~500μm為佳，以50~300μm為較佳，以80~250μm為更佳。又，與中間層層積之黏著劑層的厚度以5~50μm為佳，以7~40μm為特佳，進而以10~20μm為佳。(other) Between the base material and the adhesive layer, an intermediate layer made of various soft polymers may also be provided. The configuration of the intermediate layer in the first aspect is optional and does not necessarily have to be provided. For example, when using a zwitterion-containing acrylic polymer as the main component of the adhesive composition, it is preferable to use an acrylic soft polymer to form the intermediate layer. By providing such an intermediate layer, the adhesiveness between the adhesive layer and the intermediate layer can be improved, and delamination between layers can be prevented. When the intermediate layer is provided, the thickness of the adhesive layer can also be smaller than the height of the bump. That is, it is only necessary to embed the unevenness on the surface of the semiconductor wafer through the two layers of the intermediate layer and the adhesive layer. At this time, the thickness of the intermediate layer is preferably 30-500 μm, more preferably 50-300 μm, more preferably 80-250 μm. Also, the thickness of the adhesive layer laminated with the intermediate layer is preferably 5 to 50 μm, particularly preferably 7 to 40 μm, and further preferably 10 to 20 μm.

又，為了在將黏著劑層貼附於工件為止之期間保護黏著劑層之目的，黏著膠帶亦可在黏著劑層之與基材側的面為相反側的面層積有剝離膜。剝離膜的構成為任意，可例示使用剝離劑等將塑膠膜進行剝離處理而成之物。作為塑膠膜的具體例，可舉出聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等的聚酯膜、及聚丙烯、聚乙烯等的聚烯烴膜。作為剝離劑，能夠使用矽酮系、氟系、長鏈烷基系等，該等之中，以廉價且能夠得到穩定的性能之矽酮系為佳。針對剝離膜的厚度，沒有特別限制，通常20~250μm左右。In addition, the adhesive tape may have a release film laminated on the surface of the adhesive layer opposite to the substrate side for the purpose of protecting the adhesive layer until the adhesive layer is attached to the workpiece. The structure of the release film is optional, and what is obtained by peeling a plastic film using a release agent or the like can be exemplified. Specific examples of plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyester films such as polypropylene and polyethylene. Olefin film. As the release agent, silicone-based, fluorine-based, long-chain alkyl-based, etc. can be used, and among them, silicone-based, which is inexpensive and can provide stable performance, is preferable. The thickness of the release film is not particularly limited, but is usually about 20 to 250 μm.

(第2形態之黏著膠帶) 第2形態之黏著膠帶包括基材、黏著劑層、及設置在該等之間之中間層，其特徵在於，該中間層含有上述黏著性組合物。該形態的黏著膠帶特別是能夠適合使用作為背面研磨帶。 基材與針對前述第1形態已說明之物同樣，基材之中間層側的面(基材被黏著面)亦可經施行與前述同樣的處理。(Second form of adhesive tape) The adhesive tape of the second aspect includes a base material, an adhesive layer, and an intermediate layer disposed between them, wherein the intermediate layer contains the above-mentioned adhesive composition. The adhesive tape of this form can be used suitably especially as a back grinding tape. The base material is the same as that described for the above-mentioned first embodiment, and the surface of the base material on the side of the intermediate layer (the surface to be adhered to the base material) can also be subjected to the same treatment as described above.

(中間層) 在基材的一面形成有包括前述黏著性組合物之中間層。將黏著膠帶使用作為背面研磨帶時，黏著劑層與中間層的合計厚度，具有能夠埋入半導體晶圓表面的凹凸之厚度即可。因而，黏著膠帶被貼附在設置有凸塊之半導體晶圓表面時，黏著劑層與中間層的合計厚度比凸塊高度更大即可。具體而言，合計厚度以凸塊高度之1.0倍以上為佳，以1.2~3倍為較佳，以1.4~2倍為更佳。又，在此所謂凸塊高度，是指設置在半導體晶圓之凸塊高度的最大值。又，此時之黏著劑層的中間層的合計厚度，具體而言，以20~300μm為佳，以30~200μm為較佳，以40~150μm為更佳。(middle layer) An intermediate layer comprising the aforementioned adhesive composition is formed on one side of the substrate. When the adhesive tape is used as the back grinding tape, the total thickness of the adhesive layer and the intermediate layer may have a thickness capable of embedding the irregularities on the surface of the semiconductor wafer. Therefore, when the adhesive tape is attached to the surface of the semiconductor wafer provided with bumps, the total thickness of the adhesive layer and the intermediate layer should be greater than the height of the bumps. Specifically, the total thickness is preferably at least 1.0 times the bump height, more preferably 1.2 to 3 times, more preferably 1.4 to 2 times. In addition, the term "bump height" here refers to the maximum value of the height of the bumps provided on the semiconductor wafer. In addition, the total thickness of the intermediate layers of the adhesive layer at this time is, specifically, preferably 20 to 300 μm, more preferably 30 to 200 μm, more preferably 40 to 150 μm.

(黏著劑層) 黏著劑只要在常溫具有適當的感壓接著性，就沒有特別限定，以在23℃的儲存模數為0.05~0.50MPa之物為佳。在半導體晶圓的表面形成有電路等而且通常具有凹凸。黏著膠帶藉由儲存模數為上述範圍內，被貼附在具有凹凸之晶圓表面時，能夠使晶圓表面的凹凸與黏著劑層充分地接觸，且能夠使黏著劑層的接著性適當地發揮。因此，黏著膠帶確實地進行在對半導體晶圓的固定，且背面磨削時能夠適當地保護晶圓表面。從該等的觀點而言，黏著劑的儲存模數，以0.10~0.35MPa為較佳。又，黏著劑層是由能量線硬化性黏著劑形成時，所謂黏著劑的儲存模數，意指藉由能量線照射而硬化前之儲存模數。(adhesive layer) The adhesive is not particularly limited as long as it has appropriate pressure-sensitive adhesiveness at room temperature, but one with a storage modulus of 0.05-0.50 MPa at 23° C. is preferable. Circuits and the like are formed on the surface of the semiconductor wafer and generally have unevenness. When the adhesive tape has a storage modulus within the above-mentioned range, when it is attached to the surface of the wafer with unevenness, the unevenness of the wafer surface can be fully contacted with the adhesive layer, and the adhesion of the adhesive layer can be properly maintained. play. Therefore, the adhesive tape securely fixes the semiconductor wafer and properly protects the wafer surface during back grinding. From these viewpoints, the storage modulus of the adhesive is preferably 0.10-0.35 MPa. In addition, when the adhesive layer is formed of an energy ray-curable adhesive, the storage modulus of the adhesive means the storage modulus before hardening by irradiation of energy rays.

黏著劑層的厚度，以小於40μm為佳，以5~35μm為較佳，以10~30μm為更佳。將黏著劑層如此地薄化時，因為能夠減少在黏著膠帶之剛性較低的部分的比例，所以磨削精確度提升，且容易進一步防止背面磨削時產生之半導體晶片的缺損。又，亦能夠減低黏著劑在半導體晶圓表面的殘留附著。The thickness of the adhesive layer is preferably less than 40 μm, more preferably 5-35 μm, more preferably 10-30 μm. When the adhesive layer is thinned in this way, since the ratio of the less rigid portion of the adhesive tape can be reduced, the grinding accuracy is improved, and it is easy to further prevent chipping of the semiconductor wafer that occurs during back grinding. In addition, it is also possible to reduce the residual adhesion of the adhesive on the surface of the semiconductor wafer.

黏著劑層可由，例如，丙烯酸系黏著劑、胺甲酸乙酯系黏著劑、橡膠系黏著劑、矽酮系黏著劑等所形成，以丙烯酸系黏著劑為佳。 又，黏著劑層以由能量線硬化性黏著劑所形成為佳。藉由黏著劑層是由能量線硬化性黏著劑所形成，在照射能量線而硬化前，將在23℃之彈性模數設為上述範圍之同時，在硬化後能夠將剝離力容易地設定在1000mN/50mm以下。The adhesive layer can be formed of, for example, acrylic adhesives, urethane adhesives, rubber adhesives, silicone adhesives, etc., preferably acrylic adhesives. Also, the adhesive layer is preferably formed of an energy ray curable adhesive. Since the adhesive layer is formed of an energy ray-curable adhesive, the elastic modulus at 23°C is within the above range before curing by irradiation with energy rays, and the peeling force can be easily set after curing. Below 1000mN/50mm.

(其它) 在第2形態的黏著膠帶，亦與第1形態同樣地，為了在將黏著劑層貼附於工件為止之期間保護黏著劑層之目的，亦可在黏著劑層之與基材側的面為相反側的面層積有剝離膜。(other) In the adhesive tape of the second aspect, as in the first aspect, for the purpose of protecting the adhesive layer until the adhesive layer is attached to the workpiece, the surface of the adhesive layer on the substrate side may be A release film is laminated on the opposite surface.

(黏著膠帶的製造方法) 作為本發明的黏著膠帶10的製造方法，沒有特別限制，能夠使用習知的方法而製造。例如，將設置在剝離膜上之黏著劑層貼合在基材的一面，而能夠製造將剝離膜貼附在黏著劑層表面的第1形態之黏著膠帶。被貼附在黏著劑層表面之剝離膜，在黏著膠帶的使用前適當地剝離而除去即可。(Manufacturing method of adhesive tape) It does not specifically limit as a manufacturing method of the adhesive tape 10 of this invention, It can manufacture using a well-known method. For example, the adhesive tape of the first form in which the release film is bonded to the surface of the adhesive layer can be produced by bonding the adhesive layer provided on the release film to one surface of the substrate. The release film attached to the surface of the adhesive layer may be properly peeled off and removed before use of the adhesive tape.

又，將設置在剝離膜上之中間層貼合在基材的一面，將剝離膜剝離之後，將設置在剝離膜上之黏著劑層貼合在露出的中間層上，而能夠製造將剝離膜貼附在黏著劑層表面的第2形態之黏著膠帶。被貼附在黏著劑層表面之剝離膜，在黏著膠帶的使用前適當地剝離而除去即可。作為在剝離膜上形成黏著劑層或中間層之方法，將本發明的黏著性組合物使用習知的塗佈方法直接塗佈剝離膜上，進行加熱乾燥而使溶劑從塗佈膜揮發之方法為簡便的。In addition, the intermediate layer provided on the release film is bonded to one side of the base material, and after the release film is peeled off, the adhesive layer provided on the release film is bonded to the exposed intermediate layer, and the release film can be manufactured. Adhesive tape of the second form attached to the surface of the adhesive layer. The release film attached to the surface of the adhesive layer may be properly peeled off and removed before use of the adhesive tape. As a method of forming an adhesive layer or an intermediate layer on a release film, the adhesive composition of the present invention is directly coated on the release film using a known coating method, and then heated and dried to evaporate the solvent from the coated film. for simplicity.

又，亦能夠將黏著性組合物直接塗佈在基材的一面，而形成黏著劑層或中間層。作為黏著性組合物的塗佈方法，可舉出旋轉塗佈法、噴霧塗佈法、棒塗佈法、刮刀塗佈法、輥塗佈法、刀片塗佈法、模塗佈法、凹版塗佈法等。Moreover, it is also possible to apply an adhesive composition directly on one surface of a base material, and form an adhesive layer or an intermediate layer. Examples of coating methods for the adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating. Buffalo, etc.

(黏著膠帶的使用方法) 本發明的黏著膠帶能夠適合使用作為切割膠帶、背面研磨帶。作為切割膠帶，能夠使用於半導體晶圓、BGA型封裝等的切割。特別適合作為接觸切割膠帶之面的凹凸較大的半導體晶圓、BGA型封裝用的切割膠帶。切割方法沒有特別限定，可為使用旋轉圓型刀刃之刀片切割，亦可為使用雷射光之切割。(How to use the adhesive tape) The adhesive tape of this invention can be used suitably as a dicing tape and a back grinding tape. As a dicing tape, it can be used for dicing of a semiconductor wafer, a BGA type package, etc. It is especially suitable as a dicing tape for semiconductor wafers and BGA-type packages with large unevenness on the surface contacting the dicing tape. The cutting method is not particularly limited, and may be blade cutting using a rotating circular blade, or cutting using laser light.

其次，說明使用本發明的黏著膠帶之晶圓背面磨削方法。在晶圓的背面磨削，是將黏著膠帶貼附在表面形成有電路之半導體晶圓的電路面，邊保護電路面邊將晶圓背面進行磨削，而成為預定厚度的晶圓。Next, a wafer backside grinding method using the adhesive tape of the present invention will be described. Grinding on the back of the wafer is to attach an adhesive tape to the circuit surface of a semiconductor wafer with a circuit formed on the surface, and grind the back of the wafer while protecting the circuit surface to obtain a wafer of predetermined thickness.

半導體晶圓可為矽晶圓，而且亦可為鎵‧砷等的化合物半導體晶圓。在晶圓表面形成電路，能夠使用包含蝕刻法、剝落法等先前被泛用的方法之各式各樣的方法而進行。在半導體晶圓的電路形成步驟形成預定的電路。又，亦可在半導體晶圓表面形成有凸塊。此種晶圓的磨削前之厚度沒有特別限定，通常為500~1000μm左右。又，半導體晶圓表面形狀沒有特別限定，本發明的黏著膠帶特別是能夠適合使用於保護在電路表面形成有凸塊之晶圓的表面。The semiconductor wafer may be a silicon wafer, and may also be a compound semiconductor wafer such as gallium‧arsenic. Forming circuits on the wafer surface can be performed using various methods including conventional methods such as an etching method and a lift-off method. A predetermined circuit is formed in a circuit forming step of a semiconductor wafer. In addition, bumps may be formed on the surface of the semiconductor wafer. The thickness of such a wafer before grinding is not particularly limited, but is usually about 500 to 1000 μm. Also, the surface shape of the semiconductor wafer is not particularly limited, but the adhesive tape of the present invention can be used particularly suitably for protecting the surface of a wafer on which bumps are formed on the circuit surface.

本發明的黏著膠帶，具有顯示如上述的獨特的彈性行為之黏著劑層或中間層，在加熱條件下顯示能夠充分地追隨凸塊的凹凸之黏彈性。在貼附本發明的黏著膠帶時，較佳為在降低黏著劑層或中間層的儲存模數的狀態下進行。因而，將黏著膠帶貼附在半導體晶圓，以在40~60℃左右的溫度進行為佳。若貼附時的溫度太高時，則中間層和黏著劑層過度地軟化且流動化，而有從黏著膠帶的側面漏出之情形。The adhesive tape of the present invention has an adhesive layer or an intermediate layer exhibiting the above-mentioned unique elastic behavior, and exhibits viscoelasticity capable of sufficiently following unevenness of bumps under heating conditions. When affixing the adhesive tape of this invention, it is preferable to carry out in the state which lowered the storage modulus of an adhesive layer or an intermediate layer. Therefore, it is better to attach the adhesive tape to the semiconductor wafer at a temperature of about 40-60°C. If the temperature at the time of attaching is too high, the intermediate layer and the adhesive layer are excessively softened and fluidized, and may leak from the side of the adhesive tape.

在加熱下貼附黏著膠帶時，黏著劑層或中間層被埋入至形成有凸塊之晶圓面，而將凹凸差消除。又，因為藉由貼附後進行放冷，黏著劑層或中間層的彈性模數回復，且黏著劑層或中間層的彈性模數變高，所以能夠將晶圓保持在平坦的狀態。又，因為本發明的黏著膠帶對晶圓的表面形狀之追隨性較高，而且常態時黏著劑層或中間層為較硬質，所以即便將黏著膠帶捲起成為捲物狀，黏著劑不會在端部漏出，而能夠減低端部外觀不良。When the adhesive tape is attached under heating, the adhesive layer or the intermediate layer is buried on the surface of the wafer on which the bumps are formed, and the unevenness is eliminated. In addition, since the elastic modulus of the adhesive layer or the intermediate layer recovers and becomes higher by allowing the adhesive layer or the intermediate layer to cool down after attaching, the wafer can be kept in a flat state. Also, because the adhesive tape of the present invention has a high followability to the surface shape of the wafer, and the adhesive layer or intermediate layer is relatively hard under normal conditions, even if the adhesive tape is rolled into a roll shape, the adhesive will not The end part leaks out, and can reduce the appearance defect of the end part.

背面磨削在貼附有黏著膠帶之狀態下，藉由使用研磨機及用以將晶圓固定的吸附台面等之習知的手法來進行。背面磨削步驟之後，亦可進行將因磨削而產生的粉碎層除去之處理。背面磨削後的半導體晶圓之厚度，沒有特別限定，較佳為10~400μm，特佳為25~300μm左右。The backside grinding is carried out by a known method using a grinder, a suction table for fixing the wafer, etc. in a state where the adhesive tape is attached. After the back grinding step, a treatment for removing the pulverized layer generated by grinding may also be performed. The thickness of the semiconductor wafer after backside grinding is not particularly limited, but is preferably 10-400 μm, and most preferably about 25-300 μm.

背面磨削步驟後，將黏著膠帶從電路面剝離。若使用本發明的黏著膠帶時，則在晶圓的背面磨削時能夠確實地保持晶圓，且能夠防止切削水浸入至電路面。After the back grinding step, the adhesive tape is peeled off the circuit face. When the adhesive tape of the present invention is used, the wafer can be reliably held during backside grinding of the wafer, and infiltration of cutting water onto the circuit surface can be prevented.

而且，本發明的黏著膠帶，能夠適合使用在藉由所謂預切割法而進行附凸塊的晶圓之晶片化，具體而言，能夠適合使用在以下之半導體晶片的製造方法， 在將半導體晶圓表面形成有溝、或形成有改質區域之半導體晶圓的背面進行磨削，且藉由該磨削而將半導體晶圓個片化成為半導體晶片之步驟中， 從具有凸塊之半導體晶圓表面形成比該晶圓厚度更淺的切入深度之溝、或是從半導體晶圓的表面或背面在半導體晶圓的內部形成改質區域， 將上述黏著膠帶貼附在該電路形成面作為表面保護膠帶， 將表面貼附有黏著膠帶且形成有前述溝或改質區域之半導體晶圓，從背面側進行磨削，且將前述溝或改質區域作為起點而個片化成為複數個晶片(晶片集合體)。Furthermore, the adhesive tape of the present invention can be suitably used for wafering of wafers with bumps by a so-called pre-dicing method, and specifically, can be suitably used for the following semiconductor wafer manufacturing methods, In the step of grinding the back surface of the semiconductor wafer with grooves formed on the surface of the semiconductor wafer or with the modified region formed thereon, and separating the semiconductor wafer into semiconductor wafers by the grinding, From the surface of the semiconductor wafer with bumps, forming a groove with a shallower incision depth than the thickness of the wafer, or forming a modified region inside the semiconductor wafer from the surface or back of the semiconductor wafer, The above-mentioned adhesive tape is attached to the circuit formation surface as a surface protection tape, A semiconductor wafer with an adhesive tape attached to the surface and the aforementioned groove or modified region formed is ground from the back side, and the aforementioned groove or modified region is taken as a starting point to be sliced into a plurality of wafers (wafer assembly ).

在黏著膠帶的貼附之較佳態樣與前述同樣。藉由使用本發明的黏著膠帶，因為在晶圓(晶片)與黏著劑層之間能夠得到較高的密著性，所以磨削水不浸入電路面且能夠防止晶片污染。A preferred aspect of attaching the adhesive tape is the same as described above. By using the adhesive tape of the present invention, since high adhesion can be obtained between the wafer (chip) and the adhesive layer, the grinding water does not infiltrate the circuit surface and contamination of the wafer can be prevented.

隨後，使用預定方法而進行晶片拾取。又，亦可在晶片拾取之前，將晶片集合體轉印至其它黏著膠帶(拾取膠帶)，隨後進行晶片拾取。Subsequently, wafer pickup is performed using a predetermined method. In addition, prior to wafer pickup, the wafer assembly may be transferred to another adhesive tape (pickup tape), and wafer pickup may be performed thereafter.

在黏著膠帶的黏著劑層為能量線硬化性的情況中，對黏著劑層照射能量線而使黏著劑層硬化。其次，將拾取膠帶貼附在晶片集合體的背面側，且以能夠拾取的方式進行位置及方向對準。此時，配置在晶片集合體的外周側之環狀框亦貼合在拾取膠帶，而將拾取膠帶的外周緣部固定在環狀框。拾取膠帶可同時貼合在晶片集合體及環狀框，亦可依照各別的時間點進行貼合。其次，僅將黏著膠帶剝離，而將晶片集合體轉印至拾取膠帶上。When the adhesive layer of the adhesive tape is energy ray curable, the adhesive layer is irradiated with energy rays to harden the adhesive layer. Next, a pick-up tape is attached to the back side of the wafer assembly, and the position and direction are aligned so that it can be picked up. At this time, the ring-shaped frame arranged on the outer peripheral side of the wafer assembly is also bonded to the pick-up tape, and the outer peripheral edge portion of the pick-up tape is fixed to the ring-shaped frame. The pick-up tape can be bonded to the wafer assembly and the ring frame at the same time, or it can be bonded at different timings. Next, only the adhesive tape is peeled off, and the wafer assembly is transferred onto the pick-up tape.

隨後，視需要將拾取膠帶進行擴展而將晶片間隔分離，將位於拾取膠帶上之各個半導體晶片拾取且固定化在基板等的上面，而製造半導體裝置。Then, if necessary, the pick-up tape is expanded to separate the wafers, and the individual semiconductor wafers on the pick-up tape are picked up and fixed on the upper surface of a substrate or the like to manufacture a semiconductor device.

又，拾取膠帶沒有特別限定，例如，能夠由具有基材、及設置在基材的一面之黏著劑層之黏著膠帶所構成。拾取膠帶的黏著力在剝離時比背面研磨帶的黏著力更大即可。又，較佳為在將晶片從拾取膠帶拾取時具有能夠減低黏著力的性質。因而，作為拾取膠帶，能夠適合使用能量線硬化性黏著膠帶、發泡性易剝離膜等。Moreover, the pick-up tape is not specifically limited, For example, it can be comprised with the adhesive tape which has a base material and the adhesive agent layer provided in one side of the base material. It is sufficient that the pick-up tape adheres stronger than the backgrind tape when peeled. Moreover, it is preferable to have the property which can reduce the adhesive force when picking up a wafer from a pick-up tape. Therefore, as the pick-up tape, an energy ray-curable adhesive tape, a foamable easy-to-peel film, and the like can be suitably used.

又，亦能夠使用接著膠帶代替拾取膠帶。所謂接著膠帶，可舉出薄膜狀接著劑與剝離膜之積層體、切割膠帶與薄膜狀接著劑之積層體、由具有切割膠帶與晶粒接合膠帶雙方的功能之接著劑層及剝離片所構成之切割‧晶粒接合膠帶等。又，在將拾取膠帶貼附之前，亦可將薄膜狀接著劑貼合在經個片化的半導體晶圓的背面側。使用薄膜狀接著劑時，薄膜狀接著劑亦可與晶圓為相同形狀。Moreover, it is also possible to use an adhesive tape instead of a pick-up tape. Adhesive tapes include laminates of film-like adhesives and release films, laminates of dicing tapes and film-like adhesives, adhesive layers and release sheets that have both functions of dicing tapes and die-bonding tapes Dicing‧Die bonding tape, etc. In addition, before attaching the pick-up tape, a film-like adhesive may be attached to the back side of the singulated semiconductor wafer. When a film-form adhesive is used, the film-form adhesive may have the same shape as the wafer.

在使用接著膠帶的情況、和在貼附拾取膠帶之前將薄膜狀接著劑貼合在經個片化的半導體晶圓的背面側的情況等情況中，存在於接著膠帶和拾取膠帶上之複數個半導體晶片，是與被分割成為與半導體晶片相同形狀的接著劑層一起被拾取。然後，半導體晶片透過接著劑層而被固定在基板等的上面，以製造半導體裝置。接著劑層的分割，可藉由雷射和擴展而進行，而且亦可藉由拾取時的張力而進行。In the case of using an adhesive tape and the case where a film-like adhesive is bonded to the rear side of the singulated semiconductor wafer before attaching the pick-up tape, a plurality of The semiconductor wafer is picked up together with the adhesive layer divided into the same shape as the semiconductor wafer. Then, the semiconductor wafer is fixed on the upper surface of a substrate or the like through an adhesive layer to manufacture a semiconductor device. The division of the adhesive layer can be carried out by laser and expansion, and it can also be carried out by the tension when picking up.

以上，針對本發明的黏著膠帶，概略地說明了作為切割膠帶、背面研磨帶的用途，但是本發明的黏著膠帶之用途沒有特別限定，能夠使用於具有凹凸表面之各種工件的保持、和暫時的保護等等。 實施例As mentioned above, the use of the adhesive tape of the present invention as a dicing tape and back grinding tape has been roughly described, but the use of the adhesive tape of the present invention is not particularly limited, and it can be used for holding various workpieces with uneven surfaces, and temporarily protection and so on. Example

以下，基於實施例而更詳細地說明本發明，但是本發明不被該等例子限制。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples.

在本發明之測定方法、評價方法如以下所述。 [質量平均分子量(Mw)] 含兩性離子的丙烯酸系聚合物之質量平均分子量(Mw)，是在以下的條件下進行凝膠滲透層析法(GPC)而求取， 管柱：TSKgel Super AWM-H×2支(6.0mmI. D.×15cml×2支) 管柱LOT No.：S0095, S0096 流量：6.0mL/分鐘 檢測器：HLC-8320GPC 內藏RI檢測器/UV-8320(選項) 檢測器條件：RI：Pol(+), Res(0.5s)/UV：λ(280nm).Pol(+), Res(0.5s) 試料濃度：1.0g/L 注入量：40μL 壓力：2.84MPa 管柱溫度：40℃ 系統溫度：40℃ 沖提液：10mM LiBr + 20mM TEA in DMAcThe measurement method and evaluation method in the present invention are as follows. [Mass average molecular weight (Mw)] The mass average molecular weight (Mw) of the acrylic polymer containing zwitterions is obtained by gel permeation chromatography (GPC) under the following conditions, Column: TSKgel Super AWM-H×2 pieces (6.0mmI. D.×15cml×2 pieces) Column LOT No.: S0095, S0096 Flow rate: 6.0mL/min Detector: HLC-8320GPC built-in RI detector/UV-8320 (option) Detector conditions: RI: Pol(+), Res(0.5s)/UV: λ(280nm).Pol(+), Res(0.5s) Sample concentration: 1.0g/L Injection volume: 40μL Pressure: 2.84MPa Column temperature: 40°C System temperature: 40°C Eluent: 10mM LiBr + 20mM TEA in DMAc

[彈性模數的測定] 針對實施例及比較例所製造的黏著性組合物，在下述的裝置及條件下測定彈性模數。 試料調製：將各黏著性組合物塗佈在剝離膜上且乾燥，而且與另外的剝離膜貼合。藉此，得到在剝離膜之間層積有厚度40μm的黏著劑層之積層體。重複進行將該積層體之一方的剝離膜除去且將黏著劑層彼此層積，以製造厚度2000μm的測定用試料。 動態彈性模數測定裝置：TA Instruments公司製，製品名「ARES」 測定起始溫度：-60℃ 測定結束溫度：120℃ 升溫速度：4℃/分鐘 頻率：1Hz[Measurement of modulus of elasticity] The elastic modulus was measured on the following apparatus and conditions about the adhesive composition manufactured in the Example and the comparative example. Sample preparation: Each adhesive composition was apply|coated and dried on the release film, and it bonded together with another release film. Thereby, a laminate in which an adhesive layer with a thickness of 40 μm was laminated between release films was obtained. The peeling film of one side of this laminated body was removed and the adhesive layer was laminated|stacked repeatedly, and the sample for measurement of thickness 2000 micrometers was manufactured. Dynamic elastic modulus measurement device: manufactured by TA Instruments, product name "ARES" Measurement start temperature: -60°C Measurement end temperature: 120°C Heating rate: 4°C/min Frequency: 1Hz

[糊劑殘渣評價] 將實施例1~4、比較例1、2所製造的黏著膠帶切斷成為25mm寬度的長條狀，且貼附在一面經鏡面研磨的矽晶圓(直徑6英吋)之鏡面研磨面。黏著膠帶的貼附，是在23℃、50%RH(相對濕度)的條件下，使用2.5kg滾輪往復進行。黏著膠帶貼附後，靜置20分鐘且將黏著膠帶剝離。使用拉伸試驗機(ORIENTEC公司製，製品名「TENSILON」)且在剝離速度300mm/分鐘、剝離角度180∘的條件下進行剝離。剝離後，目視觀察晶圓表面，確認有無糊劑殘渣。 基於以下的基準判定糊劑殘渣。 A：目視無糊劑殘渣 B：目視有糊劑殘渣[Paste residue evaluation] The adhesive tapes produced in Examples 1-4 and Comparative Examples 1 and 2 were cut into strips with a width of 25 mm, and attached to the mirror-polished surface of a silicon wafer (diameter 6 inches) that had been mirror-polished. The sticking of the adhesive tape was carried out under the conditions of 23°C and 50%RH (relative humidity), using a 2.5kg roller to reciprocate. After the adhesive tape was attached, it was left to stand for 20 minutes and the adhesive tape was peeled off. Peeling was performed under conditions of a peeling speed of 300 mm/min and a peeling angle of 180° using a tensile tester (manufactured by Orientec Corporation, product name "TENSILON"). After peeling, the wafer surface was visually observed to check for the presence or absence of paste residue. The paste residue was determined based on the following criteria. A: There is no paste residue visually B: There is paste residue visually

[切割性] 使用實施例1~4、比較例1、2製造的黏著膠帶而進行矽晶圓的切割，藉由計算晶片飛散而評價切割性。使用桌上型貼合機(FUJiPLA公司製、製品名「LPD3226Meister6」)，將黏著膠帶貼附在一面經鏡面研磨的矽晶圓(直徑6英吋、厚度200μm)的鏡面研磨面。貼附條件設為溫度23℃、貼附速度0.4m/分鐘。在矽晶圓貼附有黏著膠帶的狀態下，將矽晶圓切割成為10mm×10mm的大小而作為晶片。使用切割裝置(DISCO公司製、製品名「DFD-6361」)，將刀片轉數設為4500rpm，將切斷速度設為50mm/秒。切割後的正方形晶片從黏著膠帶上剝離時，計算剝離後的晶片數。此時，不是成為製品之晶圓端部的晶片(三角形晶片)不包含在飛散數內。評價是針對正方形晶片總數而進行。基於以下的基準而判定切割性。 A：晶片飛散數小於3個 B：晶片飛散數3個以上且小於10個 C：晶片飛散數10個以上[cutting properties] Silicon wafers were diced using the adhesive tapes produced in Examples 1 to 4 and Comparative Examples 1 and 2, and the dicability was evaluated by calculating wafer scattering. Using a desktop laminating machine (manufactured by FUJiPLA, product name "LPD3226Meister6"), an adhesive tape was attached to the mirror-polished surface of a mirror-polished silicon wafer (diameter 6 inches, thickness 200 μm). The sticking conditions were set at a temperature of 23°C and a sticking speed of 0.4 m/min. In the state where the adhesive tape was attached to the silicon wafer, the silicon wafer was cut into a size of 10 mm×10 mm to obtain wafers. Using a cutting device (manufactured by DISCO Corporation, product name "DFD-6361"), the number of revolutions of the blade was set at 4500 rpm, and the cutting speed was set at 50 mm/sec. When the diced square wafers were peeled from the adhesive tape, the number of wafers after peeling was counted. At this time, wafers (triangular wafers) which are not wafer ends to be products are not included in the number of scattering. The evaluation was performed for the total number of square wafers. Cuttability was judged based on the following criteria. A: The number of chips scattered is less than 3 B: The number of wafer scattering is 3 or more and less than 10 C: The number of chips scattered is 10 or more

[埋入性評價(小凸塊用)] 使用實施例5~8、比較例3、4製造的黏著膠帶而進行埋入性評價。 使用LINTEC股份公司製貼合機「RAD-3510F/12」，將實施例5~8及比較例3、4製造的黏著膠帶貼附在附有Cu製柱狀物高度10μm、間距30~100μm、俯視直徑42μm的柱狀物之晶圓(Waltz公司製、8英吋晶圓、晶圓材質Si)。又，貼附時將裝置的貼合台面之溫度設為23℃，將貼合輥設為60℃，且將輥壓力設為0.3MPa，將貼附速度設為10mm/秒。貼合後，使用數位顯微鏡(股份公司KEYENCE製、製品名「VHX-1000」)從基材側測定在凸塊周邊產生的圓形空隙之直徑，基於以下的基準而評價埋入性。空隙的直徑越小，表示對凸塊的埋入性越高。 A：空隙的直徑小於90μm B：空隙的直徑90μm以上且小於100μm C：空隙的直徑100μm以上[Embedding property evaluation (for small bumps)] Embedding property evaluation was performed using the adhesive tape manufactured in Examples 5-8 and Comparative Examples 3 and 4. Using the laminating machine "RAD-3510F/12" manufactured by Lintec Co., Ltd., the adhesive tapes manufactured in Examples 5 to 8 and Comparative Examples 3 and 4 were attached to Cu pillars with a height of 10 μm and a pitch of 30 to 100 μm. Wafer (manufactured by Waltz, 8-inch wafer, wafer material Si) with pillars with a diameter of 42 μm in plan view. In addition, when sticking, the temperature of the bonding table of the apparatus was set at 23° C., the bonding roll was set at 60° C., the roll pressure was set at 0.3 MPa, and the sticking speed was set at 10 mm/sec. After bonding, the diameter of the circular void formed around the bump was measured from the substrate side using a digital microscope (manufactured by KEYENCE Co., Ltd., product name "VHX-1000"), and embedding properties were evaluated based on the following criteria. The smaller the diameter of the void, the higher the embedding property in the bump. A: The diameter of the void is less than 90 μm B: The diameter of the void is 90 μm or more and less than 100 μm C: The diameter of the void is 100 μm or more

[埋入性評價(中凸塊用)] 使用附有Cu製柱狀物高度45μm、間距30~100μm、俯視之直徑42μm的柱狀物之晶圓(Waltz公司製、8英吋晶圓、晶圓材質Si)，除此之外，與上述小凸塊用同樣地進行評價埋入性。 基於以下的基準而進行評價埋入性。 A：空隙的直徑小於120μm B：空隙的直徑120μm以上且小於130μm C：空隙的直徑130μm以上[Embedding property evaluation (for middle bump)] A wafer (manufactured by Waltz, 8-inch wafer, wafer material Si) with pillars made of Cu with a height of 45 μm, a pitch of 30 to 100 μm, and a diameter of 42 μm in plan view was used. Embedding properties were evaluated in the same manner for the above-mentioned small bumps. The embedding property was evaluated based on the following criteria. A: The diameter of the void is less than 120 μm B: The diameter of the void is 120 μm or more and less than 130 μm C: The diameter of the void is 130 μm or more

[端部外觀] 將實施例5~8及比較例3、4所製造的黏著膠帶，以捲收在直徑3英吋的芯材成為捲物狀的狀態，在23℃、50%RH(相對濕度)的環境下放置一星期。放置後，在捲物側部使用光學數位顯微鏡(倍率100倍)而評價有無源自於黏著劑層或中間層的成分漏出。 A：無法觀察到成分漏出 B：能夠觀察到成分漏出[end appearance] The adhesive tapes produced in Examples 5 to 8 and Comparative Examples 3 and 4 were rolled into a core material with a diameter of 3 inches to form a roll, and placed in an environment of 23°C and 50%RH (relative humidity) Leave it for a week. After standing, the presence or absence of component leakage from the adhesive layer or intermediate layer was evaluated using an optical digital microscope (magnification: 100 times) on the side of the roll. A: Leakage of components cannot be observed B: Leakage of components can be observed

[基材] 在以下的實施例及比較例，使用低密度聚乙烯聚合物之FUNCREA LEA型(厚度120μm、GUNZE公司製)作為基材。又，含兩性離子的丙烯酸系聚合物如以下所述而製造。[Substrate] In the following examples and comparative examples, a FUNCREA LEA type (thickness 120 μm, manufactured by Gunze Corporation) of a low-density polyethylene polymer was used as a substrate. Moreover, the zwitterion-containing acrylic polymer was produced as follows.

[含兩性離子的丙烯酸系聚合物1] 在附攪拌裝置的反應容器內，加入丙烯酸正丁酯(BA)93質量份、丙烯酸二甲胺基乙酯(DMAEA)5質量份、丙烯酸2-羥基乙酯(HEA)2質量份、起始劑之偶氮雙異丁腈(AIBN)及溶劑之乙酸乙酯180質量份，一邊攪拌一邊導入氮氣30分鐘。隨後，使反應系統上升至60℃為止之後，進行攪拌24小時，而得到BA/DMAEA/HEA(質量比)為93/5/2的預聚合物溶液1 (質量平均分子量78000)。將所得到的預聚合物溶液1以成為固體成分30%之方式而添加甲基乙基酮進行稀釋。在此，於室溫下將3.88質量份丙烷磺內酯慢慢地滴下且進行攪拌3小時。使反應系統上升至60℃為止之後，進一步使其反應48小時，而得到玻璃轉移溫度(Tg)為-30℃、質量平均分子量(Mw) 為100300、分子量分佈(Mw/Mn) 為10.4、在-30℃及40℃具有tanδ之極大尖峰、且含兩性離子單元的比例為3質量%之含兩性離子的丙烯酸系聚合物1。[Zwitterion-containing acrylic polymer 1] In the reaction vessel with stirring device, add 93 parts by mass of n-butyl acrylate (BA), 5 parts by mass of dimethylaminoethyl acrylate (DMAEA), 2 parts by mass of 2-hydroxyethyl acrylate (HEA), starting Azobisisobutyronitrile (AIBN) as the solvent and 180 parts by mass of ethyl acetate as the solvent were introduced with nitrogen gas for 30 minutes while stirring. Then, after raising the reaction system to 60 degreeC, it stirred for 24 hours, and obtained the prepolymer solution 1 (mass average molecular weight 78000) whose BA/DMAEA/HEA (mass ratio) was 93/5/2. The obtained prepolymer solution 1 was diluted by adding methyl ethyl ketone so that the solid content would be 30%. Here, 3.88 parts by mass of propane sultone was slowly dropped and stirred at room temperature for 3 hours. After raising the reaction system to 60°C, it was further reacted for 48 hours to obtain a glass transition temperature (Tg) of -30°C, a mass average molecular weight (Mw) of 100,300, a molecular weight distribution (Mw/Mn) of 10.4, and Zwitterion-containing acrylic polymer 1 having extremely large peaks of tan δ at -30°C and 40°C and having a ratio of zwitterion-containing units of 3% by mass.

[含兩性離子的丙烯酸系聚合物2] 在附攪拌裝置的反應容器內，加入丙烯酸正丁酯95質量份、丙烯酸二甲胺基乙酯3質量份、丙烯酸2-羥基乙酯2質量份、偶氮雙異丁腈、乙酸乙酯180質量份，一邊攪拌邊導入氮氣30分鐘。隨後，使反應系統上升至60℃為止之後，進行攪拌24小時，而得到BA/DMAEA/HEA(質量比)為95/3/2的預聚合物溶液2 (質量平均分子量128000)。將所得到的預聚合物溶液2以成為固體成分30%之方式而添加甲基乙基酮進行稀釋。在此，於室溫下將2.33質量份丙烷磺內酯慢慢地滴下且進行攪拌3小時。使反應系統上升至60℃為止之後，進一步使其反應48小時，而得到Tg為-24℃、Mw為165000、Mw/Mn為10.3、在-24℃及50℃具有tanδ之極大尖峰、且含兩性離子單元的比例為3質量%之含兩性離子的丙烯酸系聚合物2。[Zwitterion-containing acrylic polymer 2] In a reaction vessel with a stirring device, add 95 parts by mass of n-butyl acrylate, 3 parts by mass of dimethylaminoethyl acrylate, 2 parts by mass of 2-hydroxyethyl acrylate, azobisisobutyronitrile, and 180 parts by mass of ethyl acetate. parts by mass, nitrogen gas was introduced for 30 minutes while stirring. Then, after raising the reaction system to 60 degreeC, it stirred for 24 hours, and obtained the prepolymer solution 2 (mass average molecular weight 128000) whose BA/DMAEA/HEA (mass ratio) was 95/3/2. The obtained prepolymer solution 2 was diluted by adding methyl ethyl ketone so that the solid content would be 30%. Here, 2.33 parts by mass of propane sultone was slowly dropped and stirred at room temperature for 3 hours. After raising the reaction system to 60°C, it was further reacted for 48 hours to obtain a Tg of -24°C, a Mw of 165,000, a Mw/Mn of 10.3, and a very large peak of tanδ at -24°C and 50°C, and containing The ratio of zwitterionic units is 3% by mass of the zwitterion-containing acrylic polymer 2 .

[含兩性離子的丙烯酸系聚合物3] 在附攪拌裝置的反應容器內，加入丙烯酸正丁酯50質量份、丙烯酸2-乙基己酯(2EHA)47質量份、丙烯酸二甲胺基乙酯3質量份、偶氮雙異丁腈、乙酸乙酯180質量份，一邊攪拌一邊導入氮氣30分鐘。隨後，使反應系統上升至60℃為止之後，進行攪拌24小時，而得到BA/2EHA/DMAEA(質量比)為50/47/3的預聚合物溶液3 (質量平均分子量86000)。將所得到的預聚合物溶液3以成為固體成分30%之方式而添加甲基乙基酮進行稀釋。在此，於室溫下將2.33質量份丙烷磺內酯慢慢地滴下且進行攪拌3小時。使反應系統上升至60℃為止之後，進一步使其反應48小時，而得到Tg為-40℃、Mw為110500、Mw/Mn為11.2、在-40℃及70℃具有tanδ之極大尖峰、且含兩性離子單元的比例為5質量%之含兩性離子的丙烯酸系聚合物3。[Zwitterion-containing acrylic polymer 3] In the reaction vessel with stirring device, add 50 mass parts of n-butyl acrylate, 47 mass parts of 2-ethylhexyl acrylate (2EHA), 3 mass parts of dimethylaminoethyl acrylate, azobisisobutyronitrile, 180 parts by mass of ethyl acetate was stirred, and nitrogen gas was introduced for 30 minutes. Then, after raising the reaction system to 60 degreeC, it stirred for 24 hours, and obtained the prepolymer solution 3 (mass average molecular weight 86000) whose BA/2EHA/DMAEA (mass ratio) was 50/47/3. The obtained prepolymer solution 3 was diluted by adding methyl ethyl ketone so that the solid content would be 30%. Here, 2.33 parts by mass of propane sultone was slowly dropped and stirred at room temperature for 3 hours. After raising the reaction system to 60°C, it was further reacted for 48 hours to obtain a Tg of -40°C, a Mw of 110500, a Mw/Mn of 11.2, and a very large peak of tanδ at -40°C and 70°C, and containing The ratio of the zwitterionic unit is 5% by mass of the zwitterion-containing acrylic polymer 3 .

[含兩性離子的丙烯酸系聚合物4] 在附攪拌裝置的反應容器內，加入丙烯酸正丁酯97質量份、丙烯酸二甲胺基乙酯3質量份、偶氮雙異丁腈、乙酸乙酯180質量份，一邊攪拌一邊導入氮氣30分鐘。隨後，使反應系統上升至60℃為止之後，進行攪拌24小時，而得到BA/DMAEA(質量比)為97/3的預聚合物溶液4 (質量平均分子量111000)。將所得到的預聚合物溶液4以成為固體成分30%之方式而添加甲基乙基酮進行稀釋。在此，於室溫下將2.33質量份丙烷磺內酯慢慢地滴下且進行攪拌3小時。使反應系統上升至60℃為止之後，進一步使其反應48小時，而得到Tg為-33℃、Mw為142700、Mw/Mn為10.9、在-30℃及60℃具有tanδ之極大尖峰、且含兩性離子單元的比例為4質量%之含兩性離子的丙烯酸系聚合物4。[Zwitterion-containing acrylic polymer 4] Add 97 parts by mass of n-butyl acrylate, 3 parts by mass of dimethylaminoethyl acrylate, 180 parts by mass of azobisisobutyronitrile, and 180 parts by mass of ethyl acetate into a reaction vessel with a stirring device, and introduce nitrogen gas for 30 minutes while stirring . Then, after raising the reaction system to 60 degreeC, it stirred for 24 hours, and obtained the prepolymer solution 4 (mass average molecular weight 111000) whose BA/DMAEA (mass ratio) was 97/3. The obtained prepolymer solution 4 was diluted by adding methyl ethyl ketone so that the solid content would be 30%. Here, 2.33 parts by mass of propane sultone was slowly dropped and stirred at room temperature for 3 hours. After raising the reaction system to 60°C, it was further reacted for 48 hours to obtain a Tg of -33°C, a Mw of 142700, a Mw/Mn of 10.9, and a very large peak of tanδ at -30°C and 60°C, and containing The ratio of zwitterionic units is 4% by mass of zwitterion-containing acrylic polymer 4 .

調製不含有兩性離子結構之黏著性聚合物及中間層用組合物。 [黏著性聚合物A] 調製由丙烯酸丁酯(BA)86質量份、甲基丙烯酸甲酯(MMA)8質量份、丙烯酸(AA)1質量份、丙烯酸2-羥基乙酯(2HEA)5質量份所構成之丙烯酸系共聚物樹脂的溶液(黏著劑主劑、質量平均分子量720000、固體成分35.0質量%)。 相對於該黏著劑主劑100質量份，添加0.2質量份(固體成分)作為交聯劑之多價異氰酸酯化合物(製品名「BHS-8515」、TOYOCHEM公司製、固體成分37.5質量%)且攪拌後，得到黏著性聚合物A。Preparation of an adhesive polymer and a composition for an intermediate layer that does not contain a zwitterionic structure. [Adhesive Polymer A] Prepare an acrylic copolymer consisting of 86 parts by mass of butyl acrylate (BA), 8 parts by mass of methyl methacrylate (MMA), 1 part by mass of acrylic acid (AA), and 5 parts by mass of 2-hydroxyethyl acrylate (2HEA). A solution of a material resin (adhesive main agent, mass average molecular weight 720,000, solid content 35.0% by mass). 0.2 parts by mass (solid content) of a polyvalent isocyanate compound (product name "BHS-8515", manufactured by TOYOCHEM Co., Ltd., solid content 37.5% by mass) as a crosslinking agent was added to 100 parts by mass of the main adhesive agent and stirred , to obtain adhesive polymer A.

[黏著性聚合物B] 調製由丙烯酸2-乙基己酯(2EHA)59.5質量份、乙酸乙烯酯(Vac)30質量份、丙烯酸(AA)0.5質量份、丙烯酸2-羥基乙酯(2HEA)10質量份所構成之丙烯酸系共聚物樹脂的溶液(黏著劑主劑、質量平均分子量700000。固體成分35.0質量%)。 相對於該黏著劑主劑100質量份，添加1.9質量份(固體成分)作為交聯劑之多價異氰酸酯化合物(製品名「BHS-8515」、TOYOCHEM公司製、固體成分37.5質量%)且攪拌後，得到黏著性聚合物B。[Adhesive Polymer B] Prepare acrylic acid composed of 59.5 parts by mass of 2-ethylhexyl acrylate (2EHA), 30 parts by mass of vinyl acetate (Vac), 0.5 parts by mass of acrylic acid (AA), and 10 parts by mass of 2-hydroxyethyl acrylate (2HEA). A solution of a copolymer resin (adhesive main agent, mass average molecular weight 700,000, solid content 35.0% by mass). After adding 1.9 parts by mass (solid content) of a polyvalent isocyanate compound (product name "BHS-8515", manufactured by TOYOCHEM Corporation, solid content 37.5% by mass) as a crosslinking agent to 100 parts by mass of the main adhesive agent, and stirring , to obtain adhesive polymer B.

[中間層用組合物C] 準備由丙烯酸丁酯91質量份及丙烯酸9質量份所構成之質量平均分子量600,000的丙烯酸酯共聚物。 又，除此之外，得到對由丙烯酸正丁酯(BA)62質量份、甲基丙烯酸甲酯(MMA)10質量份、及丙烯酸2-羥基乙酯(2HEA)28質量份所構成之丙烯酸共聚物，將2-異氰酸酯乙基甲基丙烯酸酯(2-isocyanate ethyl methacrylate；製品名「KARENZ MOI」(註冊商標)、昭和電工公司製)以相對於2HEA100莫耳%，加成率成為80莫耳%之方式加成而成的樹脂溶液(固體成分35.0質量%)。 相對於上述丙烯酸酯共聚物100質量份(固體成分)，將樹脂溶液以固體成分基準計為10質量份的比例混合，而得到中間層用組合物C。[Composition C for middle layer] An acrylate copolymer having a mass average molecular weight of 600,000 composed of 91 parts by mass of butyl acrylate and 9 parts by mass of acrylic acid was prepared. In addition, acrylic acid composed of 62 parts by mass of n-butyl acrylate (BA), 10 parts by mass of methyl methacrylate (MMA), and 28 parts by mass of 2-hydroxyethyl acrylate (2HEA) was obtained. In the copolymer, 2-isocyanate ethyl methacrylate (2-isocyanate ethyl methacrylate; product name "KARENZ MOI" (registered trademark), manufactured by Showa Denko Co., Ltd.) was added at a rate of 80 mol to 100 mol% of 2HEA. The resin solution (solid content 35.0% by mass) obtained by adding in the form of ear %. The composition C for intermediate|middle layers was obtained by mixing the resin solution at the ratio of 10 mass parts with respect to 100 mass parts (solid content) of said acrylate copolymers based on solid content.

[中間層用組合物D][Composition D for middle layer]

準備由丙烯酸丁酯91質量份及丙烯酸9質量份所構成之質量平均分子量600,000的丙烯酸酯共聚物。 An acrylate copolymer having a mass average molecular weight of 600,000 composed of 91 parts by mass of butyl acrylate and 9 parts by mass of acrylic acid was prepared.

相對於丙烯酸酯共聚物100質量份(固體成分)，添加2質量份(固體成分)之2~3官能的胺甲酸乙酯丙烯酸酯寡聚物(製品名「PU-5」、大日精化製)，而得到中間層用組合物D。 With respect to 100 parts by mass (solid content) of the acrylate copolymer, 2 to 3 functional urethane acrylate oligomers (product name "PU-5", manufactured by Dainichi Seika Chemical Co., Ltd.) were added in 2 parts by mass (solid content). ), to obtain the composition D for the intermediate layer.

測定含兩性離子的丙烯酸系聚合物1~4、黏著性聚合物A、B、中間層用組合物C、D的彈性模數。將在23℃、40℃、50℃、60℃、70℃、80℃的儲存彈性模數G’、在同溫度之動態黏彈性的tanδ、在60℃的儲存彈性模數G’(60)相對於在23℃之儲存彈性模數G’(23)之比，亦即，G’(60)/G’(23)，顯示在下表。 The modulus of elasticity of zwitterion-containing acrylic polymers 1 to 4, adhesive polymers A, B, and intermediate layer compositions C and D were measured. The storage elastic modulus G' at 23°C, 40°C, 50°C, 60°C, 70°C, and 80°C, the tanδ of dynamic viscoelasticity at the same temperature, and the storage elastic modulus G' at 60°C (60) The ratio with respect to the storage elastic modulus G'(23) at 23°C, that is, G'(60)/G'(23), is shown in the table below.

(實施例1~4、比較例1、2) (Examples 1 to 4, Comparative Examples 1 and 2)

製造具有由含兩性離子的丙烯酸系聚合物1~4、黏著性聚合物A、B所構成的黏著劑層之黏著膠帶。 An adhesive tape having an adhesive layer composed of zwitterion-containing acrylic polymers 1 to 4 and adhesive polymers A and B was produced.

將含兩性離子的丙烯酸系聚合物1~4、黏著性聚合物A或B塗佈在聚對苯二 甲酸乙二酯(PET)系剝離膜(製品名「SP-PET381031」、厚度38μm、LINTEC公司製)且使其乾燥，而得到厚度20μm的黏著劑層。將黏著劑層與前述基材貼合，而製造黏著膠帶。 Coat zwitterionic acrylic polymers 1~4, adhesive polymer A or B on polyterephthalene A ethylene formate (PET)-based release film (product name "SP-PET381031", thickness 38 μm, manufactured by Lintec Corporation) was dried to obtain an adhesive layer with a thickness of 20 μm. The adhesive layer is bonded to the aforementioned base material to manufacture an adhesive tape.

使用所得到的黏著膠帶而進行糊劑殘渣評價、切割性的評價、埋入性評價(小凸塊用)、埋入性評價(中凸塊用)、及端部外觀的評價。將結果顯示在表2。 Using the obtained adhesive tape, evaluation of paste residue, evaluation of cuttability, evaluation of embedding property (for small bumps), evaluation of embedding properties (for medium bumps), and evaluation of end appearance were performed. The results are shown in Table 2.

(實施例5~8、比較例3、4) (Examples 5 to 8, Comparative Examples 3 and 4)

製造具有由含兩性離子的丙烯酸系聚合物1~4、中間層用組合物C、D所構成的中間層之黏著膠帶。 An adhesive tape having an intermediate layer composed of zwitterion-containing acrylic polymers 1 to 4 and compositions C and D for an intermediate layer was produced.

(中間層的製造) (Manufacture of middle layer)

將含兩性離子的丙烯酸系聚合物1~4、中間層用組合物C或D塗佈在聚對苯二甲酸乙二酯(PET)系剝離膜(製品名「SP-PET381031」、厚度38μm、LINTEC公司製)且使其乾燥，而得到厚度45μm的樹脂層。藉由與同樣地製造之厚度45μm的樹脂層貼合，而成為厚度90μm的樹脂層。使樹脂層與前述基材貼合，以製造樹脂層與基材的積層體。該樹脂層在後續將成為中間層。 Coat zwitterion-containing acrylic polymers 1 to 4 and intermediate layer composition C or D on a polyethylene terephthalate (PET) release film (product name "SP-PET381031", thickness 38 μm, Lintec Corporation) and dried to obtain a resin layer with a thickness of 45 μm. A resin layer having a thickness of 90 μm was obtained by bonding to a resin layer having a thickness of 45 μm produced in the same manner. The resin layer and the aforementioned base material are bonded together to manufacture a laminate of the resin layer and the base material. This resin layer will later become the middle layer.

(黏著劑層的製造) (manufacture of adhesive layer)

調製對由丙烯酸丁酯(BA)74質量份、甲基丙烯酸甲酯(MMA)20質量份、丙烯酸2-羥基乙酯(2HEA)6質量份所構成之丙烯酸共聚物，將2-異氰酸酯乙基甲基 丙烯酸酯(2-isocyanate ethyl methacrylate；製品名「KARENZ MOI」(註冊商標)、昭和電工公司製)以相對於2HEA100莫耳%，加成率成為50莫耳%之方式加成而成的樹脂溶液(黏著劑主劑、固體成分35.0質量%)。 Preparation of 2-isocyanate ethyl methyl Acrylate (2-isocyanate ethyl methacrylate; product name "KARENZ MOI" (registered trademark), manufactured by Showa Denko Co., Ltd.) is a resin solution in which the addition rate is 50 mol% relative to 100 mol% of 2HEA (Adhesive main agent, solid content 35.0% by mass).

相對於該黏著劑主劑100質量份，添加1.0質量份作為光聚合起始劑之1-羥基環己基苯基酮(製品名「Irgacure184」、BASF公司製)、及0.2質量份(固體成分)作為交聯劑之多價異氰酸酯化合物(製品名「CORONATEL」、TOSOH公司製)，攪拌後，得到黏著劑組合物。其次，塗佈在聚對苯二甲酸乙二酯(PET)系剝離膜(製品名「SP-PET381031」、厚度38μm、LINTEC公司製)且使其乾燥而在剝離膜上形成厚度20μm的黏著劑層，且與聚對苯二甲酸乙二酯(PET)系剝離膜(製品名「SP-PET382150」、厚度38μm、LINTEC公司製)貼合，而得到具有黏著劑層之積層體。 1.0 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name "Irgacure 184", manufactured by BASF Corporation) as a photopolymerization initiator and 0.2 parts by mass (solid content) were added to 100 parts by mass of the main adhesive agent A polyvalent isocyanate compound (product name "CORONATEL", manufactured by TOSOH Corporation) as a crosslinking agent was stirred to obtain an adhesive composition. Next, apply and dry a polyethylene terephthalate (PET) release film (product name "SP-PET381031", thickness 38 μm, manufactured by LINTEC Co., Ltd.) to form an adhesive with a thickness of 20 μm on the release film. layer, and bonded to a polyethylene terephthalate (PET)-based release film (product name "SP-PET382150", thickness 38 μm, manufactured by Lintec Corporation) to obtain a laminate having an adhesive layer.

(黏著膠帶的製造) (manufacture of adhesive tape)

從具有黏著劑層之積層體將一方的PET膜除去，且貼合在前述樹脂層與基材的積層體之樹脂層面。該結果，得到由PET膜/黏著劑層/樹脂層/基材所構成之黏著膠帶。樹脂層成為黏著劑層與基材之間的中間層。 One PET film was removed from the laminate having the adhesive layer, and bonded to the resin layer of the laminate of the resin layer and the base material. As a result, an adhesive tape composed of PET film/adhesive layer/resin layer/substrate was obtained. The resin layer becomes an intermediate layer between the adhesive layer and the base material.

使用所得到的黏著膠帶而進行糊劑殘渣評價、切割性的評價、埋入性評價(小凸塊用)、埋入性評價(中凸塊用)、及端部外觀的評價。將結果顯示在表3。 Using the obtained adhesive tape, evaluation of paste residue, evaluation of cuttability, evaluation of embedding property (for small bumps), evaluation of embedding properties (for medium bumps), and evaluation of end appearance were performed. The results are shown in Table 3.

如上所述，在本發明中，作為黏著性組合物的主成分之聚合物，使用依照溫度而黏彈性行為不同的部位而成之聚合物、亦即，具有含兩性離子結構的重複單元之聚合物。因此，能夠提供一種黏著膠帶，其在貼附時及保管時容易控制黏著劑層(或中間層)的流動性，且在貼附時追隨工件的凹凸面，而且在保管時黏著性組合物漏出較少。 As described above, in the present invention, as the polymer of the main component of the adhesive composition, a polymer having a site having a different viscoelastic behavior depending on temperature, that is, a polymer having a repeating unit containing a zwitterion structure is used. thing. Therefore, it is possible to provide an adhesive tape that is easy to control the fluidity of the adhesive layer (or intermediate layer) during attachment and storage, and that follows the uneven surface of the workpiece during attachment, and that the adhesive composition leaks out during storage. less.

無。none.

Claims (3)

一種黏著膠帶，包括基材及黏著劑層，其中該基材為樹脂製薄膜，該黏著劑層包括如下述之黏著性組合物，在23℃的儲存模數G’(23)為1.0×10⁵Pa以上，在50℃之儲存模數G’(50)為2.5×10⁵Pa以下，在60℃之動態黏彈性的tanδ為0.5以上，而且包括丙烯酸系聚合物作為主成分。 An adhesive tape comprising a base material and an adhesive layer, wherein the base material is a resin film, the adhesive layer comprises the following adhesive composition, and the storage modulus G'(23) at 23°C is 1.0×10 ⁵ Pa or more, the storage modulus G'(50) at 50°C is 2.5×10 ⁵ Pa or less, the dynamic viscoelasticity tanδ at 60°C is 0.5 or more, and contains acrylic polymer as the main component. 一種黏著膠帶，包括基材、黏著劑層、以及基材與黏著劑層之間之中間層，其中該基材為樹脂製薄膜，該中間層包括如下述之黏著性組合物，在23℃的儲存模數G’(23)為1.0×10⁵Pa以上，在50℃之儲存模數G’(50)為2.5×10⁵Pa以下，在60℃之動態黏彈性的tanδ為0.5以上，而且包括丙烯酸系聚合物作為主成分。 An adhesive tape, comprising a base material, an adhesive layer, and an intermediate layer between the base material and the adhesive layer, wherein the base material is a resin film, and the intermediate layer includes an adhesive composition as follows, at 23°C The storage modulus G'(23) is above 1.0×10 ⁵ Pa, the storage modulus G'(50) at 50°C is below 2.5×10 ⁵ Pa, and the tanδ of dynamic viscoelasticity at 60°C is above 0.5, and Contains acrylic polymer as the main ingredient. 如申請專利範圍第1或2項所述之黏著膠帶，其中該黏著性組合物在60℃的儲存模數G’(60)相對於在23℃的儲存模數G’(23)之比、G’(60)/G’(23)為0.1~0.7。 The adhesive tape as described in item 1 or 2 of the patent application, wherein the ratio of the storage modulus G'(60) of the adhesive composition at 60°C to the storage modulus G'(23) at 23°C, G'(60)/G'(23) is 0.1~0.7.