TW201619319A - Thermal release adhesive tape - Google Patents
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Abstract
Description
本發明係關於一種熱剝離型黏著片。 The present invention relates to a heat-peelable adhesive sheet.
先前,於切斷電子零件之材料時,為了將該材料固定,使用黏著片。於進行該切斷時,有時會產生所小片化之電子材料自黏著片脫落而飛散之所謂晶片飛散。近年來,於模組零件、傳感器等電子零件之加工時,有時會於凹凸面(例如封裝樹脂面、電極圖案面等)貼合黏著片,上述晶片飛散之問題變得顯著。 Previously, when the material of the electronic component was cut, an adhesive sheet was used in order to fix the material. When this cutting is performed, the so-called wafer scattering in which the small-sized electronic material is detached from the adhesive sheet and scattered is sometimes generated. In recent years, in the processing of electronic components such as module parts and sensors, an adhesive sheet may be bonded to an uneven surface (for example, a sealing resin surface or an electrode pattern surface), and the problem of scattering of the above-mentioned wafer becomes remarkable.
另一方面,作為對電子零件之材料進行切斷時使用之黏著片,已知藉由加熱而使黏著力降低之黏著片(例如專利文獻1)。若使用此種黏著片,則能夠實現黏著力之提高,並且能夠獲得切斷後能將被加工物良好地剝離之程度之剝離性。然而,此種黏著片存在雖然對平面被接著體表現出特定之固定性,但對凹凸面被接著體未表現出充分之固定性之問題。 On the other hand, as an adhesive sheet used for cutting a material of an electronic component, an adhesive sheet having a reduced adhesive force by heating is known (for example, Patent Document 1). When such an adhesive sheet is used, the adhesive strength can be improved, and the peeling property can be obtained to the extent that the workpiece can be favorably peeled off after cutting. However, such an adhesive sheet has a problem of exhibiting a certain degree of fixation to a planar adherend, but does not exhibit sufficient fixation of the uneven surface by the adherend.
[專利文獻1]日本專利特開2002-121510號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-121510
黏著片之黏著力例如可藉由於黏著劑層中添加增黏樹脂而提高。若添加增黏樹脂,則黏著劑層自身之黏著力提高,能夠獲得對被 接著面為平面之被接著體具有充分之固定性之黏著片。然而,對於如電極圖案面般具有微細之凹凸面之被接著體,即便使用此種黏著片,亦不能獲得充分之固定性,無法解決上述晶片飛散之問題。 The adhesion of the adhesive sheet can be increased, for example, by the addition of a tackifying resin to the adhesive layer. If a tackifying resin is added, the adhesion of the adhesive layer itself is improved, and the pair can be obtained. The surface is then a flat adhesive sheet having a sufficiently fixed adhesive. However, in the case of the adherend having a fine uneven surface like the electrode pattern surface, even if such an adhesive sheet is used, sufficient fixation cannot be obtained, and the problem of the above-described wafer scattering cannot be solved.
本發明係為了解決上述先前之問題而成者,其目的在於,提供一種熱剝離型黏著片,其為可適宜地於電子零件之材料之加工時使用之黏著片,且不僅對被接著面為平面之被接著體表現出充分之固定性,對具有凹凸面之被接著體亦表現出充分之固定性。 The present invention has been made in order to solve the above-mentioned problems, and an object thereof is to provide a heat-peelable adhesive sheet which is an adhesive sheet which can be suitably used for processing a material of an electronic component, and which is not only The adherend of the flat surface exhibits sufficient fixation, and the adherend having the uneven surface also exhibits sufficient fixation.
本發明之熱剝離型黏著片為具備黏著劑層之熱剝離型黏著片,且該熱剝離型黏著片包含抗靜電材料,該黏著劑層包含黏著劑及熱膨脹性微球,構成該黏著劑之基礎聚合物包含源自含有具有支鏈結構之側鏈之(甲基)丙烯酸烷基酯的結構單元A,該結構單元A之含有比率於該基礎聚合物中為20重量%以上。 The heat-peelable adhesive sheet of the present invention is a heat-peelable adhesive sheet having an adhesive layer, and the heat-peelable adhesive sheet comprises an antistatic material, and the adhesive layer comprises an adhesive and heat-expandable microspheres constituting the adhesive. The base polymer comprises a structural unit A derived from an alkyl (meth)acrylate containing a side chain having a branched structure, and the content ratio of the structural unit A is 20% by weight or more in the base polymer.
於一實施形態中,上述黏著劑層包含上述抗靜電材料。 In one embodiment, the adhesive layer comprises the antistatic material.
於一實施形態中,本發明之熱剝離型黏著片進而包含基材,該基材包含上述抗靜電材料。 In one embodiment, the heat-peelable adhesive sheet of the present invention further comprises a substrate comprising the above-mentioned antistatic material.
於一實施形態中,本發明之熱剝離型黏著片進而具備設置於上述基材之與上述黏著劑層相反之側的抗靜電層,該抗靜電層包含上述抗靜電材料。 In one embodiment, the heat-peelable pressure-sensitive adhesive sheet of the present invention further includes an antistatic layer provided on a side opposite to the pressure-sensitive adhesive layer of the substrate, and the antistatic layer includes the antistatic material.
於一實施形態中,本發明之熱剝離型黏著片進而具備設置於上述基材與上述黏著劑層之間的抗靜電層,該抗靜電層包含上述抗靜電材料。 In one embodiment, the heat-peelable pressure-sensitive adhesive sheet of the present invention further includes an antistatic layer provided between the substrate and the adhesive layer, and the antistatic layer contains the antistatic material.
於一實施形態中,上述結構單元A之具有支鏈結構之側鏈之碳數為5以上。 In one embodiment, the side chain of the structural unit A having a branched structure has a carbon number of 5 or more.
於一實施形態中,上述黏著劑層進而包含增黏樹脂,該增黏樹脂之含有比例相對於上述基礎聚合物100重量份為1重量份~80重量 份。 In one embodiment, the adhesive layer further comprises a tackifying resin, and the content of the tackifying resin is from 1 part by weight to 80% by weight based on 100 parts by weight of the base polymer. Share.
於一實施形態中,本發明之熱剝離型黏著片對於PET膜之黏著力為2N/20mm以上。 In one embodiment, the heat-peelable adhesive sheet of the present invention has an adhesion to the PET film of 2 N/20 mm or more.
根據本發明之另一實施形態,提供一種電子零件之製造方法。該電子零件之製造方法包括如下步驟:於上述熱剝離型黏著片上貼附電子零件材料後,對該電子零件材料進行切斷加工。 According to another embodiment of the present invention, a method of manufacturing an electronic component is provided. The method of manufacturing an electronic component includes the steps of: cutting an electronic component material onto the heat-peelable adhesive sheet, and then cutting the electronic component material.
根據本發明之另一實施形態,提供一種電子零件。該電子零件係利用上述製造方法而製造。 According to another embodiment of the present invention, an electronic component is provided. This electronic component is manufactured by the above manufacturing method.
根據本發明,藉由將包含源自含有具有支鏈結構之側鏈之丙烯酸系單體之結構單元A的基礎聚合物用作黏著劑層之基礎聚合物,可獲得對凹凸面之追隨性優異、並且具有充分之黏著力之黏著片。此種黏著片於對電子零件之材料進行切斷之步驟中可適宜地用作固定該材料之黏著片,能夠有助於防止切斷該材料時之晶片飛散。 According to the present invention, by using a base polymer comprising a structural unit A derived from an acrylic monomer having a side chain having a branched structure as a base polymer of an adhesive layer, excellent followability to the uneven surface can be obtained. And an adhesive sheet with sufficient adhesion. Such an adhesive sheet can be suitably used as an adhesive sheet for fixing the material in the step of cutting the material of the electronic component, and can help prevent the wafer from scattering when the material is cut.
進而,本發明之黏著片為於黏著劑層中包含熱膨脹性微球之熱剝離型黏著片。本發明之熱剝離型黏著片於對電子零件之材料進行加工(例如切斷)時在固定該材料方面表現出充分之黏著力,並且於加工後藉由加熱而表現出適當之剝離性。 Further, the pressure-sensitive adhesive sheet of the present invention is a heat-peelable pressure-sensitive adhesive sheet comprising heat-expandable microspheres in an adhesive layer. The heat-peelable adhesive sheet of the present invention exhibits sufficient adhesion in fixing the material when processing (e.g., cutting) the material of the electronic component, and exhibits appropriate peelability by heating after processing.
10‧‧‧黏著劑層 10‧‧‧Adhesive layer
20‧‧‧基材 20‧‧‧Substrate
30‧‧‧抗靜電層 30‧‧‧Antistatic layer
40‧‧‧彈性層 40‧‧‧Elastic layer
100、200、300‧‧‧黏著片 100, 200, 300‧‧‧ adhesive sheets
圖1係本發明之一實施形態之熱剝離型黏著片之概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing a heat-peelable pressure-sensitive adhesive sheet according to an embodiment of the present invention.
圖2(a)及(b)係本發明之另一實施形態之熱剝離型黏著片之概略剖面圖。 2(a) and 2(b) are schematic cross-sectional views showing a heat-peelable pressure-sensitive adhesive sheet according to another embodiment of the present invention.
圖3係本發明之其他實施形態之熱剝離型黏著片之概略剖面圖。 Fig. 3 is a schematic cross-sectional view showing a heat-peelable pressure-sensitive adhesive sheet according to another embodiment of the present invention.
A.熱剝離型黏著片之整體構成A. The overall composition of the thermal peeling adhesive sheet
圖1係本發明之一實施形態之熱剝離型黏著片之概略剖面圖。熱 剝離型黏著片100具備黏著劑層10。黏著劑層10包含黏著劑及複數個熱膨脹性微球。本發明之熱剝離型黏著片藉由加熱而使該熱膨脹性微球膨脹或發泡,於表面產生凹凸,其結果,黏著力降低,於需要剝離被接著體時表現出適當之剝離性。兼顧黏著力及剝離性之本發明之熱剝離型黏著片例如可適宜地於對電子零件材料進行加工時用作臨時固定該加工物之黏著片。再者,於該實施形態中,熱剝離型黏著片100進而包含基材20。於圖示例中例示於基材20之單側配置有黏著劑層10之例,但黏著劑層亦可配置於基材之兩側。 Fig. 1 is a schematic cross-sectional view showing a heat-peelable pressure-sensitive adhesive sheet according to an embodiment of the present invention. heat The peeling type adhesive sheet 100 is provided with the adhesive layer 10. The adhesive layer 10 contains an adhesive and a plurality of heat-expandable microspheres. In the heat-peelable pressure-sensitive adhesive sheet of the present invention, the heat-expandable microspheres are swelled or foamed by heating, and irregularities are formed on the surface. As a result, the adhesive force is lowered, and when peeling off the adherend, it is necessary to exhibit appropriate peelability. The heat-peelable pressure-sensitive adhesive sheet of the present invention which has both adhesion and peelability can be suitably used, for example, as an adhesive sheet for temporarily fixing the workpiece when the electronic component material is processed. Furthermore, in this embodiment, the heat-peelable pressure-sensitive adhesive sheet 100 further includes a substrate 20. Although an example in which the adhesive layer 10 is disposed on one side of the substrate 20 is exemplified in the illustrated example, the adhesive layer may be disposed on both sides of the substrate.
上述熱剝離型黏著片包含抗靜電材料。於一實施形態中,抗靜電材料包含於黏著劑層中。此外,於其他之實施形態中,抗靜電材料包含於基材中。抗靜電材料亦可包含於黏著劑層及基材二者中。抗靜電材料之詳細內容將於後面敍述。 The above heat-peelable adhesive sheet contains an antistatic material. In one embodiment, the antistatic material is included in the adhesive layer. Further, in other embodiments, the antistatic material is included in the substrate. The antistatic material may also be included in both the adhesive layer and the substrate. The details of the antistatic material will be described later.
圖2(a)及(b)係本發明之進而另一實施形態之熱剝離型黏著片之概略剖面圖。該熱剝離型黏著片200、200'進而具備抗靜電層30。抗靜電層30包含抗靜電材料。抗靜電層30可設置於基材20之與黏著劑層10相反之側(圖2(a)),亦可設置於黏著劑層10與基材20之間(圖2(b))。較佳為,抗靜電層設置於基材之與黏著劑層相反之側。再者,於基材之兩側配置黏著劑層時,上述抗靜電層可配置於基材與黏著劑層之間。 2(a) and 2(b) are schematic cross-sectional views showing a heat-peelable pressure-sensitive adhesive sheet according to still another embodiment of the present invention. The heat-peelable adhesive sheets 200 and 200' further include an antistatic layer 30. The antistatic layer 30 contains an antistatic material. The antistatic layer 30 may be provided on the opposite side of the substrate 20 from the adhesive layer 10 (Fig. 2(a)), or may be provided between the adhesive layer 10 and the substrate 20 (Fig. 2(b)). Preferably, the antistatic layer is disposed on the opposite side of the substrate from the adhesive layer. Further, when the adhesive layer is disposed on both sides of the substrate, the antistatic layer may be disposed between the substrate and the adhesive layer.
本發明之熱剝離型黏著片中,藉由將包含源自含有具有支鏈結構之側鏈(以下亦稱為支鏈結構側鏈)之(甲基)丙烯酸烷基酯之結構單元A的基礎聚合物用作黏著劑層之基礎聚合物,可獲得對凹凸面之追隨性優異、並且具有充分之黏著力之黏著片。另一方面,本申請之發明人等發現於具備由包含特定量之結構單元A之基礎聚合物構成之黏著劑層之黏著片上貼附電子零件材料時,該電子零件材料容易損傷之新的技術問題。本發明係亦能解決此種新技術問題之發明,即,本發 明係提供一種能提高對凹凸面之追隨性、並且藉由包含抗靜電材料而能防止作為被接著體之電子零件材料之損傷之熱剝離型黏著片之發明。本發明之熱剝離型黏著片不僅對被接著面為平面之電子零件材料具有優異之固定性,對具有各種各樣之凹凸面之電子零件材料亦具有優異之固定性,能夠防止將該電子零件材料供於切斷步驟中時之晶片飛散。此外,本發明之熱剝離型黏著片能夠防止作為被接著體之電子零件材料之損傷(例如短路)。 In the heat-peelable adhesive sheet of the present invention, the basis of the structural unit A derived from an alkyl (meth)acrylate having a side chain having a branched structure (hereinafter also referred to as a side chain of a branched structure) is contained. The polymer is used as a base polymer of the adhesive layer, and an adhesive sheet excellent in followability to the uneven surface and having sufficient adhesion can be obtained. On the other hand, the inventors of the present application found a new technique in which an electronic component material is easily damaged when an electronic component material is attached to an adhesive sheet having an adhesive layer composed of a base polymer containing a specific amount of the structural unit A. problem. The present invention is also capable of solving the invention of such a new technical problem, that is, the present invention The invention provides an invention of a heat-peelable adhesive sheet which can improve the followability of the uneven surface and can prevent damage of the electronic component material as the adherend by including an antistatic material. The heat-peelable adhesive sheet of the present invention has excellent fixation not only for an electronic component material whose flat surface is flat, but also has excellent fixing property for an electronic component material having various irregularities, and can prevent the electronic component from being fixed. The material is used to scatter the wafer during the cutting step. Further, the heat-peelable adhesive sheet of the present invention can prevent damage (e.g., short circuit) of the electronic component material as the adherend.
圖3係本發明之進而另一實施形態之熱剝離型黏著片之概略剖面圖。該熱剝離型黏著片300進而具備彈性層40。彈性層40可與黏著劑層鄰接設置,於一實施形態中,如圖示例所示,設置於黏著劑層10與基材20之間。此外,彈性層亦可設置於基材之與黏著劑層相反之側,此外,亦可設置於基材之兩側。藉由具備彈性層,對具有凹凸面之被接著體之追隨性提高。此外,具備彈性層之黏著片於剝離時進行加熱時,黏著劑層之面方向之變形(膨脹)受到限制,厚度方向優先變形。其結果,剝離性提高。再者,亦可使上述抗靜電材料包含於彈性層中。 Fig. 3 is a schematic cross-sectional view showing a heat-peelable pressure-sensitive adhesive sheet according to still another embodiment of the present invention. The heat-peelable adhesive sheet 300 further includes an elastic layer 40. The elastic layer 40 may be disposed adjacent to the adhesive layer, and in one embodiment, is disposed between the adhesive layer 10 and the substrate 20 as shown in the example. In addition, the elastic layer may be disposed on the opposite side of the substrate from the adhesive layer, or may be disposed on both sides of the substrate. By providing the elastic layer, the followability of the adherend having the uneven surface is improved. Further, when the adhesive sheet having the elastic layer is heated at the time of peeling, deformation (expansion) in the surface direction of the adhesive layer is restricted, and the thickness direction is preferentially deformed. As a result, the peelability is improved. Furthermore, the above antistatic material may be included in the elastic layer.
雖未圖示,但以保護黏著面為目的,本發明之熱剝離型黏著片可於黏著劑層之外側設置剝離襯墊直至被供於使用。本發明之熱剝離型黏著片於將剝離襯墊剝離時產生之剝離帶電較少,因此,能夠防止作為被接著體之電子零件材料之損傷(例如短路)。 Although not shown, for the purpose of protecting the adhesive surface, the heat-peelable adhesive sheet of the present invention may be provided with a release liner on the outer side of the adhesive layer until it is used. Since the heat-peelable pressure-sensitive adhesive sheet of the present invention has less peeling charge generated when the release liner is peeled off, it is possible to prevent damage (for example, short circuit) of the electronic component material as the adherend.
將本發明之熱剝離型黏著片貼附於聚對苯二甲酸乙二酯(PET)膜時之23℃下之黏著力a1較佳為2N/20mm以上,更佳為3N/20mm~20N/20mm,進而較佳為4N/20mm~10N/20mm。若為此種範圍,則能夠獲得作為對電子零件材料等進行切斷加工時之臨時固定用片有用之熱剝離型黏著片。於本說明書中,黏著力係指利用基於JIS Z 0237:2000之方法測定之黏著力。具體之測定方法將於後面敍述。再者,本發明之熱剝離型黏著片為藉由加熱而使黏著力降低之黏著片,上述「23℃下之黏著力」係指使黏著力降低之前之黏著力。 The adhesion a1 at 23 ° C when the heat-peelable adhesive sheet of the present invention is attached to a polyethylene terephthalate (PET) film is preferably 2 N/20 mm or more, more preferably 3 N/20 mm to 20 N/ 20 mm, and further preferably 4 N/20 mm to 10 N/20 mm. When it is such a range, it is possible to obtain a heat-peelable pressure-sensitive adhesive sheet which is useful as a temporary fixing sheet for cutting an electronic component material or the like. In this specification, adhesion refers to the use of JIS Z based The adhesion measured by the method of 0237:2000. The specific measurement method will be described later. Further, the heat-peelable pressure-sensitive adhesive sheet of the present invention is an adhesive sheet which is reduced in adhesion by heating, and the above-mentioned "adhesion force at 23 ° C" means an adhesive force before the adhesion is lowered.
將本發明之熱剝離型黏著片之黏著面貼附於聚對苯二甲酸乙二酯膜並進行加熱後之黏著力a2較佳為0.2N/20mm以下,更佳為0.1N/20mm以下。於本說明書中,對熱剝離型黏著片之加熱係指以熱膨脹性微球膨脹或發泡而使黏著力降低之溫度‧時間進行之加熱。該加熱例如為70℃~270℃下1分鐘~10分鐘之加熱。 The adhesive force a2 after the adhesive surface of the heat-peelable pressure-sensitive adhesive sheet of the present invention is attached to the polyethylene terephthalate film and heated is preferably 0.2 N/20 mm or less, more preferably 0.1 N/20 mm or less. In the present specification, the heating of the heat-peelable pressure-sensitive adhesive sheet refers to heating at a temperature at which the heat-expandable microspheres are expanded or foamed to lower the adhesion. The heating is, for example, heating at 70 ° C to 270 ° C for 1 minute to 10 minutes.
將本發明之熱剝離型黏著片之黏著面貼附於聚對苯二甲酸乙二酯膜時之黏著力(即加熱前之黏著力(a1))與加熱後之黏著力(a2)之比(a2/a1)較佳為0.5以下,更佳為0.1以下。(a2/a1)之下限較佳為0.0001,更佳為0.0005。 The adhesive force (i.e., the adhesive force before heating (a1)) and the adhesive force after heating (a2) when the adhesive surface of the heat-peelable adhesive sheet of the present invention is attached to the polyethylene terephthalate film (a2/a1) is preferably 0.5 or less, more preferably 0.1 or less. The lower limit of (a2/a1) is preferably 0.0001, more preferably 0.0005.
如上所述,本發明之熱剝離型黏著片藉由於特定之溫度下進行加熱而於黏著面產生凹凸。對本發明之熱剝離型黏著片進行加熱後之黏著面之表面粗糙度Ra較佳為3μm以上,更佳為5μm以上。若為此種範圍,則加熱後黏著力降低或消失,可獲得能使被接著體容易地剝離之黏著片。再者,黏著面之表面粗糙度Ra係指於無被接著體之狀態下進行加熱後之黏著片之黏著面之表面粗糙度Ra。表面粗糙度Ra可基於JIS B 0601:1994來測定。 As described above, the heat-peelable pressure-sensitive adhesive sheet of the present invention generates irregularities on the adhesive surface by heating at a specific temperature. The surface roughness Ra of the adhesive surface after heating the heat-peelable pressure-sensitive adhesive sheet of the present invention is preferably 3 μm or more, and more preferably 5 μm or more. If it is such a range, the adhesive force will be reduced or disappeared after heating, and the adhesive sheet which can be peeled easily by the adhesive body is obtained. Further, the surface roughness Ra of the adhesive surface refers to the surface roughness Ra of the adhesive surface of the adhesive sheet which is heated without being subjected to the adherend. The surface roughness Ra can be measured based on JIS B 0601:1994.
B.抗靜電材料B. Antistatic material
作為上述抗靜電材料之含有形態,例如可列舉:(1)作為添加物包含於黏著劑層中之形態、(2)作為添加物包含於基材中之形態、(3)包含於與黏著劑層或基材不同之層(抗靜電層)中之形態等。此外,作為形態(3)中之抗靜電層,例如可列舉:包含樹脂之抗靜電層(形態(3a))、由金屬或金屬氧化物構成之抗靜電層(形態(3b))等。較佳為形 態(2)或(3),更佳為形態(3a)。此外,就透明性之觀點而言,可較佳選擇形態(2)或(3a),更佳為(3a)。若製成形態(2)或(3a)而含有抗靜電材料,則能夠獲得透明性優異之熱剝離型黏著片(例如透光率70%~90%)。此種熱剝離型黏著片容易隔著黏著片而識別被接著體。本發明之熱剝離型黏著片中,包含熱膨脹性微球之黏著劑層於光學上具有濁度,因此,較佳為提高其他構件之透明性,從而提高熱剝離型黏著片整體之透明性。此外,若選擇形態(1)或(3)即使抗靜電材料不包含於基材中而使用,則能夠防止抗靜電材料之經時滲漏,能夠獲得品質方面之穩定性優異之熱剝離型黏著片。因此,特別較佳為以形態(3a)之方式含有抗靜電材料,根據該形態,能夠獲得透明性、品質方面之穩定性等優異之熱剝離型黏著片。於進而另一實施形態中,可列舉使抗靜電材料包含於彈性層中之太陽、使用金屬箔作為基材等基材自身作為抗靜電材料發揮作用之態樣等。 Examples of the form of the antistatic material include (1) a form in which the additive is contained in the adhesive layer, (2) a form which is included as an additive in the substrate, and (3) inclusion in the adhesive. The form or the like in a layer or an anti-static layer of a substrate. In addition, examples of the antistatic layer in the form (3) include an antistatic layer containing a resin (form (3a)), an antistatic layer (form (3b)) composed of a metal or a metal oxide, and the like. Preferred shape State (2) or (3), more preferably form (3a). Further, from the viewpoint of transparency, the form (2) or (3a) can be preferably selected, and more preferably (3a). When the antistatic material is contained in the form (2) or (3a), a heat-peelable pressure-sensitive adhesive sheet having excellent transparency (for example, a light transmittance of 70% to 90%) can be obtained. Such a heat-peelable adhesive sheet easily recognizes the adherend through the adhesive sheet. In the heat-peelable pressure-sensitive adhesive sheet of the present invention, since the pressure-sensitive adhesive layer containing the heat-expandable microspheres has optical haze, it is preferable to improve the transparency of the other members, thereby improving the transparency of the entire heat-peelable pressure-sensitive adhesive sheet. In addition, when the antistatic material is not contained in the substrate, the shape (1) or (3) can be prevented from leaking over time, and the heat-peelable adhesion excellent in quality stability can be obtained. sheet. Therefore, it is particularly preferable to contain an antistatic material in the form of the form (3a), and according to this aspect, it is possible to obtain a heat-peelable pressure-sensitive adhesive sheet which is excellent in transparency and stability in terms of quality. In still another embodiment, the sun, the use of a metal foil as a base material, and the like, the antistatic material may be used as an antistatic material.
上述抗靜電材料可根據抗靜電材料之形態來調整其含有比率。抗靜電材料之含有比率相對於熱剝離型黏著片之重量較佳為0.00001重量%~10重量%,更佳為0.0001重量%~5重量%。 The above antistatic material can be adjusted in accordance with the form of the antistatic material. The content ratio of the antistatic material is preferably 0.00001% by weight to 10% by weight, and more preferably 0.0001% by weight to 5% by weight based on the weight of the heat-peelable pressure-sensitive adhesive sheet.
B-1.抗靜電材料作為添加物包含於黏著劑層中之形態(形態(1)) B-1. A form in which an antistatic material is contained in an adhesive layer as an additive (morphology (1))
上述形態(1)中,上述抗靜電材料包含於黏著劑層形成用組合物中,藉由利用該黏著劑層形成用組合物形成黏著劑層,從而形成包含抗靜電材料之黏著劑層。於此種情形時,關於黏著劑層中之抗靜電材料之含有比率,相對於構成黏著劑層之基礎聚合物100重量份,較佳為0.01重量份~10重量份,更佳為0.05重量份~5重量份。若為此種範圍,則能夠防止貼附於電子零件材料時該電子零件材料之損傷。 In the above aspect (1), the antistatic material is contained in the adhesive layer-forming composition, and the adhesive layer is formed by using the adhesive layer-forming composition to form an adhesive layer containing an antistatic material. In this case, the content ratio of the antistatic material in the adhesive layer is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.05 parts by weight, based on 100 parts by weight of the base polymer constituting the adhesive layer. ~5 parts by weight. If it is such a range, damage of the electronic component material at the time of sticking to an electronic component material can be prevented.
作為上述黏著劑層形成用組合物中所含之抗靜電材料,例如可列舉導電性聚合物、離子性液體等。此種抗靜電材料可單獨使用,亦 可混合使用2種以上。 The antistatic material contained in the composition for forming an adhesive layer may, for example, be a conductive polymer or an ionic liquid. This antistatic material can be used alone, Two or more types can be used in combination.
(離子性液體) (ionic liquid)
離子性液體為液狀之有機化合物,係指於室溫下呈液狀之熔融鹽(離子性化合物),其對於黏著劑組合物中之基礎聚合物之相容性良好。藉此,能夠抑制離子性液體於黏著劑層之表面偏析,防止黏著力之經時降低、因轉移至被接著體而引起之污染。再者,相容性係指利用適當之混合方法(熔融掺合、溶液掺合)將離子性液體與基礎聚合物混合時,均勻地混合、不易分相之性質。 The ionic liquid is a liquid organic compound, and is a molten salt (ionic compound) which is liquid at room temperature, and which has good compatibility with the base polymer in the adhesive composition. Thereby, it is possible to suppress the segregation of the ionic liquid on the surface of the adhesive layer, and to prevent the deterioration of the adhesive force over time and the contamination caused by the transfer to the adherend. Further, compatibility refers to a property of uniformly mixing and being difficult to phase-separate when an ionic liquid is mixed with a base polymer by an appropriate mixing method (melt blending, solution blending).
此外,若使用離子性液體,則能夠形成表現出優異之抗靜電性之黏著劑層。藉由使用離子性液體能獲得優異之抗靜電性之詳細理由尚不明確,推測如下。即,由於離子性液體為液狀,因此與通常使用之界面活性劑相比,分子運動更容易,由於電荷之產生而容易進行分子之再排列。因此,認為使用離子性液體之情形時,由分子再排列帶來之電荷中和機制發揮作用,由此能夠獲得優異之抗靜電效果。此外,由於離子性液體於室溫下呈液狀,因此與固體之鹽相比,更容易進行向黏著劑之添加及分散或溶解。進而,由於離子性液體無蒸汽壓(不揮發性),因此不會經時消失,具有能持續獲得抗靜電性之特徵。 Further, when an ionic liquid is used, an adhesive layer exhibiting excellent antistatic properties can be formed. The detailed reason why the excellent antistatic property can be obtained by using an ionic liquid is not clear, and it is presumed as follows. That is, since the ionic liquid is in a liquid state, molecular motion is easier than that of a commonly used surfactant, and molecular rearrangement is facilitated by the generation of electric charges. Therefore, in the case of using an ionic liquid, it is considered that a charge neutralization mechanism by molecular rearrangement acts, whereby an excellent antistatic effect can be obtained. Further, since the ionic liquid is liquid at room temperature, it is easier to add, disperse or dissolve the adhesive than the solid salt. Further, since the ionic liquid has no vapor pressure (non-volatile), it does not disappear over time, and has a feature that the antistatic property can be continuously obtained.
關於上述離子性液體之含有比率,相對於構成黏著劑層之基礎聚合物100重量份,較佳為0.01重量份~10重量份,更佳為0.01重量份~8重量份,更佳為0.1重量份~5重量份。若於此種範圍,則能夠獲得充分之抗靜電效果。 The content ratio of the ionic liquid is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.01 parts by weight to 8 parts by weight, even more preferably 0.1% by weight based on 100 parts by weight of the base polymer constituting the pressure-sensitive adhesive layer. Parts ~ 5 parts by weight. If it is in such a range, a sufficient antistatic effect can be obtained.
作為上述離子性液體,只要能獲得本發明之效果,則可使用任意適當之離子性液體。離子性液體較佳為含氮鎓鹽、含硫鎓鹽或含磷鎓鹽,更佳為使用包含下述通式(A)~(E)表示之有機陽離子成分及陰離子成分之鹽。其原因在於能表現出優異之抗靜電能力。 As the ionic liquid, any appropriate ionic liquid can be used as long as the effects of the present invention can be obtained. The ionic liquid is preferably a nitrogen-containing phosphonium salt, a sulfur-containing phosphonium salt or a phosphorus-containing phosphonium salt, and more preferably a salt containing an organic cationic component and an anionic component represented by the following general formulae (A) to (E). The reason for this is that it exhibits excellent antistatic ability.
式(A)中,Ra表示碳數4~20之烴基,Rb及Rc分別獨立地表示氫或碳數1~16之烴基。再者,Ra、Rb及Rc可包含雜原子。此外,氮原子藉由雙鍵進行鍵合之情形時,不存在Rc。 In the formula (A), Ra represents a hydrocarbon group having 4 to 20 carbon atoms, and Rb and Rc each independently represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms. Further, Ra, Rb and Rc may contain a hetero atom. Further, when the nitrogen atom is bonded by a double bond, Rc does not exist.
式(B)中,Rd表示碳數2~20之烴基,Re、Rf及Rg分別獨立地表示氫或碳數1~16之烴基。Rd、Re、Rf及Rg可包含雜原子。 In the formula (B), Rd represents a hydrocarbon group having 2 to 20 carbon atoms, and Re, Rf and Rg each independently represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms. Rd, Re, Rf, and Rg may contain heteroatoms.
式(C)中,Rh表示碳數2~20之烴基,Ri、Rj及Rk分別獨立地表示氫或碳數1~16之烴基。Rh、Ri、Rj及Rk可包含雜原子。 In the formula (C), Rh represents a hydrocarbon group having 2 to 20 carbon atoms, and Ri, Rj and Rk each independently represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms. Rh, Ri, Rj, and Rk may contain a hetero atom.
式(D)中,Z表示氮、硫、或磷原子,Rl、Rm、Rn及Ro分別獨立地表示碳數1~20之烴基,且可包含雜原子。其中,Z為硫原子之情形時,不存在Ro。 In the formula (D), Z represents a nitrogen, sulfur or phosphorus atom, and R1, Rm, Rn and Ro each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom. Wherein, when Z is a sulfur atom, there is no Ro.
式(E)中,Rp表示碳數1~18之烴基,且可包含雜原子。 In the formula (E), Rp represents a hydrocarbon group having 1 to 18 carbon atoms, and may contain a hetero atom.
作為式(A)表示之陽離子,可列舉吡啶鎓陽離子、哌啶鎓陽離子、吡咯烷鎓陽離子、具有吡咯啉骨架之陽離子、具有吡咯骨架之陽離子等。例如可列舉吡啶鎓陽離子、哌啶鎓陽離子、吡咯烷鎓陽離子、具有吡咯啉骨架之陽離子、具有吡咯骨架之陽離子等。作為具體例,例如可列舉:1-乙基吡啶鎓陽離子、1-丁基吡啶鎓陽離子、1-己基吡啶鎓陽離子、1-丁基-3-甲基吡啶鎓陽離子、1-丁基-4-甲基吡啶鎓陽離子、1-己基-3-甲基吡啶鎓陽離子、1-丁基-3,4-二甲基吡啶鎓陽離子等吡啶鎓陽離子;1-丙基哌啶鎓陽離子、1-戊基哌啶鎓陽離子、1,1-二甲基哌啶鎓陽離子、1-甲基-1-乙基哌啶鎓陽離子、1-甲基-1-丙 基哌啶鎓陽離子、1-甲基-1-丁基哌啶鎓陽離子、1-甲基-1-戊基哌啶鎓陽離子、1-甲基-1-己基哌啶鎓陽離子、1-甲基-1-庚基哌啶鎓陽離子、1-乙基-1-丙基哌啶鎓陽離子、1-乙基-1-丁基哌啶鎓陽離子、1-乙基-1-戊基哌啶鎓陽離子、1-乙基-1-己基哌啶鎓陽離子、1-乙基-1-庚基哌啶鎓陽離子、1,1-二丙基哌啶鎓陽離子、1-丙基-1-丁基哌啶鎓陽離子、1,1-二丁基哌啶鎓陽離子等哌啶鎓陽離子;1,1-二甲基吡咯烷鎓陽離子、1-甲基-1-乙基吡咯烷鎓陽離子、1-甲基-1-丙基吡咯烷鎓陽離子、1-甲基-1-丁基吡咯烷鎓陽離子、1-甲基-1-戊基吡咯烷鎓陽離子、1-甲基-1-己基吡咯烷鎓陽離子、1-甲基-1-庚基吡咯烷鎓陽離子、1-乙基-1-丙基吡咯烷鎓陽離子、1-乙基-1-丁基吡咯烷鎓陽離子、1-乙基-1-戊基吡咯烷鎓陽離子、1-乙基-1-己基吡咯烷鎓陽離子、1-乙基-1-庚基吡咯烷鎓陽離子、1,1-二丙基吡咯烷鎓陽離子、1-丙基-1-丁基吡咯烷鎓陽離子、1,1-二丁基吡咯烷鎓陽離子等吡咯烷鎓陽離子;2-甲基-1-吡咯啉陽離子、1-乙基-2-苯基吲哚陽離子、1,2-二甲基吲哚陽離子、1-乙基咔唑陽離子等。 Examples of the cation represented by the formula (A) include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, and the like. For example, a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, and the like can be given. Specific examples thereof include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, and 1-butyl-4. a pyridinium cation such as a methylpyridinium cation, a 1-hexyl-3-methylpyridinium cation or a 1-butyl-3,4-dimethylpyridinium cation; a 1-propylpiperidinium cation, 1- Pentyl piperidinium cation, 1,1-dimethyl piperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propene Isopiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl 1,1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidine Ruthenium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1,1-dipropyl piperidinium cation, 1-propyl-1-butene a piperidinium cation such as a piperidinium cation or a 1,1-dibutylpiperidinium cation; a 1,1-dimethylpyrrolidinium cation, a 1-methyl-1-ethylpyrrolidinium cation, 1 -methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrole Alkane cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl 1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrole Pyrrolidinium cations such as alkane cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation; 2-methyl-1-pyrroline cation, 1-ethyl a -2-phenylphosphonium cation, a 1,2-dimethylhydrazine cation, a 1-ethylcarbazole cation, or the like.
作為式(B)表示之陽離子,可列舉:咪唑鎓陽離子、四氫嘧啶鎓陽離子、二氫嘧啶鎓陽離子等。例如可列舉:咪唑鎓陽離子、四氫嘧啶鎓陽離子、二氫嘧啶鎓陽離子等。作為具體例,例如可列舉:1,3-二甲基咪唑鎓陽離子、1,3-二乙基咪唑鎓陽離子、1-乙基-3-甲基咪唑鎓陽離子、1-丁基-3-甲基咪唑鎓陽離子、1-己基-3-甲基咪唑鎓陽離子、1-辛基-3-甲基咪唑鎓陽離子、1-癸基-3-甲基咪唑鎓陽離子、1-十二烷基-3-甲基咪唑鎓陽離子、1-十四烷基-3-甲基咪唑鎓陽離子、1,2-二甲基-3-丙基咪唑鎓陽離子、1-乙基-2,3-二甲基咪唑鎓陽離子、1-丁基-2,3-二甲基咪唑鎓陽離子、1-己基-2,3-二甲基咪唑鎓陽離子等咪唑鎓陽離子;1,3-二甲基-1,4,5,6-四氫嘧啶鎓陽離子、1,2,3-三甲基-1,4,5,6-四氫嘧啶鎓陽離子、1,2,3,4-四甲基-1,4,5,6-四氫嘧啶鎓陽離 子、1,2,3,5-四甲基-1,4,5,6-四氫嘧啶鎓陽離子等四氫嘧啶鎓陽離子;1,3-二甲基-1,4-二氫嘧啶鎓陽離子、1,3-二甲基-1,6-二氫嘧啶鎓陽離子、1,2,3-三甲基-1,4-二氫嘧啶鎓陽離子、1,2,3-三甲基-1,6-二氫嘧啶鎓陽離子、1,2,3,4-四甲基-1,4-二氫嘧啶鎓陽離子、1,2,3,4-四甲基-1,6-二氫嘧啶鎓陽離子等二氫嘧啶鎓陽離子等及1-丁基-3-甲基吡啶鎓雙醯亞胺等1-丁基-3-甲基吡啶鎓陽離子。 Examples of the cation represented by the formula (B) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation. For example, an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, etc. are mentioned. Specific examples include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3- Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-mercapto-3-methylimidazolium cation, 1-dodecyl 3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-di Imidazolium cations such as methylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation; 1,3-dimethyl-1 , 4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1 , 4,5,6-tetrahydropyrimidine Tetrahydropyrimidinium cation such as 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation; 1,3-dimethyl-1,4-dihydropyrimidine Cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl- 1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydrogen A 1-butyl-3-methylpyridinium cation such as a dihydropyrimidinium cation such as a pyrimidine sulfonium cation or a 1-butyl-3-methylpyridinium bis-imideimine.
作為式(C)表示之陽離子,可列舉:吡唑鎓陽離子、二氫化吡唑鎓陽離子等。例如可列舉:吡唑鎓陽離子、二氫化吡唑鎓陽離子等。作為具體例,例如可列舉:1-甲基吡唑鎓陽離子、3-甲基吡唑鎓陽離子、1-乙基-2-甲基二氫化吡唑鎓陽離子等。 Examples of the cation represented by the formula (C) include a pyrazolium cation, a dihydropyrazolium cation, and the like. For example, a pyrazolium cation, a dihydropyrazolium cation, etc. are mentioned. Specific examples thereof include a 1-methylpyrazolium cation, a 3-methylpyrazolium cation, and a 1-ethyl-2-methyldihydropyrazolium cation.
作為式(D)表示之陽離子,可列舉:四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子等。此外,亦可使用該等陽離子之烷基之一部分經烯基、烷氧基、或環氧基取代之陽離子。此外,Rl、Rm、Rn及Ro如上所述為碳數1~20之烴基,較佳為碳數1~20之烷基。此外,Rl、Rm、Rn及Ro亦可為芳香環基或脂環基。作為式(D)表示之陽離子之具體例,可列舉:四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子、或上述烷基之一部分經烯基、烷氧基、進而環氧基取代而成之陽離子等。作為具體例,例如可列舉:N,N-二甲基-N-乙基-N-丙基銨陽離子、N,N-二甲基-N-乙基-N-丁基銨陽離子、N,N-二甲基-N-乙基-N-戊基銨陽離子、N,N-二甲基-N-乙基-N-己基銨陽離子、N,N-二甲基-N-乙基-N-庚基銨陽離子、N,N-二甲基-N-乙基-N-壬基銨陽離子、N,N-二甲基-N,N-二丙基銨陽離子、N,N-二甲基-N-丙基-N-丁基銨陽離子、N,N-二甲基-N-丙基-N-戊基銨陽離子、N,N-二甲基-N-丙基-N-己基銨陽離子、N,N-二甲基-N-丙基-N-庚基銨陽離子、N,N-二甲基-N-丁基-N-己基銨陽離子、N,N-二甲基-N-丁基-N-庚基銨陽離子、N,N-二甲基-N-戊基-N-己基銨陽離子、N,N-二甲基-N,N-二己基 銨陽離子、三甲基庚基銨陽離子、N,N-二乙基-N-甲基-N-丙基銨陽離子、N,N-二乙基-N-甲基-N-戊基銨陽離子、N,N-二乙基-N-甲基-N-庚基銨陽離子、N,N-二乙基-N-丙基-N-戊基銨陽離子、三乙基甲基銨陽離子、三乙基丙基銨陽離子、三乙基戊基銨陽離子、三乙基庚基銨陽離子、N,N-二丙基-N-甲基-N-乙基銨陽離子、N,N-二丙基-N-甲基-N-戊基銨陽離子、N,N-二丙基-N-丁基-N-己基銨陽離子、N,N-二丙基-N,N-二己基銨陽離子、N,N-二丁基-N-甲基-N-戊基銨陽離子、N,N-二丁基-N-甲基-N-己基銨陽離子、三辛基甲基銨陽離子、N-甲基-N-乙基-N-丙基-N-戊基銨陽離子、四甲基銨陽離子、四乙基銨陽離子、四丁基銨陽離子、四己基銨陽離子、三丁基乙基銨陽離子、三甲基癸基銨陽離子、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨陽離子、縮水甘油基三甲基銨陽離子、二烯丙基二甲基銨陽離子等四烷基銨陽離子;三甲基鋶陽離子、三乙基鋶陽離子、三丁基鋶陽離子、三己基鋶陽離子、二乙基甲基鋶陽離子、二丁基乙基鋶陽離子、二甲基癸基鋶陽離子等三烷基鋶陽離子;四甲基鏻陽離子、四乙基鏻陽離子、四丁基鏻陽離子、四己基鏻陽離子、鏻陽離子、三乙基甲基鏻陽離子、三丁基乙基鏻陽離子、三甲基癸基鏻陽離子等四烷基鏻陽離子等。 Examples of the cation represented by the formula (D) include a tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkylphosphonium cation. Further, a cation in which one of the alkyl groups of the cations is substituted with an alkenyl group, an alkoxy group or an epoxy group may also be used. Further, R1, Rm, Rn and Ro are a hydrocarbon group having 1 to 20 carbon atoms as described above, and preferably an alkyl group having 1 to 20 carbon atoms. Further, Rl, Rm, Rn and Ro may be an aromatic ring group or an alicyclic group. Specific examples of the cation represented by the formula (D) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, or a part of the above alkyl group via an alkenyl group, an alkoxy group, and further an epoxy group. A cation or the like substituted by a base. Specific examples thereof include N,N-dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, and N. N-dimethyl-N-ethyl-N-pentyl ammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl- N-heptyl ammonium cation, N,N-dimethyl-N-ethyl-N-decyl ammonium cation, N,N-dimethyl-N,N-dipropyl ammonium cation, N,N-di Methyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N-propyl-N-amylammonium cation, N,N-dimethyl-N-propyl-N- Hexyl ammonium cation, N,N-dimethyl-N-propyl-N-heptyl ammonium cation, N,N-dimethyl-N-butyl-N-hexyl ammonium cation, N,N-dimethyl -N-butyl-N-heptyl ammonium cation, N,N-dimethyl-N-pentyl-N-hexylammonium cation, N,N-dimethyl-N,N-dihexyl Ammonium cation, trimethylheptyl ammonium cation, N,N-diethyl-N-methyl-N-propyl ammonium cation, N,N-diethyl-N-methyl-N-pentyl ammonium cation , N,N-diethyl-N-methyl-N-heptyl ammonium cation, N,N-diethyl-N-propyl-N-pentyl ammonium cation, triethylmethyl ammonium cation, three Ethylpropylammonium cation, triethylammonium ammonium cation, triethylheptyl ammonium cation, N,N-dipropyl-N-methyl-N-ethylammonium cation, N,N-dipropyl -N-methyl-N-amyl ammonium cation, N,N-dipropyl-N-butyl-N-hexylammonium cation, N,N-dipropyl-N,N-dihexyl ammonium cation, N , N-dibutyl-N-methyl-N-amylammonium cation, N,N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl -N-ethyl-N-propyl-N-amyl ammonium cation, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrahexylammonium cation, tributylethylammonium cation, three Methyl decyl ammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium cation, glycidyl trimethyl ammonium cation, diallyl dimethyl Tetraalkyl group such as ammonium cation Ammonium cation; trimethyl phosphonium cation, triethyl phosphonium cation, tributyl phosphonium cation, trihexyl phosphonium cation, diethyl methyl phosphonium cation, dibutyl ethyl phosphonium cation, dimethyl fluorenyl ruthenium cation, etc. Trialkylsulfonium cation; tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, phosphonium cation, triethylmethyl phosphonium cation, tributylethyl phosphonium cation, trimethyl A tetraalkylphosphonium cation such as a quinone-based cation or the like.
於本發明中,於上述陽離子成分之中,就能獲得特別優異之抗靜電能之方面而言,較佳使用式(A)表示之陽離子(特別係1-乙基吡啶鎓陽離子、1-丁基吡啶鎓陽離子、1-己基吡啶鎓陽離子、1-丁基-3-甲基吡啶鎓陽離子、1-丁基-4-甲基吡啶鎓陽離子、1-己基-3-甲基吡啶鎓陽離子、1-丁基-3,4-二甲基吡啶鎓陽離子等吡啶鎓陽離子)、式(D)表示之陽離子(特別係三乙基甲基銨陽離子、三丁基乙基銨陽離子、三甲基癸基銨陽離子、二乙基甲基鋶陽離子、二丁基乙基鋶陽離子、二甲基癸基鋶陽離子、三乙基甲基鏻陽離子、三丁基乙基鏻陽離子、三甲基癸基鏻陽離子等非對稱之四烷基銨陽離子、三烷基鋶陽離子、 四烷基鏻陽離子、或N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨陽離子、二烯丙基二甲基銨陽離子、縮水甘油基三甲基銨陽離子等)等。 In the present invention, among the above cationic components, in terms of obtaining particularly excellent antistatic energy, it is preferred to use a cation represented by the formula (A) (particularly 1-ethylpyridinium cation, 1-butyl) Pyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, a pyridinium cation such as a 1-butyl-3,4-dimethylpyridinium cation or a cation represented by the formula (D) (particularly a triethylmethylammonium cation, a tributylethylammonium cation, a trimethyl group) Mercaptoammonium cation, diethylmethyl phosphonium cation, dibutylethyl phosphonium cation, dimethyl decyl sulfonium cation, triethylmethyl phosphonium cation, tributyl ethyl phosphonium cation, trimethyl fluorenyl An asymmetric tetraalkylammonium cation such as a phosphonium cation, a trialkyl phosphonium cation, Tetraalkylphosphonium cation, or N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, diallyldimethylammonium cation, glycidyl trimethyl Ammonium cations, etc.).
作為式(E)表示之陽離子之具體例,可列舉具有例如甲基、乙基、丙基、丁基、己基、辛基、壬基、癸基、十二烷基、十三烷基、十四烷基、十八烷基等碳數1~18之烷基作為Rp之鋶鹽。 Specific examples of the cation represented by the formula (E) include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, a tridecyl group, and a decyl group. An alkyl group having 1 to 18 carbon atoms such as a tetraalkyl group or an octadecyl group is used as the phosphonium salt of Rp.
作為上述陰離子成分,只要能夠與上述陽離子成分一起形成離子性液體,則可使用任意適當之陰離子成分。例如可列舉:Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-、(CF3SO2)(CF3CO)N等。疏水性之陰離子成分具有不易滲出於黏著劑表面之傾向,就低污染性之觀點而言較佳使用。進而,包含氟原子之陰離子成分能夠獲得低熔點之離子性化合物,因此特別較佳使用。 As the anion component, any suitable anion component can be used as long as it can form an ionic liquid together with the above cationic component. For example, Cl - , Br - , I - , AlCl 4 - , Al 2 Cl 7 - , BF 4 - , PF 6 - , ClO 4 - , NO 3 - , CH 3 COO - , CF 3 COO - , CH 3 SO 3 - , CF 3 SO 3 - , (CF 3 SO 2 ) 2 N - , (CF 3 SO 2 ) 3 C - , AsF 6 - , SbF 6 - , NbF 6 - , TaF 6 - , F (HF n - , (CN) 2 N - , C 4 F 9 SO 3 - , (C 2 F 5 SO 2 ) 2 N - , C 3 F 7 COO - , (CF 3 SO 2 )(CF 3 CO)N Wait. The hydrophobic anionic component tends to be less likely to penetrate the surface of the adhesive, and is preferably used from the viewpoint of low contamination. Further, since an anion component containing a fluorine atom can obtain an ionic compound having a low melting point, it is particularly preferably used.
本發明中之離子性液體可自上述陽離子成分與陰離子成分之組合中適當選擇並使用,例如可列舉:1-丁基吡啶鎓四氟硼酸鹽、1-丁基吡啶鎓六氟磷酸鹽、1-丁基-3-甲基吡啶鎓四氟硼酸鹽、1-丁基-3-甲基吡啶鎓三氟甲磺酸鹽、1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺、1-丁基-3-甲基吡啶鎓雙(五氟乙磺醯基)醯亞胺、1-己基吡啶鎓四氟硼酸鹽、1,1-二甲基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-乙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丁基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-戊基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-己基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-庚基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丁基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-戊基 吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-己基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-庚基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-丙基-1-丁基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丁基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺、1-丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-戊基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二甲基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-乙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-戊基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-己基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-庚基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-戊基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-己基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-庚基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-丙基-1-丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二甲基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-乙基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丁基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-戊基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-己基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-庚基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丙基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丁基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-戊基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-己基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-庚基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丙基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-丙基-1-丁基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、 1,1-二丁基吡咯烷鎓雙(五氟乙磺醯基)醯亞胺、1-丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-戊基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二甲基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-乙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-戊基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-己基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-庚基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-戊基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-己基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-庚基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-丙基-1-丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、2-甲基-1-吡咯啉四氟硼酸鹽、1-乙基-2-苯基吲哚四氟硼酸鹽、1,2-二甲基吲哚四氟硼酸鹽、1-乙基咔唑四氟硼酸鹽、1-乙基-3-甲基咪唑鎓四氟硼酸鹽、1-乙基-3-甲基咪唑鎓乙酸鹽、1-乙基-3-甲基咪唑鎓三氟乙酸鹽、1-乙基-3-甲基咪唑鎓七氟丁酸鹽、1-乙基-3-甲基咪唑鎓三氟甲磺酸鹽、1-乙基-3-甲基咪唑鎓全氟丁磺酸鹽、1-乙基-3-甲基咪唑鎓雙氰胺鹽、1-乙基-3-甲基咪唑鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓三(三氟甲磺醯基)甲基化物、1-丁基-3-甲基咪唑鎓四氟硼酸鹽、1-丁基-3-甲基咪唑鎓六氟磷酸鹽、1-丁基-3-甲基咪唑鎓三氟乙酸鹽、1-丁基-3-甲基咪唑鎓七氟丁酸鹽、1-丁基-3-甲基咪唑鎓三氟甲磺酸鹽、1-丁基-3-甲基咪唑鎓全氟丁磺酸鹽、1-丁基-3-甲基咪唑鎓雙(三氟甲磺醯基)醯亞胺、1-己基-3-甲基咪唑鎓溴化物、1-己基-3-甲基咪唑鎓氯化物、1-己基-3-甲基咪唑鎓四氟硼酸鹽、1-己基-3-甲基咪唑鎓六氟磷酸鹽、1-己基-3-甲基咪唑鎓三氟甲磺酸鹽、 1-辛基-3-甲基咪唑鎓四氟硼酸鹽、1-辛基-3-甲基咪唑鎓六氟磷酸鹽、1-己基-2,3-二甲基咪唑鎓四氟硼酸鹽、1,2-二甲基-3-丙基咪唑鎓雙(三氟甲磺醯基)醯亞胺、1-甲基吡唑鎓四氟硼酸鹽、3-甲基吡唑鎓四氟硼酸鹽、N,N-二甲基-N-乙基-N-丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-丁基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-壬基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N,N-二丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-丁基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-己基銨雙(三氟甲磺醯基)亞胺鹽、N,N-二甲基-N-丙基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丁基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丁基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-戊基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N,N-二己基銨雙(三氟甲磺醯基)醯亞胺、三甲基庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-丙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、三乙基丙基銨雙(三氟甲磺醯基)醯亞胺、三乙基戊基銨雙(三氟甲磺醯基)醯亞胺、三乙基庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N-甲基-N-乙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N-甲基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N-丁基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N,N-二己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丁基-N-甲基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丁基-N-甲基-N-己基銨雙(三氟甲磺醯基) 醯亞胺、三辛基甲基銨雙(三氟甲磺醯基)醯亞胺、N-甲基-N-乙基-N-丙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、1-丁基吡啶鎓(三氟甲磺醯基)三氟乙醯胺、1-丁基-3-甲基吡啶鎓(三氟甲磺醯基)三氟乙醯胺、1-乙基-3-甲基咪唑鎓(三氟甲磺醯基)三氟乙醯胺、四己基銨雙(三氟甲磺醯基)醯亞胺、二烯丙基二甲基銨四氟硼酸鹽、二烯丙基二甲基銨三氟甲磺酸鹽、二烯丙基二甲基銨雙(三氟甲磺醯基)醯亞胺、二烯丙基二甲基銨雙(五氟乙磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨四氟硼酸鹽、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨三氟甲磺酸鹽、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(五氟乙磺醯基)醯亞胺、縮水甘油基三甲基銨三氟甲磺酸鹽、縮水甘油基三甲基銨雙(三氟甲磺醯基)醯亞胺、縮水甘油基三甲基銨雙(五氟乙磺醯基)醯亞胺、二烯丙基二甲基雙(五氟乙磺醯基)醯亞胺等。 The ionic liquid in the present invention can be appropriately selected and used from the combination of the above cationic component and anionic component, and examples thereof include 1-butylpyridinium tetrafluoroborate and 1-butylpyridinium hexafluorophosphate. -butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonate Indenylamine, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-hexylpyridinium tetrafluoroborate, 1,1-dimethylpyrrolidine Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpyrrolidine Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentylpyrrolidine Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-heptylpyrrolidinium Bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butylpyrrolidinium Bis(trifluoromethanesulfonate Indenylamine, 1-ethyl-1-pentyl Pyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrole Alkyl bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium Bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propylpiperidinium bis(trifluoromethanesulfonate醯imino, 1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dimethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1 -Methyl-1-ethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1 -Methyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1 -Methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1- Ethyl-1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butylpiperidinium bis(trifluoromethanesulfonyl)anthracene Amine, 1-ethyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone , 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(trifluoromethanesulfonyl) quinone imine, 1 -propyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1 - dimethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl- 1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl- 1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1 -heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1 -butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine 1-ethyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1 , 1-dipropylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-pentylpiperidinium Bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dimethylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpiperidinium bis ( Pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butylpiperidinium bis ( Pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis (five Fluoroethinyl) quinone imine, 1-methyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpiperidinium bis (five Fluoroethinyl) quinone imine, 1-ethyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpiperidinium bis (five Fluoroethinyl) quinone imine, 1-ethyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(pentafluoro Ethylsulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butylpiperidinium bis(pentafluoroethanesulfonate醯基) Imine, 1,1-dibutylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindole Tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethyloxazole tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-B 3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3 -methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyandiamide, 1-ethyl 3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-3 -methylimidazolium tris(trifluoromethanesulfonyl)methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate , 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazole Bis(trifluoromethanesulfonyl) quinone imine, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetra Fluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate ,N,N-Dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-butylammonium Bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl --N-ethyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-heptyl ammonium bis(trifluoromethanesulfonyl)醯imino, N,N-dimethyl-N-ethyl-N-decyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N,N-dipropyl Alkyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-butylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N- Dimethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-hexylammonium bis(trifluoromethanesulfonate Indenyl)imide salt, N,N-dimethyl-N-propyl-N-heptyl ammonium double (three Fluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N- Butyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-pentyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone , N,N-Dimethyl-N,N-dihexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N-diethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-amyl ammonium bis (three Fluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N -propyl-N-amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl propyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl amyl ammonium bis (three Fluoromethanesulfonyl) quinone imine, triethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl-N-ethylammonium bis (three Fluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N -butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N- propyl-N,N-dihexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dibutyl-N-methyl-N-amyl ammonium bis(trifluoromethanesulfonyl) Yttrium, N,N-dibutyl-N-methyl-N-hexylammonium bis(trifluoromethanesulfonyl) Yttrium, trioctylmethylammonium bis(trifluoromethanesulfonyl) quinone imine, N-methyl-N-ethyl-N-propyl-N-amyl ammonium bis(trifluoromethanesulfonate Iridium imine, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide , 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium Tetrafluoroborate, diallyldimethylammonium triflate, diallyldimethylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium double (pentafluoroethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl- N-methyl-N-(2-methoxyethyl)ammonium triflate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (Trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) quinone imine, Glycidyl trimethylammonium triflate, glycidyl trimethylammonium bis(trifluoromethanesulfonyl) quinone imine, glycidyl tris Ammonium bis (pentafluoroethane sulfonyl acyl) (PEI), diallyldimethylammonium bis (pentafluoroethanesulfonyl sulfo acyl) (PEI) and the like.
作為離子性液體之合成方法,只要能夠獲得作為目標之離子性液體,則無特別限定,通常,可使用文獻「離子性液體-開發之最前線與未來-」[CMC股份有限公司出版發行]中記載之鹵化物法、氫氧化物法、酸酯法、錯合法、或中和法等。此外,亦可採用市售之離子性液體。 The synthesis method of the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, and in general, the document "Ionic liquid - the forefront and future of development -" (in CMC Co., Ltd.) can be used. The halide method, the hydroxide method, the acid ester method, the wrong method, or the neutralization method described. In addition, commercially available ionic liquids can also be used.
(導電性聚合物) (conductive polymer)
作為上述導電性聚合物,只要能夠獲得本發明之效果則可使用任意適當之聚合物。例如可列舉聚噻吩、聚苯胺、聚吡咯等。 As the above conductive polymer, any appropriate polymer can be used as long as the effect of the present invention can be obtained. For example, polythiophene, polyaniline, polypyrrole, etc. are mentioned.
B-2.抗靜電材料作為添加物包含於基材中之形態(形態(2)) B-2. Form of the antistatic material contained in the substrate as an additive (morphology (2))
作為上述形態(2)中使用之抗靜電材料,只要能夠獲得本發明之效果則可使用任意適當之抗靜電材料。例如可使用B-1項中記載之導電性聚合物、後述B-3項中記載之抗靜電劑等。 As the antistatic material used in the above aspect (2), any appropriate antistatic material can be used as long as the effect of the present invention can be obtained. For example, the conductive polymer described in the item B-1, the antistatic agent described in the item B-3 to be described later, or the like can be used.
上述形態(2)中,抗靜電材料之含有比率相對於基材之總重量較 佳為20重量%以下,更佳為0.05重量%~10重量%。 In the above form (2), the content ratio of the antistatic material is relatively larger than the total weight of the substrate. It is preferably 20% by weight or less, more preferably 0.05% by weight to 10% by weight.
作為使基材中含有抗靜電材料之方法,只要係上述抗靜電材料能夠均勻混合於基材所使用之樹脂中之方法則無特別限定,例如可列舉使用加熱輥、班伯里混合機、加壓捏合機、雙螺桿混練機等使其包含於基材中之方法。 The method of including the antistatic material in the substrate is not particularly limited as long as the antistatic material can be uniformly mixed in the resin used for the substrate, and examples thereof include a heating roller, a Banbury mixer, and a heating roller. A method of including a kneading machine, a twin-screw kneading machine, and the like in a substrate.
B-3.抗靜電材料包含於與黏著劑層或基材不同之層(抗靜電層)中之形態(形態(3)) B-3. The form in which the antistatic material is contained in a layer (antistatic layer) different from the adhesive layer or the substrate (morphology (3))
如上所述,作為形態(3)中之抗靜電層,例如可列舉包含樹脂之抗靜電層(形態(3a))、由金屬或金屬氧化物構成之抗靜電層(形態(3b))等。 As described above, the antistatic layer in the form (3) may, for example, be an antistatic layer (form (3a)) containing a resin, an antistatic layer (form (3b)) made of a metal or a metal oxide, or the like.
上述抗靜電層之表面電阻率較佳為1.0×1013Ω/□以下,更佳為1.0×1012Ω/□以下,進而較佳為1.0×1011Ω/□以下。若為此種範圍,則於貼附於電子零件材料時,能夠防止該電子零件材料之損傷。表面電阻率可基於JIS K 6911來測定(於23℃/50%氣氛下、電極面積:20cm2、施加電壓:500V、施加時間:30秒、使用同心圓電極(探針))。 The surface resistivity of the antistatic layer is preferably 1.0 × 10 13 Ω / □ or less, more preferably 1.0 × 10 12 Ω / □ or less, still more preferably 1.0 × 10 11 Ω / □ or less. If it is such a range, when it attaches to an electronic component material, damage of this electronic component material can be prevented. The surface resistivity can be measured based on JIS K 6911 (in 23 ° C / 50% atmosphere, electrode area: 20 cm 2 , applied voltage: 500 V, application time: 30 seconds, using a concentric electrode (probe)).
<包含樹脂之抗靜電層(形態(3a))> <Antistatic layer containing resin (Form (3a))>
於一實施形態中,抗靜電層包含抗靜電材料及黏著劑樹脂(形態(3a-1))。 In one embodiment, the antistatic layer comprises an antistatic material and an adhesive resin (form (3a-1)).
於該實施形態(形態(3a-1))中,作為上述抗靜電層中所含之抗靜電材料,例如可列舉:四級銨鹽、吡啶鎓鹽、具有第1、第2、第3胺基等陽離子性官能基之陽離子型抗靜電劑;磺酸鹽、或硫酸酯鹽、膦酸鹽、磷酸酯鹽等具有陰離子性官能基之陰離子型抗靜電劑;烷基甜菜鹼及其衍生物、咪唑啉及其衍生物、丙胺酸及其衍生物等兩性離子型抗靜電劑;胺基醇及其衍生物、甘油及其衍生物、聚乙二醇及其衍生物等非離子型抗靜電劑;使具有上述陽離子型、陰離子型、兩性離子型之離子導電性基之單體聚合或共聚而獲得之離子導電性聚合物 等。該等化合物可單獨使用,亦可混合使用2種以上。 In the embodiment (3a-1), examples of the antistatic material contained in the antistatic layer include a quaternary ammonium salt, a pyridinium salt, and a first, second, and third amines. a cationic antistatic agent having a cationic functional group; an anionic antistatic agent having an anionic functional group such as a sulfonate, a sulfate salt, a phosphonate or a phosphate ester; an alkylbetaine and a derivative thereof Zwitterionic antistatic agents such as imidazolines and their derivatives, alanine and its derivatives; nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and its derivatives, polyethylene glycol and its derivatives An ion conductive polymer obtained by polymerizing or copolymerizing a monomer having the above cationic, anionic or zwitterionic ionic conductive group Wait. These compounds may be used singly or in combination of two or more.
作為上述陽離子型之抗靜電劑之具體例,例如可列舉:烷基三甲基銨鹽、醯氧基醯胺丙基三甲基銨甲基硫酸鹽、烷基苄基甲基銨鹽、醯基氯化膽鹼、聚甲基丙烯酸二甲基胺基乙酯等具有四級銨基之(甲基)丙烯酸酯共聚物、聚乙烯基苄基三甲基氯化銨等具有四級銨基之苯乙烯共聚物、聚二烯丙基二甲基氯化銨等具有四級銨基之二烯丙基胺共聚物等。該等化合物可單獨使用,另外亦可混合使用2種以上。 Specific examples of the cationic antistatic agent include an alkyltrimethylammonium salt, a decyloxyguanamine propyltrimethylammonium methylsulfate, an alkylbenzylmethylammonium salt, and an anthracene. a quaternary ammonium group such as a (meth) acrylate copolymer having a quaternary ammonium group such as choline chloride or polydimethylaminoethyl methacrylate, or polyvinylbenzyltrimethylammonium chloride A diallylamine copolymer having a quaternary ammonium group such as a styrene copolymer or a polydiallyldimethylammonium chloride. These compounds may be used singly or in combination of two or more.
作為上述陰離子型之抗靜電劑之具體例,例如可列舉:烷基磺酸鹽、烷基苯磺酸鹽、烷基硫酸酯鹽、烷基乙氧基硫酸酯鹽、烷基磷酸酯鹽、含磺酸基之苯乙烯共聚物等。該等化合物可單獨使用,另外亦可混合使用2種以上。 Specific examples of the anionic antistatic agent include an alkylsulfonate, an alkylbenzenesulfonate, an alkylsulfate, an alkylethoxysulfate, and an alkyl phosphate. a sulfonic acid group-containing styrene copolymer or the like. These compounds may be used singly or in combination of two or more.
作為上述兩性離子型之抗靜電劑之具體例,例如可列舉烷基甜菜鹼、烷基咪唑鎓甜菜鹼、羧基甜菜鹼(carbobetaine)接枝共聚物等。該等化合物可單獨使用,另外亦可混合使用2種以上。 Specific examples of the above-mentioned zwitterionic antistatic agent include an alkylbetaine, an alkylimidazolium betaine, and a carbobetaine graft copolymer. These compounds may be used singly or in combination of two or more.
作為上述非離子型之抗靜電劑之具體例,例如可列舉:脂肪酸烷醇醯胺、二(2-羥基乙基)烷基胺、聚氧乙烯烷基胺、脂肪酸甘油酯、聚氧乙烯二醇脂肪酸酯、山梨糖醇酐脂肪酸酯、聚氧山梨糖醇酐脂肪酸酯、聚氧乙烯烷基苯基醚、聚氧乙烯烷基醚、聚乙二醇、聚氧乙烯二胺、包含聚醚與聚酯與聚醯胺之共聚物、甲氧基聚乙二醇(甲基)丙烯酸酯等。該等化合物可單獨使用,另外亦可混合使用2種以上。 Specific examples of the nonionic antistatic agent include fatty acid alkanolamine, bis(2-hydroxyethyl)alkylamine, polyoxyethylene alkylamine, fatty acid glyceride, and polyoxyethylene II. Alcohol fatty acid esters, sorbitan fatty acid esters, polyoxysorbitol fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, polyethylene glycols, polyoxyethylene diamines, It comprises a copolymer of a polyether and a polyester and a polyamine, a methoxypolyethylene glycol (meth) acrylate, or the like. These compounds may be used singly or in combination of two or more.
作為構成上述抗靜電層之黏著劑樹脂,可使用任意適當之樹脂。例如可列舉:聚酯系樹脂、丙烯酸系樹脂、聚乙烯系樹脂、胺基甲酸酯系樹脂、三聚氰胺系樹脂、環氧系樹脂等。此外,亦可併用交聯劑。作為交聯劑,例如可列舉:羥甲基化或者烷基醇化之三聚氰胺 系化合物、尿素系化合物、乙二醛系化合物、丙烯醯胺系化合物、環氧系化合物、異氰酸酯系化合物等。 As the adhesive resin constituting the antistatic layer, any appropriate resin can be used. For example, a polyester resin, an acrylic resin, a polyethylene resin, a urethane resin, a melamine resin, an epoxy resin, etc. are mentioned. Further, a crosslinking agent may also be used in combination. As the crosslinking agent, for example, melamine or alkyl alcoholated melamine can be exemplified. A compound, a urea compound, a glyoxal compound, a acrylamide compound, an epoxy compound, an isocyanate compound, or the like.
於其他實施形態中,上述抗靜電層由導電性聚合物形成(形態(3a-2))。作為導電性聚合物,只要能獲得本發明之效果則可使用任意適當之聚合物。例如可列舉聚噻吩、聚苯胺、聚吡咯等。 In still another embodiment, the antistatic layer is formed of a conductive polymer (morphology (3a-2)). As the conductive polymer, any appropriate polymer can be used as long as the effects of the present invention can be obtained. For example, polythiophene, polyaniline, polypyrrole, etc. are mentioned.
作為包含樹脂(黏著劑樹脂、導電性聚合物)之抗靜電層之形成方法,例如可列舉如下之方法:將用任意適當之溶劑對上述抗靜電材料與黏著劑樹脂進行稀釋而調製之抗靜電層形成用組合物、或用任意適合之溶劑對上述導電性聚合物進行稀釋而調製之抗靜電層形成用組合物塗佈於基材、黏著劑層或彈性層並進行乾燥之方法。 Examples of the method for forming the antistatic layer containing a resin (adhesive resin or conductive polymer) include an antistatic method prepared by diluting the antistatic material and the adhesive resin with any appropriate solvent. The layer forming composition or the antistatic layer forming composition prepared by diluting the conductive polymer with any suitable solvent is applied to a substrate, an adhesive layer or an elastic layer and dried.
作為上述塗覆液中使用之溶劑,可列舉:水;甲基乙基酮、丙酮、乙酸乙酯、四氫呋喃、二烷、環己酮、正己烷、甲苯、二甲苯、甲醇、乙醇、正丙醇、異丙醇等有機溶劑等。該等溶劑可單獨使用,亦可混合使用2種以上。 Examples of the solvent used in the coating liquid include water; methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, and An organic solvent such as an alkane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-propanol or isopropanol. These solvents may be used singly or in combination of two or more.
作為上述塗覆液之塗佈方法,可採用任意適當之方法。例如可列舉:輥塗法、凹版塗佈法、逆轉輥塗佈法、輥刷法、噴塗法、氣刀塗佈法、浸漬法、簾幕塗佈法等。 As the coating method of the above coating liquid, any appropriate method can be employed. For example, a roll coating method, a gravure coating method, a reverse roll coating method, a roll brush method, a spray coating method, an air knife coating method, a dipping method, a curtain coating method, and the like can be mentioned.
包含樹脂之抗靜電層之厚度較佳為0.01μm~5μm,更佳為0.03μm~1μm。於該抗靜電層之厚度未達0.01μm時,有不能穩定表現出抗靜電功能之虞。此外,於抗靜電層之厚度大於5μm時,有產生由塗佈不均等引起之外觀不良之虞。 The thickness of the antistatic layer containing the resin is preferably from 0.01 μm to 5 μm, more preferably from 0.03 μm to 1 μm. When the thickness of the antistatic layer is less than 0.01 μm, there is a possibility that the antistatic function cannot be stably exhibited. Further, when the thickness of the antistatic layer is more than 5 μm, there is a problem that the appearance is poor due to uneven coating.
<由金屬或金屬氧化物構成之抗靜電層(形態(3b))> <Antistatic layer composed of metal or metal oxide (morph (3b))>
上述形態(3b)中,抗靜電層只要能獲得本發明之效果則可由任意適當之金屬或金屬氧化物形成。作為金屬,例如可列舉:銦、錫、銻、金、銀、銅、鋁、鎳、鉻、鈦、鐵、鈷、碘化銅、及該等之合金或混合物。其中較佳為鋁。此外,作為金屬氧化物,例如可列舉氧化 銦錫、氧化銦鋅、氧化錫、氧化銻、氧化銦等。 In the above form (3b), the antistatic layer may be formed of any appropriate metal or metal oxide as long as the effect of the present invention can be obtained. Examples of the metal include indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, copper iodide, and alloys or mixtures thereof. Among them, aluminum is preferred. Further, as the metal oxide, for example, oxidation is exemplified Indium tin, indium zinc oxide, tin oxide, antimony oxide, indium oxide, and the like.
作為由金屬或金屬氧化物構成之抗靜電層之形成方法,例如可列舉:真空蒸鍍法、濺射法、離子鍍法、化學蒸鍍法、噴霧熱解法、化學鍍法、電鍍法等。此外,亦可將金屬膜或金屬氧化物膜層積層於基材、黏著劑層或彈性層,形成抗靜電層。 Examples of the method for forming the antistatic layer made of a metal or a metal oxide include a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, a spray pyrolysis method, an electroless plating method, and a plating method. Further, a metal film or a metal oxide film may be laminated on the substrate, the adhesive layer or the elastic layer to form an antistatic layer.
由金屬或金屬氧化物構成之抗靜電層之厚度較佳為2nm~1000nm,更佳為5nm~500nm。 The thickness of the antistatic layer composed of a metal or a metal oxide is preferably from 2 nm to 1000 nm, more preferably from 5 nm to 500 nm.
C.黏著劑層 C. Adhesive layer
上述黏著劑層較佳為包含黏著劑與熱膨脹性微球。此外,黏著劑層如B項中所說明般亦可包含抗靜電材料。 The above adhesive layer preferably contains an adhesive and heat-expandable microspheres. Further, the adhesive layer may also contain an antistatic material as described in the item B.
上述黏著劑層之厚度較佳為300μm以下,更佳為5μm~150μm,進而較佳為10μm~100μm。黏著劑層之厚度大於300μm時,有產生如下之不良情況之虞:使用設備受到限制、生產性顯著降低、供於切割等切斷步驟時之加工精度(切斷面之直線性、晶片缺口等)降低等不良情況。 The thickness of the above adhesive layer is preferably 300 μm or less, more preferably 5 μm to 150 μm, still more preferably 10 μm to 100 μm. When the thickness of the adhesive layer is more than 300 μm, there are cases in which the following problems occur: the use of the device is limited, the productivity is remarkably lowered, and the processing precision for the cutting step such as cutting (straight line of the cut surface, wafer notch, etc.) ) Reduce other undesirable conditions.
上述黏著劑層之於25℃下利用奈米壓痕法測定之彈性模數較佳為0.1MPa~100MPa,更佳為0.5MPa~50MPa,進而較佳為0.8MPa~30MPa。利用奈米壓痕法測定之彈性模數係指:遍及負載時、卸載時而連續測定將壓頭壓入至試樣(黏著面)時之對壓頭之負載荷重與壓入深度,由獲得之負載荷重-壓入深度曲線求出之彈性模數。本說明書中,利用奈米壓痕法測定之彈性模數係指將測定條件設為荷重:1mN、負載‧卸載速度:0.1mN/s、保持時間:1s,並如上所述進行測定而成之彈性模數。此外,黏著劑層之利用奈米壓痕法測定之彈性模數係指選擇不存在熱膨脹性微球之部分並利用上述測定方法測定之彈性模數,即黏著劑之彈性模數。 The elastic modulus of the above adhesive layer measured by a nanoindentation method at 25 ° C is preferably from 0.1 MPa to 100 MPa, more preferably from 0.5 MPa to 50 MPa, still more preferably from 0.8 MPa to 30 MPa. The elastic modulus measured by the nanoindentation method means that the load load and the indentation depth of the indenter when the indenter is pressed into the sample (adhesive surface) are continuously measured throughout the load and at the time of unloading, The load modulus - the modulus of elasticity obtained by the indentation depth curve. In the present specification, the elastic modulus measured by the nanoindentation method means that the measurement conditions are as follows: load: 1 mN, load ‧ unloading speed: 0.1 mN/s, holding time: 1 s, and measured as described above. Elastic modulus. Further, the elastic modulus of the adhesive layer measured by the nanoindentation method means the elastic modulus which is selected by the above measurement method, which is the portion where the heat-expandable microspheres are not present, that is, the elastic modulus of the adhesive.
上述黏著劑層包含抗靜電材料時,黏著劑層之表面電阻率較佳 為1.0×1013Ω/□以下,更佳為1.0×1012Ω/□以下,進而較佳為1.0×1011Ω/□以下。若為此種範圍,則於貼附於電子零件材料時,能夠防止該電子零件材料之損傷。 When the adhesive layer contains an antistatic material, the surface resistivity of the adhesive layer is preferably 1.0 × 10 13 Ω / □ or less, more preferably 1.0 × 10 12 Ω / □ or less, further preferably 1.0 × 10 11 Ω. /□ below. If it is such a range, when it attaches to an electronic component material, damage of this electronic component material can be prevented.
(黏著劑) (adhesive)
作為上述黏著劑,較佳使用丙烯酸系黏著劑。作為丙烯酸系黏著劑,例如可列舉:將使用(甲基)丙烯酸烷基酯之1種或2種以上作為單體成分而成之丙烯酸系聚合物(均聚物或共聚物)作為基礎聚合物之丙烯酸系黏著劑等。 As the above adhesive, an acrylic adhesive is preferably used. An acrylic polymer (homopolymer or copolymer) in which one or two or more kinds of (meth)acrylic acid alkyl esters are used as a monomer component is used as a base polymer. Acrylic adhesives, etc.
構成上述黏著劑之基礎聚合物包含源自具有支鏈結構側鏈之(甲基)丙烯酸烷基酯之結構單元A。作為基礎聚合物,藉由使用包含結構單元A之聚合物,能夠獲得黏著力優異、且凹凸追隨性優異之熱剝離型黏著片。若將此種熱剝離型黏著片用於電子零件材料之切斷步驟時之臨時固定用,則能夠防止該材料之晶片飛散。 The base polymer constituting the above-mentioned adhesive contains a structural unit A derived from an alkyl (meth)acrylate having a side chain of a branched structure. By using the polymer containing the structural unit A as the base polymer, it is possible to obtain a heat-peelable pressure-sensitive adhesive sheet which is excellent in adhesion and excellent in unevenness followability. When such a heat-peelable pressure-sensitive adhesive sheet is used for temporary fixing in the cutting step of the electronic component material, it is possible to prevent the wafer of the material from scattering.
上述基礎聚合物中,結構單元A之含有比率較佳為20重量%以上,更佳為25重量%~99重量%,進而較佳為55重量%~99重量%。若為此種範圍,則上述效果(高黏著力、高凹凸追隨性)變顯著。 In the base polymer, the content ratio of the structural unit A is preferably 20% by weight or more, more preferably 25% by weight to 99% by weight, still more preferably 55% by weight to 99% by weight. If it is such a range, the above effect (high adhesion, high unevenness followability) becomes remarkable.
上述結構單元A之支鏈結構側鏈之碳數較佳為5以上,更佳為6~18,進而較佳為8~18。若於此種範圍時,則上述效果(高黏著力、高凹凸追隨性)變顯著。 The carbon number of the side chain of the branched structure of the structural unit A is preferably 5 or more, more preferably 6 to 18, still more preferably 8 to 18. When it is in such a range, the above effects (high adhesion, high unevenness followability) become remarkable.
作為構成上述結構單元A之(甲基)丙烯酸烷基酯,例如可列舉:(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸2-乙基丁酯、(甲基)丙烯酸2-甲基丁酯等。 Examples of the (meth)acrylic acid alkyl ester constituting the above structural unit A include isobutyl (meth)acrylate, second butyl (meth)acrylate, and tert-butyl (meth)acrylate. 2-ethylhexyl methacrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, isodecyl (meth) acrylate, 2-ethyl butyl (meth) acrylate, 2-methylbutyl (meth)acrylate or the like.
於上述結構單元A中,構成支鏈結構側鏈之烷基之碳數較佳為5以上,更佳為6~18,進而較佳為8~18。若為此種範圍,則上述效果 (高黏著力、高凹凸追隨性)變顯著。 In the above structural unit A, the number of carbon atoms of the alkyl group constituting the side chain of the branched structure is preferably 5 or more, more preferably 6 to 18, still more preferably 8 to 18. If it is such a range, the above effect (High adhesion, high bump followability) becomes significant.
作為構成上述結構單元A之(甲基)丙烯酸烷基酯以外之(甲基)丙烯酸烷基酯,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸二十烷基酯等。可較佳使用具有碳數為1~18之直鏈狀烷基之(甲基)丙烯酸烷基酯。 Examples of the alkyl (meth)acrylate other than the alkyl (meth)acrylate constituting the structural unit A include methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl). Propyl acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, bismuth (meth) acrylate Ester, decyl (meth) acrylate, ethyl (meth) acrylate, and the like. An alkyl (meth)acrylate having a linear alkyl group having 1 to 18 carbon atoms can be preferably used.
上述基礎聚合物(丙烯酸系聚合物)就改質凝聚力、耐熱性、交聯性等為目的,根據需要可包含對應於能與上述(甲基)丙烯酸烷基酯共聚之其他單體成分之單元。作為此種單體成分,例如可列舉:丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、衣康酸、馬來酸、富馬酸、巴豆酸等含羧基之單體;馬來酸酐、衣康酸酐等酸酐單體;(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基己酯、(甲基)丙烯酸羥基辛酯、(甲基)丙烯酸羥基癸酯、(甲基)丙烯酸羥基月桂酯、甲基丙烯酸(4-羥甲基環己基)甲酯等含羥基之單體;苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基之單體;(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等(甲基)丙烯酸胺基烷基酯系單體;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體;N-環己基馬來醯亞胺、N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺、N-苯基馬來醯亞胺等馬來醯亞胺系單體;N-甲基衣康醯亞胺、N-乙基衣康醯亞胺、N-丁基衣康醯亞胺、N-辛基衣康醯亞 胺、N-2-乙基己基衣康醯亞胺、N-環己基衣康醯亞胺、N-月桂基衣康醯亞胺等衣康醯亞胺系單體;N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體;乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯烷酮、甲基乙烯基吡咯烷酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌嗪、乙烯基吡嗪、乙烯基吡咯、乙烯基咪唑、乙烯基噁唑、乙烯基嗎啉、N-乙烯基羧醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等乙烯系單體;丙烯腈、甲基丙烯腈等氰基丙烯酸酯單體;(甲基)丙烯酸縮水甘油酯等含環氧基丙烯酸系單體;(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸甲氧基聚丙二醇酯等二醇系丙烯酸酯單體;(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、有機矽(甲基)丙烯酸酯等具有雜環、鹵原子、矽原子等之丙烯酸酯系單體;己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧丙烯酸酯、聚酯丙烯酸酯、胺基甲酸酯丙烯酸酯等多官能單體;異戊二烯、丁二烯、異丁烯等烯烴系單體;乙烯醚等乙烯醚系單體等。該等單體成分可單獨使用或組合使用2種以上。 The base polymer (acrylic polymer) is intended to have a modified cohesive force, heat resistance, crosslinkability, etc., and may contain a unit corresponding to another monomer component copolymerizable with the above (meth)acrylic acid alkyl ester, as needed. . Examples of such a monomer component include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; Anhydride monomer such as an acid anhydride or itaconic anhydride; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, (methyl) a hydroxyl group-containing monomer such as hydroxyoctyl acrylate, hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methacrylate; styrene sulfonic acid, olefin Propyl sulfonic acid, 2-(methyl) propylene decylamine-2-methylpropane sulfonic acid, (meth) acrylamide propylene sulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene oxime a sulfonic acid group-containing monomer such as a naphthalenesulfonic acid; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N- (N-substituted) guanamine monomer such as hydroxymethyl (meth) acrylamide or N-methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, (methyl) N,N-dimethylaminoethyl acrylate, ( (amino)alkyl (meth) acrylate such as t-butylaminoethyl methacrylate; methoxyethyl (meth)acrylate; ethoxyethyl (meth) acrylate; Methyl)alkyl alkoxyalkyl ester monomer; N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide, N-phenyl horse Maleimide monomer such as quinone imine; N-methyl itaconimine, N-ethyl itaconimine, N-butyl itaconide, N-octyl itacon Yuya Amine, N-2-ethylhexyl ketimine, N-cyclohexyl ketimine, N-lauryl ketimine, etc.; N-(methyl) Propylene methoxymethylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N-(methyl) propylene fluorenyl-8-oxy VIII Amber quinone imine monomer such as methylene succinimide; vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine , vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N-vinyl carbamide, styrene, α-methyl styrene, N- Vinyl monomer such as vinyl caprolactam; cyanoacrylate monomer such as acrylonitrile or methacrylonitrile; epoxy group-containing acrylic monomer such as glycidyl (meth)acrylate; (meth)acrylic acid a glycol-based acrylate monomer such as polyethylene glycol ester, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate or methoxypolypropylene glycol (meth)acrylate; An acrylate monomer having a heterocyclic ring, a halogen atom or a ruthenium atom, such as tetrahydrofurfuryl acrylate, fluorine (meth) acrylate or organic fluorene (meth) acrylate; hexanediol di(methyl) Acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, etc. A polyfunctional monomer; an olefin monomer such as isoprene, butadiene or isobutylene; a vinyl ether monomer such as vinyl ether; These monomer components can be used individually or in combination of 2 or more types.
關於上述與其他單體成分對應之單元之含有比率,相對於基礎聚合物100重量份,較佳為1重量份~20重量份,更佳為2重量份~15重量份,進而較佳為2重量份~10重量份。若為此種範圍,則能夠兼顧對被接著體之凹凸追隨性、黏著力、加熱剝離性之特性。 The content ratio of the unit corresponding to the other monomer component is preferably from 1 part by weight to 20 parts by weight, more preferably from 2 parts by weight to 15 parts by weight, even more preferably 2 parts by weight based on 100 parts by weight of the base polymer. Parts by weight to 10 parts by weight. When it is such a range, the characteristics of the unevenness followability, the adhesive force, and the heat peeling property of the to-be-attached body can be acquired.
上述黏著劑根據需要可包含任意適當之添加劑。作為該添加劑,例如可列舉:交聯劑、增黏劑、增塑劑(例如偏苯三酸酯系增塑 劑、均苯四酸酯系增塑劑)、顏料、染料、填充劑、抗老化劑、導電材料、紫外線吸收劑、光穩定劑、剝離調整劑、軟化劑、界面活性劑、阻燃劑、抗氧化劑等。 The above adhesive may contain any appropriate additives as needed. As the additive, for example, a crosslinking agent, a tackifier, and a plasticizer (for example, a trimellitate plasticization) may be mentioned. Agent, pyromellitate plasticizer), pigment, dye, filler, anti-aging agent, conductive material, ultraviolet absorber, light stabilizer, peeling adjuster, softener, surfactant, flame retardant, Antioxidants, etc.
作為上述增黏劑,使用任意適當之增黏劑。作為增黏劑,例如使用增黏樹脂。作為增黏樹脂之具體例,可列舉:松香系增黏樹脂(例如未改性松香、改性松香、松香酚系樹脂、松香酯系樹脂等)、萜烯系增黏樹脂(例如萜烯系樹脂、萜烯酚系樹脂、苯乙烯改性萜烯系樹脂、芳香族改性萜烯系樹脂、氫化萜烯系樹脂)、烴系增黏樹脂(例如脂肪族系烴樹脂、脂肪族系環狀烴樹脂、芳香族系烴樹脂(例如苯乙烯系樹脂、二甲苯系樹脂等)、脂肪族‧芳香族系石油樹脂、脂肪族‧脂環族系石油樹脂、氫化烴樹脂、香豆酮系樹脂、香豆酮茚系樹脂等)、酚系增黏樹脂(例如烷基酚系樹脂、二甲苯甲醛系樹脂、甲酚樹脂、酚醛清漆等)、酮系增黏樹脂、聚醯胺系增黏樹脂、環氧系增黏樹脂、彈性體系增黏樹脂等。其中較佳為松香系增黏樹脂、萜烯系增黏樹脂或酚系增黏樹脂。特別較佳為松香酚系增黏樹脂及萜烯酚系增黏樹脂。該等增黏劑與基礎聚合物表現出較良好之相容性,因此,利用使用該增黏劑獲得之黏著劑,能夠獲得穩定之凹凸追隨性。其結果,能夠獲得晶片飛散之抑制優異之熱剝離型黏著片。增黏劑可單獨使用或組合使用2種以上。 As the tackifier, any appropriate tackifier is used. As the tackifier, for example, a tackifying resin is used. Specific examples of the tackifying resin include rosin-based tackifying resins (for example, unmodified rosin, modified rosin, rosin phenol-based resin, rosin ester-based resin, etc.), and terpene-based tackifying resins (for example, terpene-based). Resin, terpene phenol resin, styrene modified terpene resin, aromatic modified terpene resin, hydrogenated terpene resin, hydrocarbon based tackifying resin (for example, aliphatic hydrocarbon resin, aliphatic ring) Hydrocarbon resin, aromatic hydrocarbon resin (for example, styrene resin, xylene resin, etc.), aliphatic ‧ aromatic petroleum resin, aliphatic ‧ alicyclic petroleum resin, hydrogenated hydrocarbon resin, coumarone Resin, coumarone oxime resin, etc.), phenolic tackifying resin (for example, alkylphenol resin, xylene formaldehyde resin, cresol resin, novolac, etc.), ketone tackifying resin, polyamine Viscose resin, epoxy tackifying resin, elastic system tackifying resin, etc. Among them, a rosin-based tackifying resin, a terpene-based tackifying resin or a phenol-based tackifying resin is preferred. Particularly preferred are rosin phenol-based tackifying resins and terpene phenol-based tackifying resins. These tackifiers exhibit good compatibility with the base polymer, and therefore, stable tack followability can be obtained by using the tackifier obtained by using the tackifier. As a result, a heat-peelable pressure-sensitive adhesive sheet excellent in suppression of wafer scattering can be obtained. The tackifier may be used alone or in combination of two or more.
上述增黏劑可使用市售品。作為市售品之增黏劑之具體例,可列舉:YASUHARA CHEMICAL公司製造之商品名「YS polystar S145」、「Mighty Ace K140」、荒川化學公司製造之商品名「Tamanol 901」等萜烯酚樹脂;住友電木公司製造之商品名「SUMILITERESIN PR-12603」、荒川化學公司製造之商品名「Tamanol 361」等松香酚樹脂;荒川化學公司製造之商品名「Tamanol 1010R」、「Tamanol 200N」等烷基酚樹脂;荒川化學公司製造之商品名「Alcon P-140」 等脂環族系飽和烴樹脂等。 A commercially available product can be used as the above tackifier. Specific examples of the tackifier of the commercially available product include terpene phenol resin such as "YS polystar S145" manufactured by YASUHARA CHEMICAL Co., Ltd., "Mighty Ace K140", and "Tamanol 901" manufactured by Arakawa Chemical Co., Ltd. The rosin phenol resin, such as the product name "Tamanol 316" manufactured by Sumitomo Chemical Co., Ltd., and the product name "Tamanol 1010R" and "Tamanol 200N" manufactured by Arakawa Chemical Co., Ltd. Phenolic resin; the brand name "Alcon P-140" manufactured by Arakawa Chemical Co., Ltd. An alicyclic saturated hydrocarbon resin or the like.
關於上述增黏劑之含量,相對於基礎聚合物100重量份,較佳為1重量份~80重量份,更佳為5重量份~70重量份,進而較佳為10重量份~50重量份,特別較佳為10重量份~40重量份。藉由添加增黏劑,能夠提高黏著力。另一方面,增黏劑之添加係阻礙黏著片之凹凸追隨性之主要原因,但於本發明中,藉由如上所述由具有源自特定之單體之結構單元A之基礎聚合物形成黏著劑層,能夠兼顧凹凸追隨性與高黏著力。 The content of the tackifier is preferably from 1 part by weight to 80 parts by weight, more preferably from 5 parts by weight to 70 parts by weight, even more preferably from 10 parts by weight to 50 parts by weight, per 100 parts by weight of the base polymer. It is particularly preferably from 10 parts by weight to 40 parts by weight. Adhesion can be improved by adding a tackifier. On the other hand, the addition of the tackifier is the main reason for hindering the unevenness of the adhesive sheet, but in the present invention, the adhesion is formed by the base polymer having the structural unit A derived from the specific monomer as described above. The agent layer can balance both the bump followability and the high adhesion.
作為上述交聯劑,例如可列舉:異氰酸酯系交聯劑、環氧系交聯劑、三聚氰胺系交聯劑、過氧化物系交聯劑、以及尿素系交聯劑、金屬醇鹽系交聯劑、金屬螯合劑系交聯劑、金屬鹽系交聯劑、碳二亞胺系交聯劑、噁唑啉系交聯劑、氮雜環丙烷系交聯劑、胺系交聯劑等。其中較佳為異氰酸酯系交聯劑或環氧系交聯劑。 Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, and a metal alkoxide crosslinking. The agent, the metal chelating agent-based crosslinking agent, the metal salt-based crosslinking agent, the carbodiimide-based crosslinking agent, the oxazoline-based crosslinking agent, the aziridine-based crosslinking agent, and the amine-based crosslinking agent. Among them, an isocyanate crosslinking agent or an epoxy crosslinking agent is preferred.
作為上述異氰酸酯系交聯劑之具體例,可列舉:伸丁基二異氰酸酯、六亞甲基二異氰酸酯等低級脂肪族聚異氰酸酯類;伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛爾酮二異氰酸酯等脂環族異氰酸酯類;2,4-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、二甲苯二異氰酸酯等芳香族異氰酸酯類;三羥甲基丙烷/甲苯二異氰酸酯3聚體加成物(日本聚胺酯工業公司製造,商品名「CORONATE L」)、三羥甲基丙烷/六亞甲基二異氰酸酯3聚物加成物(日本聚胺酯工業公司製造,商品名「CORONATE HL」)、六亞甲基二異氰酸酯之異氰脲酸酯體(日本聚胺酯工業公司製造,商品名「CORONATE HX」)等異氰酸酯加成物;等。異氰酸酯系交聯劑之含量可根據目標黏著力設定成任意適當之量,相對於基礎聚合物100重量份,代表性為0.1重量份~20重量份,更佳為0.5重量份~10重量份。 Specific examples of the above isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophor An alicyclic isocyanate such as keto diisocyanate; an aromatic isocyanate such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate or xylene diisocyanate; trimethylolpropane/toluene diisocyanate 3 Polymer adduct (manufactured by Japan Polyurethane Industry Co., Ltd., trade name "CORONATE L"), trimethylolpropane / hexamethylene diisocyanate 3 polymer adduct (manufactured by Japan Polyurethane Industry Co., Ltd., trade name "CORONATE HL" ") isocyanate adducts such as isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "CORONATE HX"); The content of the isocyanate crosslinking agent can be set to any appropriate amount in accordance with the target adhesive force, and is typically from 0.1 part by weight to 20 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the base polymer.
作為上述環氧系交聯劑,例如可列舉:N,N,N',N'-四縮水甘油基- 間苯二甲胺、二縮水甘油基苯胺、1,3-雙(N,N-縮水甘油基胺基甲基)環己烷(三菱瓦斯化學公司製造,商品名「TETRAD C」)、1,6-己二醇二縮水甘油醚(共榮社化學公司製造,商品名「Epolight 1600」)、新戊二醇二縮水甘油醚(共榮社化學公司製造,商品名「Epolight 1500NP」)、乙二醇二縮水甘油醚(共榮社化學公司製造,商品名「Epolight 40E」)、丙二醇二縮水甘油醚(共榮社化學公司製造,商品名「Epolight 70P」)、聚乙二醇二縮水甘油醚(日本油脂公司製造,商品名「EPIOL E-400」)、聚丙二醇二縮水甘油醚(日本油脂公司製造,商品名「EPIOL P-200」)、山梨糖醇聚縮水甘油醚(Nagase ChemteX公司製造,商品名「Denacol EX-611」)、甘油聚縮水甘油醚(Nagase ChemteX公司製造,商品名「Denacol EX-314」)、季戊四醇聚縮水甘油醚、聚甘油聚縮水甘油醚(Nagase ChemteX公司製造,商品名「Denacol EX-512」)、山梨糖醇酐聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、己二酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、三縮水甘油基-三(2-羥乙基)異氰脲酸酯、間苯二酚二縮水甘油醚、雙酚-S-二縮水甘油醚、分子內具有2個以上環氧基之環氧系樹脂等。環氧系交聯劑之含量可根據所需黏著力設定為任意適當之量,代表性為,相對於基礎聚合物100重量份,為0.01重量份~10重量份,更佳為0.03重量份~5重量份。 Examples of the epoxy-based crosslinking agent include N, N, N', N'-tetraglycidyl group- M-xylylenediamine, diglycidylaniline, 1,3-bis(N,N-glycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD C"), 1, 6-hexanediol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 1600"), neopentyl glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 1500NP"), B Glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 40E"), propylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 70P"), polyethylene glycol diglycidyl Ether (manufactured by Nippon Oil & Fats Co., Ltd., trade name "EPIOL E-400"), polypropylene glycol diglycidyl ether (manufactured by Nippon Oil & Fats Co., Ltd., trade name "EPIOL P-200"), sorbitol polyglycidyl ether (Nagase ChemteX) Manufactured under the trade name "Denacol EX-611"), glycerol polyglycidyl ether (manufactured by Nagase ChemteX, trade name "Denacol EX-314"), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (manufactured by Nagase ChemteX) , the product name "Denacol EX-512") Polysorbate polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl-tris(2-hydroxyethyl) Cyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, epoxy resin having two or more epoxy groups in the molecule, and the like. The content of the epoxy-based crosslinking agent can be set to any appropriate amount depending on the desired adhesive force, and is typically 0.01 parts by weight to 10 parts by weight, more preferably 0.03 parts by weight, per 100 parts by weight of the base polymer. 5 parts by weight.
(熱膨脹性微球) (heat-expandable microspheres)
作為上述熱膨脹性微球,只要為藉由加熱能膨脹或發泡之微球,則可使用任意適當之熱膨脹性微球。作為上述熱膨脹性微球,例如可使用將藉由加熱容易膨脹之物質內包於具有彈性之殼內而成之微球。此種熱膨脹性微球可利用任意適當之方法例如凝聚法、界面聚合法等來製造。 As the heat-expandable microspheres, any suitable heat-expandable microspheres can be used as long as it is a microsphere which is expanded or foamed by heating. As the heat-expandable microspheres, for example, a microsphere in which a substance which is easily expanded by heating is enclosed in a shell having elasticity can be used. Such heat-expandable microspheres can be produced by any appropriate method such as a coacervation method, an interfacial polymerization method, or the like.
作為藉由加熱容易膨脹之物質,例如可列舉:丙烷、丙烯、丁 烯、正丁烷、異丁烷、異戊烷、新戊烷、正戊烷、正己烷、異己烷、庚烷、辛烷、石油醚、甲烷之鹵化物、四烷基矽烷等低沸點液體;藉由熱解而氣化之偶氮二甲醯胺;等。 Examples of the substance which is easily swelled by heating include propane, propylene, and butyl. Low-boiling liquids such as olefin, n-butane, isobutane, isopentane, neopentane, n-pentane, n-hexane, isohexane, heptane, octane, petroleum ether, methane halide, tetraalkylnonane ; azo dimethyl hydrazine gasified by pyrolysis; and the like.
作為構成上述殼之物質,例如可列舉由下述物質構成之聚合物,該物質為:丙烯腈、甲基丙烯腈、α-氯丙烯腈、α-乙氧基丙烯腈、富馬腈等腈單體;丙烯酸、甲基丙烯酸、衣康酸、馬來酸、富馬酸、檸康酸等羧酸單體;偏氯乙烯;乙酸乙烯酯;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、丙烯酸β-羧基乙酯等(甲基)丙烯酸酯;苯乙烯、α-甲基苯乙烯、氯苯乙烯等苯乙烯單體;丙烯醯胺、取代丙烯醯胺、甲基丙烯醯胺、取代甲基丙烯醯胺等醯胺單體;等。由該等單體構成之聚合物可為均聚物,亦可為共聚物。作為該共聚物,例如可列舉:偏氯乙烯-甲基丙烯酸甲酯-丙烯腈共聚物、甲基丙烯酸甲酯-丙烯腈-甲基丙烯腈共聚物、甲基丙烯酸甲酯-丙烯腈共聚物、丙烯腈-甲基丙烯腈-衣康酸共聚物等。 Examples of the material constituting the shell include a polymer composed of acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxy acrylonitrile, and fumaronitrile. Monomer; carboxylic acid monomer such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth)acrylate, (methyl) Ethyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) acrylate such as benzyl (meth) acrylate or β-carboxyethyl acrylate; styrene monomer such as styrene, α-methyl styrene or chlorostyrene; acrylamide, substituted acrylamide; a decylamine monomer such as methacrylamide or a substituted methacrylamide; The polymer composed of the monomers may be a homopolymer or a copolymer. Examples of the copolymer include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, and methyl methacrylate-acrylonitrile copolymer. , acrylonitrile-methacrylonitrile-itaconic acid copolymer, and the like.
作為上述熱膨脹性微球,可使用無機系發泡劑或有機系發泡劑。作為無機系發泡劑,例如可列舉:碳酸銨、碳酸氫銨、碳酸氫鈉、亞硝酸銨、硼氫化鈉、各種疊氮化物類等。此外,作為有機系發泡劑,例如可列舉:三氯一氟甲烷、二氯一氟甲烷等氯氟化烷烴系化合物;偶氮二異丁腈、偶氮二甲醯胺、偶氮二甲酸鋇等偶氮系化合物;對甲苯磺醯肼、二苯基碸-3,3'-二磺醯肼、4,4'-氧代雙(苯磺醯肼)、烯丙基雙(磺醯肼)等肼系化合物;對甲苯磺醯基胺基脲、4,4'-氧代雙(苯磺醯基胺基脲)等胺基脲系化合物;5-嗎啉基-1,2,3,4-硫代三唑等三唑系化合物;N,N'-二亞硝基五亞甲基四胺、N,N'-二甲基-N,N'-二亞硝基對苯二甲醯胺;等N-亞硝基系化合物等。 As the heat-expandable microspheres, an inorganic foaming agent or an organic foaming agent can be used. Examples of the inorganic foaming agent include ammonium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium borohydride, various azide compounds, and the like. Further, examples of the organic foaming agent include chlorofluorinated alkane compounds such as trichlorofluoromethane and dichlorofluoromethane; azobisisobutyronitrile, azodimethylamine, and azodicarboxylic acid; Anthraquinone compounds such as hydrazine; p-toluenesulfonate, diphenylphosphonium-3,3'-disulfonium, 4,4'-oxobis(phenylsulfonate), allyl bis (sulfonate)肼) an isocyanic compound; an aminourea-based compound such as p-toluenesulfonylamino urea, 4,4'-oxobis(phenylsulfonylamino urea); 5-morpholinyl-1,2, a triazole compound such as 3,4-thiotriazole; N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitroso-p-benzene Dimethylamine; an N-nitroso compound or the like.
上述熱膨脹性微球亦可使用市售品。作為市售品之熱膨脹性微球之具體例,可列舉:松本油脂製藥公司製造之商品名「Matsumoto Microsphere」(型號:F-30、F-30D、F-36D、F-36LV、F-50、F-50D、F-65、F-65D、FN-100SS、FN-100SSD、FN-180SS、FN-180SSD、F-190D、F-260D、F-2800D)、Japan Fillite公司製造之商品名「Expancel」(型號:053-40、031-40、920-40、909-80、930-120)、吳羽化學工業公司製造「DAIFOAM」(型號:H750、H850、H1100、S2320D、S2640D、M330、M430、M520)、積水化學工業公司製造「ADVANCELL」(型號:EML101、EMH204、EHM301、EHM302、EHM303、EM304、EHM401、EM403、EM501)等。 A commercially available product can also be used for the above-mentioned heat-expandable microspheres. Specific examples of the heat-expandable microspheres that are commercially available are the product name "Matsumoto Microsphere" manufactured by Matsumoto Oil & Fats Pharmaceutical Co., Ltd. (Models: F-30, F-30D, F-36D, F-36LV, F-50) , F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D), the product name manufactured by Japan Fillite Co., Ltd. Expancel" (Model: 053-40, 031-40, 920-40, 909-80, 930-120), manufactured by Wu Yu Chemical Industry Co., Ltd. "DAIFOAM" (Model: H750, H850, H1100, S2320D, S2640D, M330, M430, M520), Sekisui Chemical Industry Co., Ltd. manufactures "ADVANCELL" (models: EML101, EMH204, EHM301, EHM302, EHM303, EM304, EHM401, EM403, EM501).
上述熱膨脹性微球之加熱前之粒徑較佳為0.5μm~80μm,更佳為5μm~45μm,進而較佳為10μm~20μm,特別較佳為10μm~15μm。因此,以平均粒徑來說明上述熱膨脹性微球之加熱前之顆粒尺寸時,較佳為6μm~45μm,更佳為10μm~35μm。上述粒徑與平均粒徑係利用雷射散射法中之粒度分佈測定法求出之值。 The particle diameter of the heat-expandable microspheres before heating is preferably from 0.5 μm to 80 μm, more preferably from 5 μm to 45 μm, still more preferably from 10 μm to 20 μm, still more preferably from 10 μm to 15 μm. Therefore, when the particle size of the heat-expandable microspheres before heating is described as an average particle diameter, it is preferably 6 μm to 45 μm, and more preferably 10 μm to 35 μm. The above-mentioned particle diameter and average particle diameter are values obtained by a particle size distribution measurement method in a laser scattering method.
上述熱膨脹性微球較佳為具有體積膨脹率直至達到較佳為5倍以上、更佳為7倍以上、進而較佳為10倍以上不會破裂之適宜之強度。使用此種熱膨脹性微球時,能夠藉由加熱處理而有效地降低黏著力。 The heat-expandable microspheres preferably have a volume expansion ratio of preferably 5 times or more, more preferably 7 times or more, still more preferably 10 times or more, and are not suitable for breaking. When such a heat-expandable microsphere is used, the adhesion can be effectively reduced by heat treatment.
上述黏著劑層之熱膨脹性微球之含有比率可根據所期望之黏著力之降低性等來適當設定。關於熱膨脹性微球之含有比率,相對於形成黏著劑層之基礎聚合物100重量份,例如為1重量份~150重量份,較佳為10重量份~130重量份,進而較佳為25重量份~100重量份。 The content ratio of the heat-expandable microspheres of the pressure-sensitive adhesive layer can be appropriately set depending on the desired reduction in adhesion or the like. The content ratio of the heat-expandable microspheres is, for example, 1 part by weight to 150 parts by weight, preferably 10 parts by weight to 130 parts by weight, and more preferably 25 parts by weight, based on 100 parts by weight of the base polymer forming the pressure-sensitive adhesive layer. Parts ~ 100 parts by weight.
D.基材D. Substrate
作為上述基材,例如可列舉:樹脂片、不織布、紙、金屬箔、織布、橡膠片、發泡片、該等之積層體(尤其係包含樹脂片之積層體)等。作為構成樹脂片之樹脂,例如可列舉:聚對苯二甲酸乙二酯 (PET)、聚萘二甲酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)、聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物(EVA)、聚醯胺(尼龍)、全芳香族聚醯胺(芳綸)、聚醯亞胺(PI)、聚氯乙烯(PVC)、聚苯硫醚(PPS)、氟系樹脂、聚醚醚酮(PEEK)等。作為不織布,可列舉:包含馬尼拉麻之不織布等由具有耐熱性之天然纖維形成之不織布;聚丙烯樹脂不織布、聚乙烯樹脂不織布、酯系樹脂不織布等合成樹脂不織布等。 Examples of the substrate include a resin sheet, a nonwoven fabric, paper, a metal foil, a woven fabric, a rubber sheet, a foam sheet, and a laminate (especially a laminate including a resin sheet). Examples of the resin constituting the resin sheet include polyethylene terephthalate. (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene vinyl acetate Copolymer (EVA), polyamide (nylon), wholly aromatic polyamine (aramid), polyimine (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine resin , polyetheretherketone (PEEK), and the like. Examples of the nonwoven fabric include non-woven fabrics made of natural fibers having heat resistance such as non-woven fabrics of Manila hemp, synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabrics, polyethylene resin nonwoven fabrics, and ester resin nonwoven fabrics.
於一實施形態中,如B項中所說明般,上述基材可包含抗靜電材料。作為包含抗靜電材料之基材,例如可使用混練抗靜電材料之樹脂片。該樹脂片可由包含樹脂與抗靜電材料之基材形成用組合物形成。於其他實施形態中,作為基材,使用金屬箔等,基材自身亦可為抗靜電材料。 In one embodiment, the substrate may comprise an antistatic material as described in Section B. As the substrate containing the antistatic material, for example, a resin sheet in which an antistatic material is kneaded can be used. The resin sheet may be formed of a composition for forming a substrate comprising a resin and an antistatic material. In another embodiment, a metal foil or the like is used as the substrate, and the substrate itself may be an antistatic material.
上述基材之厚度可根據所需強度或柔軟性、以及使用目的等設定為任意適當之厚度。基材之厚度較佳為1000μm以下,更佳為1μm~1000μm,進而較佳為1μm~500μm,特別較佳為3μm~300μm,最佳為5μm~250μm。 The thickness of the base material can be set to any appropriate thickness depending on the required strength, flexibility, and purpose of use. The thickness of the substrate is preferably 1000 μm or less, more preferably 1 μm to 1000 μm, still more preferably 1 μm to 500 μm, particularly preferably 3 μm to 300 μm, and most preferably 5 μm to 250 μm.
上述基材可實施表面處理。作為表面處理,例如可列舉:電暈處理、鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、離子化輻射處理、利用底塗劑之塗佈處理等。若進行此種表面處理,則能夠提高黏著劑層與基材之密著性。 The above substrate can be subjected to surface treatment. Examples of the surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, coating treatment using a primer, and the like. When such a surface treatment is performed, the adhesion between the adhesive layer and the substrate can be improved.
作為上述有機塗佈材料,例如可列舉塑膠硬塗材料II(CMC出版,(2004))中記載之材料。較佳為使用胺基甲酸酯系聚合物,更佳為使用聚丙烯酸胺基甲酸酯、聚酯胺基甲酸酯或該等之前驅物。其原因在於,對基材之塗覆‧塗佈簡便、並且工業上可選擇多種物質而能夠廉價地獲取。該胺基甲酸酯系聚合物例如為包含異氰酸酯單體與含醇性羥基之單體(例如含羥基之丙烯酸化合物或含羥基酯之化合物)之反 應混合物的聚合物。有機塗佈材料作為任意之添加劑可包含聚胺等擴鏈劑、抗老化劑、氧化穩定劑等。對有機塗佈層之厚度並無特別限定,例如為0.1μm~10μm左右較為適合,較佳為0.1μm~5μm左右,更佳為0.5μm~5μm左右。 Examples of the organic coating material include materials described in Plastic Hard Coating Material II (CMC Publishing, (2004)). It is preferred to use a urethane-based polymer, more preferably a polyacrylic acid urethane, a polyester urethane or the precursors. The reason for this is that the coating of the substrate is simple and easy to apply, and a variety of substances can be selected industrially and can be obtained at low cost. The urethane-based polymer is, for example, a counter-containing monomer comprising an isocyanate monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl group-containing acrylic compound or a hydroxyl group-containing compound). The polymer of the mixture should be. The organic coating material may contain, as an optional additive, a chain extender such as a polyamine, an anti-aging agent, an oxidation stabilizer, or the like. The thickness of the organic coating layer is not particularly limited, and is, for example, about 0.1 μm to 10 μm, preferably about 0.1 μm to 5 μm, more preferably about 0.5 μm to 5 μm.
E.彈性層E. Elastic layer
如上所述,本發明之熱剝離型黏著片可進而具備彈性層。 As described above, the heat-peelable pressure-sensitive adhesive sheet of the present invention may further comprise an elastic layer.
上述彈性層包含基礎聚合物,作為該基礎聚合物,可使用黏著性之聚合物。作為構成彈性層之基礎聚合物,例如可列舉:丙烯酸系聚合物:天然橡膠、合成橡膠(例如腈系、二烯系、丙烯酸系)等橡膠系聚合物;聚烯烴系、聚酯系等熱塑性彈性體;乙烯基烷基醚系聚合物;有機矽系聚合物;聚酯系聚合物;聚醯胺系聚合物;胺基甲酸酯系聚合物;苯乙烯-二烯嵌段共聚物;乙烯-乙酸乙烯酯共聚物;聚胺基甲酸酯系聚合物;聚丁二烯;軟質聚氯乙烯;輻射硬化型聚合物等。構成上述彈性層之基礎聚合物可與形成上述黏著劑層之基礎聚合物相同,亦可不同。上述彈性層亦可為由上述基礎聚合物形成之發泡膜。該發泡膜可利用任意適當之方法獲得。再者,彈性層與黏著劑層可藉由有無熱膨脹性微球(彈性層不包含熱膨脹性微球)來區別。 The above elastic layer contains a base polymer, and as the base polymer, an adhesive polymer can be used. Examples of the base polymer constituting the elastic layer include a rubber-based polymer such as an acrylic polymer: a natural rubber or a synthetic rubber (for example, a nitrile-based, a diene-based or an acrylic-based), and a thermoplastic such as a polyolefin or a polyester. Elastomer; vinyl alkyl ether polymer; organic lanthanide polymer; polyester polymer; polyamine polymer; urethane polymer; styrene-diene block copolymer; Ethylene-vinyl acetate copolymer; polyurethane-based polymer; polybutadiene; soft polyvinyl chloride; radiation-curable polymer. The base polymer constituting the above elastic layer may be the same as or different from the base polymer forming the above adhesive layer. The elastic layer may also be a foamed film formed of the above base polymer. The foamed film can be obtained by any suitable method. Further, the elastic layer and the adhesive layer can be distinguished by the presence or absence of heat-expandable microspheres (the elastic layer does not contain heat-expandable microspheres).
作為構成彈性層之基礎聚合物之上述丙烯酸系聚合物例如為使用(甲基)丙烯酸烷基酯之1種或2種以上作為單體成分之丙烯酸系聚合物(均聚物或共聚物)。作為該(甲基)丙烯酸烷基酯之具體例,可列舉具有碳數20以下之直鏈狀或支鏈狀烷基之(甲基)丙烯酸烷基酯。此外,上述丙烯酸系聚合物亦可包含與能與(甲基)丙烯酸烷基酯共聚之其他單體成分對應之單元。作為此種單體成分,例如可列舉:丙烯酸、甲基丙烯酸、衣康酸、丙烯酸羥基乙酯、甲基丙烯酸羥基乙酯、丙烯酸羥基丙酯、甲基丙烯酸羥基丙酯、N-羥甲基丙烯醯胺、丙烯腈、甲基丙烯腈、丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、乙酸 乙烯酯、苯乙烯、異戊二烯、丁二烯、異丁烯、乙烯醚等。 The acrylic polymer which is a base polymer constituting the elastic layer is, for example, an acrylic polymer (homopolymer or copolymer) which uses one or two or more kinds of alkyl (meth)acrylate as a monomer component. Specific examples of the (meth)acrylic acid alkyl ester include an alkyl (meth)acrylate having a linear or branched alkyl group having 20 or less carbon atoms. Further, the acrylic polymer may further comprise a unit corresponding to another monomer component copolymerizable with the alkyl (meth)acrylate. Examples of such a monomer component include acrylic acid, methacrylic acid, itaconic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and N-methylol group. Acrylamide, acrylonitrile, methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, acetic acid Vinyl ester, styrene, isoprene, butadiene, isobutylene, vinyl ether, and the like.
上述彈性層根據需要可包含任意適當之添加劑。作為該添加劑,例如可列舉交聯劑、硫化劑、增黏劑、增塑劑、柔軟劑、填充劑、抗老化劑等。作為基礎聚合物,使用聚氯乙烯等硬質樹脂時,較佳為併用增塑劑及/或柔軟劑來形成具有目標彈性之彈性層。 The above elastic layer may contain any appropriate additives as needed. Examples of the additive include a crosslinking agent, a vulcanizing agent, a tackifier, a plasticizer, a softening agent, a filler, and an anti-aging agent. When a hard resin such as polyvinyl chloride is used as the base polymer, it is preferred to use a plasticizer and/or a softener in combination to form an elastic layer having a target elasticity.
上述彈性層之厚度較佳為3μm~200μm,更佳為5μm~100μm。若為此種範圍,則能夠充分發揮彈性層之上述功能。 The thickness of the above elastic layer is preferably from 3 μm to 200 μm, more preferably from 5 μm to 100 μm. If it is such a range, the above-mentioned function of an elastic layer can fully exhibit.
上述彈性層之於25℃下之拉伸彈性模數較佳為未達100Mpa,更佳為0.1MPa~50MPa,進而較佳為0.1MPa~10MPa。若為此種範圍,則能夠充分發揮彈性層之上述功能。 The elastic modulus of the elastic layer at 25 ° C is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, still more preferably 0.1 MPa to 10 MPa. If it is such a range, the above-mentioned function of an elastic layer can fully exhibit.
F.熱剝離型黏著片之製造方法F. Method for manufacturing thermal peeling adhesive sheet
本發明之熱剝離型黏著片可利用任意適當之方法來製造。本發明之熱剝離型黏著片例如可列舉如下之方法:於基材上直接塗覆黏著劑層形成用組合物之方法、或將於任意適當之基體上塗覆黏著劑層形成用組合物而形成之塗覆層轉印於基材之方法等。 The heat-peelable adhesive sheet of the present invention can be produced by any appropriate method. The heat-peelable pressure-sensitive adhesive sheet of the present invention may, for example, be a method in which a composition for forming an adhesive layer is directly applied onto a substrate, or a composition for forming an adhesive layer is formed on any appropriate substrate. The method of transferring the coating layer to the substrate or the like.
上述黏著劑層形成用組合物包含上述黏著劑及上述熱膨脹性微球,根據需要進而包含抗靜電材料。此外,黏著劑層形成用組合物亦可包含任意適當之溶劑。 The pressure-sensitive adhesive layer-forming composition contains the above-mentioned pressure-sensitive adhesive and the above-mentioned heat-expandable microspheres, and further contains an antistatic material as needed. Further, the composition for forming an adhesive layer may contain any appropriate solvent.
上述熱剝離型黏著片具備包含樹脂之抗靜電層時,該抗靜電層如B-3項中所說明般,可將用任意適當之溶劑對上述抗靜電材料與黏著劑樹脂進行稀釋而成之抗靜電層形成用組合物、或用任意適當之溶劑對上述導電性聚合物進行稀釋而成之抗靜電層形成用組合物塗佈於基材、黏著劑層或彈性層而形成。 When the heat-peelable pressure-sensitive adhesive sheet is provided with an antistatic layer containing a resin, the antistatic layer may be diluted with the appropriate antistatic material and the adhesive resin as described in Item B-3. The antistatic layer-forming composition or the antistatic layer-forming composition obtained by diluting the conductive polymer with any appropriate solvent is applied to a substrate, an adhesive layer or an elastic layer.
上述抗靜電層由金屬層或金屬氧化物層形成時,金屬層或金屬氧化物層如B-3項中所說明般,例如可利用真空蒸鍍法、濺射法、離子鍍法、化學蒸鍍法、噴霧熱解法、化學鍍法、電鍍法等製膜方法來 形成。此外,亦可將金屬膜或金屬氧化物膜積層於基材、黏著劑層或彈性層來形成抗靜電層。 When the antistatic layer is formed of a metal layer or a metal oxide layer, the metal layer or the metal oxide layer may be, for example, as described in the item B-3, for example, vacuum deposition, sputtering, ion plating, or chemical vaporization. Plating method, spray pyrolysis method, electroless plating method, electroplating method, etc. form. Further, a metal film or a metal oxide film may be laminated on a substrate, an adhesive layer or an elastic layer to form an antistatic layer.
對形成上述抗靜電層之時機並無特別限定,可根據熱剝離型黏著片之構成於任意適當之時機形成。例如,抗靜電層可於形成基材與黏著劑層之積層體之後形成。此外,亦可於基材上形成抗靜電層後於附抗靜電層之基材上形成黏著劑層(或者彈性層),亦可於黏著劑層上(或者彈性層上)形成抗靜電層後將附抗靜電層之黏著劑層(或者彈性層)轉印於基材。 The timing for forming the antistatic layer is not particularly limited, and may be formed at any appropriate timing depending on the configuration of the heat-peelable pressure-sensitive adhesive sheet. For example, the antistatic layer can be formed after forming a laminate of the substrate and the adhesive layer. In addition, an antistatic layer may be formed on the substrate, and then an adhesive layer (or an elastic layer) may be formed on the substrate with the antistatic layer, or an antistatic layer may be formed on the adhesive layer (or the elastic layer). The adhesive layer (or elastic layer) with the antistatic layer is transferred to the substrate.
黏著劑層具有上述彈性層時,該彈性層例如可於基材上或黏著劑層上塗覆彈性層形成用組合物來形成。此外,彈性層可將於任意適當之基體上塗覆彈性層形成用組合物而形成之塗覆層轉印來形成。 When the adhesive layer has the above elastic layer, the elastic layer can be formed, for example, by coating a composition for forming an elastic layer on a substrate or an adhesive layer. Further, the elastic layer may be formed by transferring a coating layer formed by coating the composition for forming an elastic layer on any appropriate substrate.
作為上述各組合物之塗覆方法,可採用任意適當之塗覆方法。例如可於塗佈後進行乾燥而形成各層。作為塗佈方法,例如可列舉使用複合塗敷器(Multicoater)、模塗機、凹版塗佈機、塗抹器等之塗佈方法。作為乾燥方法,例如可列舉自然乾燥、加熱乾燥等。加熱乾燥時之加熱溫度可根據作為乾燥對象之物質之特性設定為任意適當之溫度。 As the coating method of each of the above compositions, any appropriate coating method can be employed. For example, it can be dried after coating to form each layer. Examples of the coating method include a coating method using a multicoater, a die coater, a gravure coater, and an applicator. Examples of the drying method include natural drying, heat drying, and the like. The heating temperature at the time of heat drying can be set to any appropriate temperature depending on the characteristics of the substance to be dried.
G.熱剝離型黏著片之使用方法(電子零件之製造方法)G. Method of using heat-peelable adhesive sheet (manufacturing method of electronic parts)
根據本發明之另一實施態樣,提供一種電子零件之製造方法。本發明之電子零件之製造方法包括如下步驟:於上述熱剝離型黏著片上以大面積貼附獲得之電子零件材料,對該電子零件材料進行切斷加工。 According to another embodiment of the present invention, a method of fabricating an electronic component is provided. The method of manufacturing an electronic component according to the present invention includes the steps of: attaching the obtained electronic component material to the heat-peelable adhesive sheet over a large area, and cutting the electronic component material.
作為上述電子零件,例如可列舉:矽晶圓等半導體裝置用之零件;積層電容器;感應器;電阻;壓電元件;振子;LED;透明電極;等。 Examples of the electronic component include a component for a semiconductor device such as a germanium wafer, a multilayer capacitor, an inductor, a resistor, a piezoelectric element, a vibrator, an LED, a transparent electrode, and the like.
上述製造方法中,首先,於加工台上載置上述熱剝離型黏著 片,並於該熱剝離型黏著片上以大面積貼附獲得之電子零件材料。 In the above manufacturing method, first, the heat peeling type adhesion is placed on a processing table. A sheet is attached to the heat-peelable adhesive sheet with a large area attached to the electronic component material.
其後,利用任意適當之方法將上述電子零件材料切斷,可獲得電子零件。作為上述切斷加工之方法,例如可列舉使用旋轉刀、平面刀等刀具之方法,使用雷射光之方法等。 Thereafter, the electronic component material is cut by any appropriate method to obtain an electronic component. As a method of the above-described cutting processing, for example, a method using a cutter such as a rotary blade or a flat blade, a method using laser light, or the like can be mentioned.
上述切斷加工中,可於加熱下進行切斷。例如可將上述加工台加熱至30℃~150℃進行切斷加工。 In the above cutting process, the cutting can be performed under heating. For example, the processing table can be heated to 30 ° C to 150 ° C for cutting.
實施例 Example
以下,利用實施例對本發明進行具體說明,但本發明並不限定於該等實施例。實施例中之評價方法如下所述。此外,於實施例中,只要無特別說明,則「份」及「%」為重量基準。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. The evaluation methods in the examples are as follows. In addition, in the examples, "parts" and "%" are based on weight unless otherwise specified.
(1)切斷加工性 (1) Cutting processability
於熱剝離型黏著片之黏著劑層上貼附用環氧樹脂(日立化成公司製造,商品名「CEL-9200HF9」)進行封裝而成之QFN引線框(尺寸:125mm×65mm;與黏著片之貼附面為樹脂面(表面粗糙度Ra:3μm)),將其安裝固定於6吋之切割環,經由切割機全切割為250個5mm×5mm尺寸之晶片(實施藉由切割來進行之切斷加工處理),於該切割時,計算發生晶片飛散之個數,作為切斷加工性之評價。 A QFN lead frame made of epoxy resin (manufactured by Hitachi Chemical Co., Ltd., trade name "CEL-9200HF9") was attached to the adhesive layer of the heat-peelable adhesive sheet (size: 125 mm × 65 mm; and adhesive sheet) The attached surface is a resin surface (surface roughness Ra: 3 μm), which is mounted and fixed to a 6-inch cutting ring, and is completely cut into 250 wafers of 5 mm × 5 mm size by a cutter (cutting by cutting) In the dicing process, the number of wafer scatters was counted as the evaluation of the cutting workability.
切割刀使用DISCO公司製造之ZH05-SD2000-N1-110-DD。切割刀之進給速度設為70mm/S,切割刀之轉速設為50000/s。 The cutter is ZH05-SD2000-N1-110-DD manufactured by DISCO. The feed speed of the cutter is set to 70 mm/s, and the rotation speed of the cutter is set to 50000/s.
(2)加熱剝離性 (2) Heat stripping
上述(1)之切斷加工後,使用熱風乾燥器(ESPEC公司製造,商品名「SPH-201」),於130℃下實施10分鐘加熱處理。加熱處理後,以晶片為下側之方式使熱剝離型黏著片反轉,令晶片自然下落。利用此時未自然下落而殘留於熱剝離型黏著片上之晶片數評價加熱剝離性。 After the cutting process of the above (1), a hot air dryer (manufactured by ESPEC, trade name "SPH-201") was used, and heat treatment was performed at 130 ° C for 10 minutes. After the heat treatment, the heat-peelable adhesive sheet was inverted with the wafer as the lower side, and the wafer was naturally dropped. The heat peeling property was evaluated by the number of wafers remaining on the heat-peelable adhesive sheet without falling naturally at this time.
(3)黏著力測定方法 (3) Method for measuring adhesion
將熱剝離型黏著片切斷成寬度:20mm、長度:140mm之尺 寸,基於JIS Z 0237(2000年),於溫度:23±2℃及濕度:65±5%RH之氣氛下,使2kg之輥往復1次,將作為被接著體之聚對苯二甲酸乙二酯膜(商品名「lumirror S-10」東麗公司製造;厚度:25μm、寬度:20mm)壓接貼附於黏著劑層上。繼而,將附被接著體之熱剝離型黏著片置於附有設定於23℃之恆溫槽之拉伸試驗機(島津製作所公司製造,商品名「島津Autograph AG-120kN」)中,放置30分鐘。放置後,測定於23℃之溫度下將被接著體以剝離角度:180°、剝離速度(拉伸速度):300mm/min之條件自熱剝離型黏著帶剝離時之荷重,求出此時之最大荷重(測定初期之封頂除外之荷重之最大值),將該最大荷重作為熱膨脹性黏著劑層之黏著力(N/20mm)。 The heat-peelable adhesive sheet is cut into a width of 20 mm and a length of 140 mm. Inch, based on JIS Z 0237 (2000), in a temperature of 23 ± 2 ° C and humidity: 65 ± 5% RH, the 2kg roller is reciprocated once, and will be used as the adherent polyethylene terephthalate A diester film (trade name "lumirror S-10" manufactured by Toray Industries, Inc.; thickness: 25 μm, width: 20 mm) was pressure-bonded to the adhesive layer. Then, the heat-peelable adhesive sheet with the attached body was placed in a tensile tester (manufactured by Shimadzu Corporation, trade name "Shimadzu Autograph AG-120kN") with a thermostat set at 23 ° C for 30 minutes. . After standing, the load was peeled off at a temperature of 23 ° C at a peeling angle of 180°, a peeling speed (tensile speed): 300 mm/min, and the load was peeled off from the heat-peelable adhesive tape. The maximum load (the maximum value of the load except for the capping at the initial stage of measurement) was used as the adhesion of the heat-expandable pressure-sensitive adhesive layer (N/20 mm).
(4)總透光率 (4) Total light transmittance
基於JIS-6714,使用積分球式透光率測定裝置(村上色彩技術研究所公司製造,商品名「HAZE METER HM-150」測定熱剝離型黏著片之總透光率。 The total light transmittance of the heat-peelable pressure-sensitive adhesive sheet was measured using an integrating sphere type light transmittance measuring device (manufactured by Murakami Color Research Laboratory Co., Ltd., trade name "HAZE METER HM-150") in accordance with JIS-6714.
(5)剝離帶電(剝離電壓之測定) (5) Stripping electrification (measurement of stripping voltage)
於熱剝離型黏著片(寬度70mm×長度130mm)之黏著面貼合經過除電之剝離襯墊(進行有機矽處理之PET膜,東麗公司製造,商品名「Cerapeel」,厚度:38μm)之有機矽處理面,製作評價用樣品。此時,剝離襯墊之長度方向端部自熱剝離型黏著片突出30mm。此外,用手壓輥使熱剝離型黏著片與剝離襯墊於基於JIS Z 0237(2000年)之條件下(溫度:23℃,濕度50%RH)貼附。 Adhesive surface of the heat-peelable adhesive sheet (width: 70 mm × length: 130 mm) is bonded to a removable release liner (PET film made of organic tantalum, manufactured by Toray Industries, under the trade name "Cerapeel", thickness: 38 μm).矽 Processing the surface and prepare a sample for evaluation. At this time, the end portion in the longitudinal direction of the release liner protruded from the heat-peelable adhesive sheet by 30 mm. Further, the heat-peelable pressure-sensitive adhesive sheet and the release liner were attached by hand to a release liner under the conditions of JIS Z 0237 (2000) (temperature: 23 ° C, humidity: 50% RH).
將評價用樣品於23℃、50%RH之環境下放置一日後,抓住剝離襯墊之突出部分,將該剝離襯墊以剝離角度150°、剝離速度10m/min沿長度方向剝離。於相對黏著劑表面為垂直之方向距剝離襯墊與熱剝離型黏著片分離處100mm之位置,測定剝離時產生之黏著劑層表面之電壓,將其最大值作為剝離電壓。再者,作為測定器,使用電位測 定機(春日電器公司製造,商品名「KSD-0103」)。此外,測定環境設為23℃、50%RH。 After the evaluation sample was allowed to stand in an environment of 23° C. and 50% RH for one day, the protruding portion of the release liner was grasped, and the release liner was peeled off in the longitudinal direction at a peeling angle of 150° and a peeling speed of 10 m/min. The voltage of the surface of the adhesive layer generated at the time of peeling was measured at a position 100 mm from the separation of the release liner and the heat-peelable adhesive sheet in the direction perpendicular to the surface of the adhesive, and the maximum value thereof was taken as the peeling voltage. Furthermore, as a measuring device, a potential measurement is used. Fixed machine (manufactured by Kasuga Electric Co., Ltd., trade name "KSD-0103"). Further, the measurement environment was set to 23 ° C and 50% RH.
(6)黏著特性之經時穩定性 (6) Stability over time of adhesion characteristics
將熱剝離型黏著片於溫度23℃、濕度50%之氣氛下保管2個月,由上述(2)中測定之黏著力(A0)與經過2個月後之黏著力(A1),利用下述式(I)算出黏著力之變化率X%。表3中,將變化率X%未達50%之情況設為○、將變化率X%為50%以上之情況設為×。 The heat-peelable adhesive sheet was stored in an atmosphere at a temperature of 23 ° C and a humidity of 50% for 2 months, and the adhesive force (A0) measured in the above (2) and the adhesive force (A1) after 2 months were used. The formula (I) calculates the rate of change X% of the adhesive force. In Table 3, the case where the rate of change X% is less than 50% is ○, and the case where the rate of change X% is 50% or more is ×.
X(%)=(A1/A0)×100 X(%)=(A1/A0)×100
[製造例1]黏著劑層形成用組合物I之調製 [Manufacturing Example 1] Modulation of Composition I for Adhesive Layer Formation
將作為基礎聚合物之丙烯酸系聚合物(丙烯酸2-乙基己酯:丙烯酸乙酯:甲基丙烯酸甲酯:丙烯酸羥基乙酯(重量比)=30:70:5:5)100重量份、萜烯酚系增黏樹脂(YASUHARA CHEMICAL公司製造,商品名「YS polystar S145」)10重量份、異氰酸酯系交聯劑(日本聚胺酯公司製造,商品名「CORONATE L」)2重量份、交聯促進劑(Tokyo Fine Chemical公司製造,商品名「EMBILIZER OL-1」)0.03重量份、熱膨脹性微球(松本油脂製藥公司製造,商品名「Matsumoto Microsphere F-65」;150℃發泡膨脹型)30重量份與甲苯加以混合,調製樹脂溶液,將其作為黏著劑層形成用組合物I。 100 parts by weight of an acrylic polymer (2-ethylhexyl acrylate: ethyl acrylate: methyl methacrylate: hydroxyethyl acrylate (weight ratio) = 30:70:5:5) as a base polymer, 10 parts by weight of a terpene phenol-based tackifying resin (manufactured by YASUHARA CHEMICAL Co., Ltd., trade name "YS polystar S145"), 2 parts by weight of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., trade name "CORONATE L"), and crosslinking promotion 0.03 parts by weight of a heat-expandable microsphere (manufactured by Matsumoto Oil & Fats Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere F-65"; 150 ° C foam expansion type) 30, a product ("EMBILIZER OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) The parts by weight were mixed with toluene to prepare a resin solution, which was used as the composition I for forming an adhesive layer.
再者,若利用該黏著劑層形成用組合物I形成黏著劑層,則該黏著劑層中之結構單元A之含有比率相對於基礎聚合物100重量份為27重量份。 In addition, when the adhesive layer is formed by the composition 1 for forming an adhesive layer, the content ratio of the structural unit A in the adhesive layer is 27 parts by weight based on 100 parts by weight of the base polymer.
[製造例2~12]黏著劑層形成用組合物II~XII之調製 [Production Examples 2 to 12] Modulation of Compositions II to XII for Adhesive Layer Formation
如表1所示設定構成丙烯酸系聚合物之單體之種類及重量比、交聯劑之種類及調配量、以及增黏樹脂之種類及調配量,除此以外,以與製造例1同樣之方式,獲得黏著劑層形成用組合物II~XII。再者,製造例9中,調配離子性液體(離子導電性賦予劑,Japan Carlit公司製 造,商品名「PEL20A」)10重量份,調製黏著劑層形成用組合物IX。此外,製造例10中,調配離子性液體(Japan Carlit公司製造,商品名「CIL-312」),1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)亞胺鹽)3重量份,調製黏著劑層形成用組合物X。 In the same manner as in Production Example 1, except that the type and weight ratio of the monomer constituting the acrylic polymer, the type and amount of the crosslinking agent, and the type and amount of the tackifying resin were set as shown in Table 1. In the manner, the composition for forming an adhesive layer II to XII was obtained. Further, in Production Example 9, an ionic liquid (ionic conductivity imparting agent, manufactured by Japan Carlit Co., Ltd.) was prepared. 10 parts by weight of the product name "PEL20A" was prepared to prepare a composition IX for forming an adhesive layer. Further, in Production Example 10, an ionic liquid (manufactured by Japan Carlit Co., Ltd., trade name "CIL-312"), 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide salt was prepared. The adhesive composition for forming an adhesive layer X was prepared in an amount of 3 parts by weight.
表1中記載之交聯劑、增黏樹脂詳細情況如下所述。 The details of the crosslinking agent and the tackifying resin described in Table 1 are as follows.
<交聯劑> <crosslinker>
TETRAD C:三菱瓦斯化學公司製造,商品名「TETRAD C」,環氧系交聯劑 TETRAD C: manufactured by Mitsubishi Gas Chemical Co., Ltd. under the trade name "TETRAD C", epoxy crosslinking agent
<增黏樹脂> <Tackifying Resin>
Mighty Ace G125:YASUHARA CHEMICAL公司製造,商品名「Mighty Ace G125」,萜烯酚系增黏樹脂 Mighty Ace G125: manufactured by YASUHARA CHEMICAL, trade name "Mighty Ace G125", terpene phenol based tackifying resin
Tamanol 901:荒川化學工業公司製造,商品名「Tamanol 901」,萜烯酚系增黏樹脂 Tamanol 901: manufactured by Arakawa Chemical Industries, Ltd., trade name "Tamanol 901", terpene phenol-based tackifying resin
Tamanol 200N:荒川化學工業公司製造,商品名「Tamanol 200N」,烷基酚系增黏樹脂 Tamanol 200N: manufactured by Arakawa Chemical Industries, Ltd., trade name "Tamanol 200N", alkylphenol-based tackifying resin
Super ester A125:荒川化學工業公司製造,商品名「Super ester A125」,松香系增黏樹脂 Super ester A125: manufactured by Arakawa Chemical Industries Co., Ltd. under the trade name "Super ester A125", rosin-based tackifying resin
[製造例13]彈性層形成用組合物I之調製 [Manufacturing Example 13] Modulation of Composition I for Forming Elastic Layer
將丙烯酸系聚合物(丙烯酸2-乙基己酯:丙烯酸乙酯:甲基丙烯酸甲酯:丙烯酸羥基乙酯(重量比)=30:70:5:5)100重量份、異氰酸酯系交聯劑(日本聚胺酯公司製造,商品名「CORONATE L」)3重量份與甲苯加以混合,調製樹脂溶液,將其作為彈性層形成用組合物I。 Acrylic polymer (2-ethylhexyl acrylate: ethyl acrylate: methyl methacrylate: hydroxyethyl acrylate (weight ratio) = 30:70:5:5) 100 parts by weight, isocyanate crosslinking agent 3 parts by weight of (manufactured by Nippon Polyurethane Co., Ltd., trade name "CORONATE L") was mixed with toluene to prepare a resin solution, which was used as the composition I for forming an elastic layer.
[製造例14~20]彈性層形成用組合物II~VIII之調製 [Production Examples 14 to 20] Modulation of Compositions II to VIII for Forming Elastic Layer
如表2所示設定構成丙烯酸系黏著劑之單體之種類及重量比、以及交聯劑之調配量,除此以外,以與製造例12同樣之方式,獲得彈性層形成用組合物II~VIII。 The composition for forming an elastic layer II was obtained in the same manner as in Production Example 12 except that the type and the weight ratio of the monomer constituting the acrylic pressure-sensitive adhesive and the amount of the crosslinking agent were adjusted as shown in Table 2; VIII.
[實施例1] [Example 1]
將作為抗靜電材料之以1.2重量%含有聚噻吩(聚乙烯二氧噻吩聚苯乙烯磺酸酯)之水分散體(Heraeus公司製造,商品名「Clevios P」)與聚酯系樹脂溶液(東洋紡公司製造,商品名「Vylonal MD1200」,固形物成分濃度:1.2重量%)以固形物成分重量比(水分散體:樹脂溶液)為6:4之方式加以混合,進而,使用異丙醇/純水混合溶劑(異丙醇:純水=6:4(重量比))以固形物成分濃度為1重量%之方式進行稀釋,調製抗靜電層形成用組合物I。 1.2% by weight of an antistatic material containing an aqueous dispersion of polythiophene (polyethylenedioxythiophene polystyrene sulfonate) (manufactured by Heraeus Co., Ltd., trade name "Clevios P") and a polyester resin solution (Toyobo Co., Ltd.) Manufactured by the company, the trade name "Vylonal MD1200", solid content concentration: 1.2% by weight) is mixed in a weight ratio of solid content (aqueous dispersion: resin solution) of 6:4, and further, isopropanol/pure is used. The water-mixing solvent (isopropyl alcohol: pure water = 6:4 (weight ratio)) was diluted so that the solid content concentration was 1 weight%, and the composition 1 for antistatic layer formation was prepared.
將獲得之抗靜電層形成用組合物I塗佈於PET基材(東麗公司製造,商品名「lumirror S10」,厚度:100μm),進行乾燥,於基材上形成厚度50nm之抗靜電層。 The obtained antistatic layer-forming composition I was applied onto a PET substrate (manufactured by Toray Industries, Inc., trade name "lumirror S10", thickness: 100 μm), and dried to form an antistatic layer having a thickness of 50 nm on the substrate.
繼而,將製造例13中獲得之彈性層形成用組合物I塗佈於上述PET基材之與抗靜電層相反側之面,進行乾燥,於該面形成厚度15μm之彈性層。 Then, the composition for forming an elastic layer obtained in Production Example 13 was applied onto the surface of the PET substrate opposite to the antistatic layer, and dried to form an elastic layer having a thickness of 15 μm on the surface.
另外將製造例1中獲得之黏著劑層形成用組合物I塗佈於PET隔離膜(厚度:38μm)之Si處理面上,進行乾燥,形成厚度35μm之黏著劑層前驅物。將該前驅物轉印於上述彈性層之與PET基材相反側之面,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。 Further, the composition 1 for forming an adhesive layer obtained in Production Example 1 was applied onto a Si-treated surface of a PET separator (thickness: 38 μm), and dried to form an adhesive layer precursor having a thickness of 35 μm. The precursor was transferred onto the side of the elastic layer opposite to the PET substrate to obtain a heat-peelable adhesive sheet (antistatic layer (50 nm) / substrate (100 μm) / elastic layer (15 μm) / adhesive layer ( 35μm)).
將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例2] [Embodiment 2]
使用彈性層形成用組合物II,代替彈性層形成用組合物I,使用黏著劑層形成用組合物II,代替黏著劑層形成用組合物I,除此以外,以與實施例1同樣之方式,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏 著片供於上述評價(1)~(6)。將結果示於表3。 In the same manner as in the first embodiment, the composition II for forming an elastic layer was used in place of the composition I for forming an elastic layer, and the composition II for forming an adhesive layer was used instead of the composition I for forming an adhesive layer. A heat-peelable adhesive sheet (antistatic layer (50 nm) / substrate (100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)) was obtained. Hot peeling type The film is for the above evaluations (1) to (6). The results are shown in Table 3.
[實施例3] [Example 3]
將作為抗靜電材料之聚(3,4-乙烯二氧噻吩)之醇分散液(化研產業公司製造,商品名「Enocoat BP105」)與丙醇加以混合,調製包含1重量%聚(3,4-乙烯二氧噻吩)之抗靜電層形成用組合物II。 An alcohol dispersion of poly(3,4-ethylenedioxythiophene) as an antistatic material (manufactured by Kasei Kogyo Co., Ltd., trade name "Enocoat BP105") was mixed with propanol to prepare 1% by weight of poly(3, Composition II for forming an antistatic layer of 4-ethylenedioxythiophene).
使用抗靜電層形成用組合物II,代替抗靜電層形成用組合物I,使用彈性層形成用組合物III,代替彈性層形成用組合物I,使用黏著劑層形成用組合物III,代替黏著劑層形成用組合物I,除此以外,以與實施例1同樣之方式,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 The composition for forming an antistatic layer is used instead of the composition for forming an antistatic layer, and the composition for forming an elastic layer III is used instead of the composition for forming an elastic layer I, and the composition for forming an adhesive layer III is used instead of the adhesive. A heat-peelable adhesive sheet (antistatic layer (50 nm) / substrate (100 μm) / elastic layer (15 μm) / adhesive layer was obtained in the same manner as in Example 1 except for the composition I for forming a layer. (35μm)). The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例4] [Example 4]
使用彈性層形成用組合物IV,代替彈性層形成用組合物III,使用黏著劑層形成用組合物IV,代替黏著劑層形成用組合物III,除此以外,以與實施例3同樣之方式,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 In the same manner as in the third embodiment, the composition IV for forming an elastic layer was used in place of the composition III for forming an elastic layer, and the composition IV for forming an adhesive layer was used instead of the composition III for forming an adhesive layer. A heat-peelable adhesive sheet (antistatic layer (50 nm) / substrate (100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)) was obtained. The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例5] [Example 5]
使用彈性層形成用組合物V,代替彈性層形成用組合物I,使用黏著劑層形成用組合物V,代替黏著劑層形成用組合物I,除此以外,以與實施例1同樣之方式,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 In the same manner as in the first embodiment, the composition V for forming an elastic layer was used in place of the composition I for forming an elastic layer, and the composition V for forming an adhesive layer was used instead of the composition I for forming an adhesive layer. A heat-peelable adhesive sheet (antistatic layer (50 nm) / substrate (100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)) was obtained. The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例6] [Embodiment 6]
使用彈性層形成用組合物VI,代替彈性層形成用組合物I,使用黏著劑層形成用組合物VI,代替黏著劑層形成用組合物I,除此以 外,以與實施例1同樣之方式,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 The composition VI for forming an elastic layer is used instead of the composition I for forming an elastic layer, and the composition VI for forming an adhesive layer is used instead of the composition I for forming an adhesive layer. Further, in the same manner as in Example 1, a heat-peelable adhesive sheet (antistatic layer (50 nm) / substrate (100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)) was obtained. The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例7] [Embodiment 7]
使用黏著劑層形成用組合物VII,代替黏著劑層形成用組合物I,除此以外,以與實施例1同樣之方式,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 A heat-peelable adhesive sheet (antistatic layer (50 nm)/substrate was obtained in the same manner as in Example 1 except that the composition for forming an adhesive layer VII was used instead of the composition for forming an adhesive layer. 100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)). The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例8] [Embodiment 8]
作為基材,準備包含抗靜電材料之PET基材(東麗公司製造,商品名「X53 lumirror # 100」,厚度:100μm,表面電阻率:1×1010Ω/□)。 As a substrate, a PET substrate containing an antistatic material (manufactured by Toray Industries, Inc., trade name "X53 lumirror #100", thickness: 100 μm, surface resistivity: 1 × 10 10 Ω/□) was prepared.
於該包含抗靜電材料之PET基材上塗佈製造例13中獲得之彈性層形成用組合物I,進行乾燥,於該面形成厚度15μm之彈性層。 The composition for forming an elastic layer obtained in Production Example 13 was applied onto the PET substrate containing the antistatic material, and dried to form an elastic layer having a thickness of 15 μm on the surface.
另外將製造例1中獲得之黏著劑層形成用組合物I塗佈於PET隔離膜(厚度:38μm)之Si處理面上,進行乾燥,形成厚度35μm之黏著劑層前驅物。將該前驅物轉印於上述彈性層之與PET基材相反側之面,獲得熱剝離型黏著片(基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。 Further, the composition 1 for forming an adhesive layer obtained in Production Example 1 was applied onto a Si-treated surface of a PET separator (thickness: 38 μm), and dried to form an adhesive layer precursor having a thickness of 35 μm. The precursor was transferred onto the surface of the elastic layer opposite to the PET substrate to obtain a heat-peelable adhesive sheet (substrate (100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)).
將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例9] [Embodiment 9]
使用黏著劑層形成用組合物VIII,代替黏著劑層形成用組合物I,除此以外,以與實施例1同樣之方式,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 A heat-peelable adhesive sheet (antistatic layer (50 nm)/substrate was obtained in the same manner as in Example 1 except that the composition for forming an adhesive layer VIII was used instead of the composition for forming an adhesive layer. 100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)). The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例10] [Embodiment 10]
以與實施例1同樣方式,調製抗靜電層形成用組合物I。 The composition for forming an antistatic layer I was prepared in the same manner as in the first embodiment.
將該抗靜電層形成用組合物I塗佈於PET基材(東麗公司製造,商品名「lumirror S10」,厚度:100μm),進行乾燥,於基材上形成厚度50nm之抗靜電層。 This antistatic layer-forming composition I was applied onto a PET substrate (manufactured by Toray Industries, Inc., trade name "lumirror S10", thickness: 100 μm), and dried to form an antistatic layer having a thickness of 50 nm on the substrate.
繼而,將製造例13中獲得之彈性層形成用組合物I塗佈於上述抗靜電層上,進行乾燥,形成厚度15μm之彈性層。 Then, the composition for forming an elastic layer obtained in Production Example 13 was applied onto the above antistatic layer and dried to form an elastic layer having a thickness of 15 μm.
另外將製造例1中獲得之黏著劑層形成用組合物I塗佈於PET膜(厚度:38μm)上,進行乾燥,形成厚度35μm之黏著劑層前驅物。將該前驅物轉印於上述彈性層上,獲得熱剝離型黏著片(基材(100μm)/抗靜電層(50nm)/彈性層(15μm)/黏著劑層(35μm))。 Further, the composition 1 for forming an adhesive layer obtained in Production Example 1 was applied onto a PET film (thickness: 38 μm) and dried to form an adhesive layer precursor having a thickness of 35 μm. The precursor was transferred onto the above elastic layer to obtain a heat-peelable adhesive sheet (substrate (100 μm) / antistatic layer (50 nm) / elastic layer (15 μm) / adhesive layer (35 μm)).
將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例11] [Example 11]
作為抗靜電層及基材之層疊體,準備藉由蒸鍍形成有抗靜電層之PET膜(東麗公司製造,商品名「半蒸著FB-15」,厚度:50μm,總透光率:15%)。 As a laminate of the antistatic layer and the substrate, a PET film having an antistatic layer formed by vapor deposition (manufactured by Toray Industries, Inc., trade name "semi-steamed FB-15", thickness: 50 μm, total light transmittance: 15%).
繼而,將製造例13中獲得之彈性層形成用組合物I塗佈於上述積層體之基材側(即PET膜中未進行蒸鍍之面),進行乾燥,於該面形成厚度15μm之彈性層。 Then, the composition 1 for forming an elastic layer obtained in Production Example 13 was applied onto the substrate side of the laminate (that is, the surface on which the vapor deposition was not performed in the PET film), and dried to form an elastic layer having a thickness of 15 μm on the surface. Floor.
另外將製造例1中獲得之黏著劑層形成用組合物I塗佈於PET隔離膜(厚度:38μm)之Si處理面上,進行乾燥,形成厚度35μm之黏著劑層前驅物。將該前驅物轉印於上述彈性層之與上述基材相反側之面,獲得熱剝離型黏著片(抗靜電層/基材/彈性層(15μm)/黏著劑層(35μm))。 Further, the composition 1 for forming an adhesive layer obtained in Production Example 1 was applied onto a Si-treated surface of a PET separator (thickness: 38 μm), and dried to form an adhesive layer precursor having a thickness of 35 μm. The precursor was transferred onto the surface of the elastic layer opposite to the substrate to obtain a heat-peelable pressure-sensitive adhesive sheet (antistatic layer/substrate/elastic layer (15 μm)/adhesive layer (35 μm)).
將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表 3。 The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). Show the results in the table 3.
[實施例12] [Embodiment 12]
將製造例13中獲得之彈性層形成用組合物I塗佈於PET基材(東麗公司製造,商品名「lumirror S10」,厚度:100μm),進行乾燥,於該面形成厚度15μm之彈性層。 The composition 1 for forming an elastic layer obtained in Production Example 13 was applied onto a PET substrate (manufactured by Toray Industries, Inc., trade name "lumirror S10", thickness: 100 μm), and dried to form an elastic layer having a thickness of 15 μm on the surface. .
另外將製造例9中獲得之黏著劑層形成用組合物IX塗佈於PET隔離膜(厚度:38μm)之Si處理面上,進行乾燥,形成厚度35μm之黏著劑層前驅物。將該前驅物轉印於上述彈性層之與PET基材相反側之面,獲得熱剝離型黏著片(基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。再者,本實施例係於黏著劑層中包含作為抗靜電材料之離子性液體時之實驗例。 Further, the adhesive layer-forming composition IX obtained in Production Example 9 was applied onto a Si-treated surface of a PET separator (thickness: 38 μm), and dried to form an adhesive layer precursor having a thickness of 35 μm. The precursor was transferred onto the surface of the elastic layer opposite to the PET substrate to obtain a heat-peelable adhesive sheet (substrate (100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)). Further, this embodiment is an experimental example in the case where an ionic liquid as an antistatic material is contained in the adhesive layer.
將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例13] [Example 13]
除不形成彈性層以外,以與實施例1同樣之方式,獲得(抗靜電層(50nm)/基材(100μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 An antistatic layer (50 nm) / substrate (100 μm) / adhesive layer (35 μm) was obtained in the same manner as in Example 1 except that the elastic layer was not formed. The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例14] [Embodiment 14]
利用日本專利特開平4-348161號公報之實施例12中記載之方法來製作膜,將該膜(厚度:50nm)作為抗靜電層積層於PET基材(東麗公司製造,商品名「lumirror S10」,厚度:100μm)上。再者,該膜包含聚苯胺作為抗靜電材料,表面電阻率為2.5×105Ω/□。 A film was produced by the method described in Example 12 of JP-A-4-348161, and the film (thickness: 50 nm) was used as an antistatic laminated layer on a PET substrate (manufactured by Toray Industries, Inc., trade name "lumirror S10". ", thickness: 100 μm). Further, the film contains polyaniline as an antistatic material and has a surface resistivity of 2.5 × 10 5 Ω/□.
繼而,將製造例13中獲得之彈性層形成用組合物I塗佈於上述PET基材之與抗靜電層相反側之面,進行乾燥,於該面形成厚度15μm之彈性層。 Then, the composition for forming an elastic layer obtained in Production Example 13 was applied onto the surface of the PET substrate opposite to the antistatic layer, and dried to form an elastic layer having a thickness of 15 μm on the surface.
另外將製造例1中獲得之黏著劑層形成用組合物I塗佈於PET隔離 膜(厚度:38μm)之Si處理面上,進行乾燥,形成厚度35μm之黏著劑層前驅物。將該前驅物轉印於上述彈性層之與PET基材相反側之面,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。 Further, the composition 1 for forming an adhesive layer obtained in Production Example 1 was applied to PET isolation. The Si-treated surface of the film (thickness: 38 μm) was dried to form an adhesive layer precursor having a thickness of 35 μm. The precursor was transferred onto the side of the elastic layer opposite to the PET substrate to obtain a heat-peelable adhesive sheet (antistatic layer (50 nm) / substrate (100 μm) / elastic layer (15 μm) / adhesive layer ( 35μm)).
將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[實施例15] [Example 15]
將製造例13中獲得之彈性層形成用組合物I塗佈於PET基材(東麗公司製造,商品名「lumirror S10」,厚度:100μm),進行乾燥,於該面形成厚度15μm之彈性層。 The composition 1 for forming an elastic layer obtained in Production Example 13 was applied onto a PET substrate (manufactured by Toray Industries, Inc., trade name "lumirror S10", thickness: 100 μm), and dried to form an elastic layer having a thickness of 15 μm on the surface. .
另外將製造例10中獲得之黏著劑層形成用組合物X塗佈於PET隔離膜(厚度:38μm)之Si處理面上,進行乾燥,形成厚度35μm之黏著劑層前驅物。將該前驅物轉印於上述彈性層之與PET基材相反側之面,獲得熱剝離型黏著片(基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。再者,本實施例係於黏著劑層中包含作為抗靜電材料之離子性液體時之實驗例。 Further, the adhesive layer-forming composition X obtained in Production Example 10 was applied onto a Si-treated surface of a PET separator (thickness: 38 μm) and dried to form an adhesive layer precursor having a thickness of 35 μm. The precursor was transferred onto the surface of the elastic layer opposite to the PET substrate to obtain a heat-peelable adhesive sheet (substrate (100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)). Further, this embodiment is an experimental example in the case where an ionic liquid as an antistatic material is contained in the adhesive layer.
將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[比較例1] [Comparative Example 1]
使用彈性層形成用組合物VII,代替彈性層形成用組合物I,使用黏著劑層形成用組合物XI,代替黏著劑層形成用組合物I,除此以外,以與實施例1同樣之方式,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 In the same manner as in the first embodiment, the composition VII for forming an elastic layer was used instead of the composition I for forming an elastic layer, and the composition XI for forming an adhesive layer was used instead of the composition I for forming an adhesive layer. A heat-peelable adhesive sheet (antistatic layer (50 nm) / substrate (100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)) was obtained. The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[比較例2] [Comparative Example 2]
使用彈性層形成用組合物VIII,代替彈性層形成用組合物I,使 用黏著劑層形成用組合物XII,代替黏著劑層形成用組合物I,除此以外,以與實施例1同樣之方式,獲得熱剝離型黏著片(抗靜電層(50nm)/基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 The composition for forming an elastic layer VIII is used instead of the composition I for forming an elastic layer. A heat-peelable adhesive sheet (antistatic layer (50 nm)/substrate was obtained in the same manner as in Example 1 except that the composition for forming an adhesive layer XII was used instead of the composition for forming an adhesive layer. 100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)). The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
[比較例3] [Comparative Example 3]
除不形成抗靜電層以外,以與實施例1同樣之方式,獲得熱剝離型黏著片(基材(100μm)/彈性層(15μm)/黏著劑層(35μm))。將獲得之熱剝離型黏著片供於上述評價(1)~(6)。將結果示於表3。 A heat-peelable pressure-sensitive adhesive sheet (base material (100 μm) / elastic layer (15 μm) / adhesive layer (35 μm)) was obtained in the same manner as in Example 1 except that the antistatic layer was not formed. The obtained heat-peelable adhesive sheet was subjected to the above evaluations (1) to (6). The results are shown in Table 3.
由表3可知,若使用本發明之熱剝離型黏著片作為電子零件材料之切斷步驟中之臨時固定用片,則能夠防止晶片飛散。此外,本發明之熱剝離型黏著片之剝離帶電量較少。再者,如比較例3般剝離帶電量較多之黏著片有會損傷貼附之電子零件材料之虞。 As is apparent from Table 3, when the heat-peelable pressure-sensitive adhesive sheet of the present invention is used as the temporary fixing sheet in the cutting step of the electronic component material, the wafer can be prevented from scattering. Further, the peeling tape of the heat-peelable adhesive sheet of the present invention has a small amount of electricity. Further, as in Comparative Example 3, the adhesive sheet having a large amount of charge was peeled off, which may damage the attached electronic component material.
本發明之製造方法及黏著片可適宜地用於半導體晶片等晶片狀電子零件之製造。 The production method and the adhesive sheet of the present invention can be suitably used for the production of wafer-shaped electronic parts such as semiconductor wafers.
10‧‧‧黏著劑層 10‧‧‧Adhesive layer
20‧‧‧基材 20‧‧‧Substrate
100‧‧‧黏著片 100‧‧‧Adhesive tablets
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JP6974823B2 (en) * | 2016-05-31 | 2021-12-01 | 国立大学法人神戸大学 | Adhesive composition for microwave dismantling and method of dismantling adhesive |
JP6783570B2 (en) * | 2016-07-11 | 2020-11-11 | 日東電工株式会社 | Adhesive sheet |
KR20200039858A (en) | 2018-10-05 | 2020-04-17 | 삼성디스플레이 주식회사 | Adhesive member and display divice including of the same |
KR102187264B1 (en) * | 2019-09-23 | 2020-12-04 | 주식회사 아이에스시 | Apparatus for cleaning impurity of test socket |
FR3105590B1 (en) * | 2019-12-23 | 2022-12-23 | Michelin & Cie | PIEZOELECTRIC COMPOSITE MATERIALS WITH IMPROVED PIEZOELECTRIC PROPERTIES |
JP7380241B2 (en) | 2020-01-21 | 2023-11-15 | 株式会社デンソー | Brake device for vehicles |
WO2022024510A1 (en) * | 2020-07-30 | 2022-02-03 | 古河電気工業株式会社 | Composition for adhesive, film-like adhesive, and semiconductor package in which film-like adhesive is used and method for manufacturing same |
JP2023001742A (en) * | 2021-06-21 | 2023-01-06 | 日東電工株式会社 | Pressure-sensitive adhesive sheet for semiconductor element processing |
WO2023054480A1 (en) * | 2021-09-30 | 2023-04-06 | 日東電工株式会社 | Adhesive composition, adhesive sheet, and bonded body |
WO2023054484A1 (en) * | 2021-09-30 | 2023-04-06 | 日東電工株式会社 | Adhesive composition, adhesive sheet, and bonded body |
KR20240068664A (en) * | 2021-09-30 | 2024-05-17 | 닛토덴코 가부시키가이샤 | Adhesive compositions, adhesive sheets, and joints |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2001323228A (en) * | 2000-05-15 | 2001-11-22 | Nitto Denko Corp | Heat release adhesive sheet |
JP4703833B2 (en) | 2000-10-18 | 2011-06-15 | 日東電工株式会社 | Energy ray-curable heat-peelable pressure-sensitive adhesive sheet and method for producing cut pieces using the same |
JP4229817B2 (en) * | 2003-11-27 | 2009-02-25 | 電気化学工業株式会社 | Electronic member fixing sheet |
JP6004511B2 (en) * | 2010-01-26 | 2016-10-12 | 日東電工株式会社 | Adhesive optical film and image display device |
EP2602814A1 (en) * | 2010-08-06 | 2013-06-12 | Nitto Denko Corporation | Electronic component manufacturing method |
JP2012193317A (en) * | 2011-03-17 | 2012-10-11 | Nitto Denko Corp | Pressure-sensitive adhesive tape for temporary fixing of electronic part |
MY168337A (en) * | 2011-12-02 | 2018-10-31 | Denka Company Ltd | Pressure-sensitive adhesive sheet and method of manufacturing electronic component using the same |
JP2013147541A (en) * | 2012-01-17 | 2013-08-01 | Nitto Denko Corp | Polymer for adhesive, adhesive composition and heat-peelable adhesive sheet |
JP5977110B2 (en) * | 2012-07-27 | 2016-08-24 | 日東電工株式会社 | Adhesive sheet |
CN202936360U (en) * | 2012-11-30 | 2013-05-15 | 苏州斯迪克新材料科技股份有限公司 | Easily-peeling protection film for electronic component |
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