TW201807125A - Pressure sensitive adhesive sheet having release liner - Google Patents

Pressure sensitive adhesive sheet having release liner Download PDF

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Publication number
TW201807125A
TW201807125A TW106110257A TW106110257A TW201807125A TW 201807125 A TW201807125 A TW 201807125A TW 106110257 A TW106110257 A TW 106110257A TW 106110257 A TW106110257 A TW 106110257A TW 201807125 A TW201807125 A TW 201807125A
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Taiwan
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release liner
adhesive sheet
adhesive
weight
double
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TW106110257A
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Chinese (zh)
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瀬川翠
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日東電工股份有限公司
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Abstract

To provide a pressure sensitive adhesive sheet having a release liner, being a pressure sensitive adhesive sheet for a test piece for analyzing a specimen. The pressure sensitive adhesive sheet having a release liner includes: a double-sided pressure sensitive adhesive sheet having adhesive layers; a first release liner covering the first adhesive layer of the pressure sensitive adhesive sheet; and a second release liner covering the second adhesive layer of the pressure sensitive adhesive sheet. A water contact angle is 70 DEG or more with regard to one of a back face of the first release liner and a back face of the second release liner.

Description

附剝離襯墊之黏著片Adhesive sheet with release liner

本發明係關於一種用於製造用以分析樣本之試驗片之附剝離襯墊之黏著片。The present invention relates to an adhesive sheet with a release liner for manufacturing a test piece for analyzing a sample.

業界廣泛使用進行血糖濃度之測定等之各種樣本測定設備。使用此種設備之測定例如係藉由如下方式而進行:將血液樣本等樣本取樣於試驗片,並將保持有該樣本之試驗片放置於測定設備,檢測試驗片中之試劑與該樣本反應時之電流等。作為揭示上述測定設備所使用之試驗片之先前技術文獻,可列舉日本專利申請公開2006-308458號公報。日本專利申請公開2015-054921號公報係與用於此種試驗片之黏著片相關之先前技術文獻。Various sample measurement equipment for measuring blood glucose concentration and the like are widely used in the industry. The measurement using such a device is performed, for example, by sampling a blood sample or the like on a test piece, and placing the test piece holding the sample in the measuring device, and detecting when a reagent in the test piece reacts with the sample. The current etc. As a prior art document which discloses the test piece used for the said measuring apparatus, the Japanese patent application publication 2006-308458 is mentioned. Japanese Patent Application Publication No. 2015-054921 is a prior art document related to an adhesive sheet used for such a test piece.

上述試驗片例如包含基板或間隔片、蓋(例如親水性膜)等複數個構件,為了將基板與蓋接合,可較佳地使用雙面接著性之黏著片(雙面黏著片)。該雙面黏著片於基板與蓋之間亦發揮作為間隔片功能,且具有將樣本引導至電極之通路(亦稱為毛細管)。又,於上述雙面黏著片設置有用以注入與血液等樣本進行反應之試劑之孔,於將該雙面黏著片之一黏著面貼合於基板後,上述試劑被注入至設置於黏著片之孔。其後,經過將蓋貼合於雙面黏著片之另一黏著面並將基板與蓋接合等步驟而製造試驗片。 於如上所述之試驗片之製造中,視向設置於上述黏著片之孔注入試劑之精度,存在無法將試劑之至少一部分注入至孔中而產生注入不良之情況。於該情形時,藉由對於存在注入不良之試驗片再次進行試劑之注入操作,可有效地利用試驗片。然而,例如血糖濃度測定所使用之試劑通常包含酶等而昂貴,故而存在欲避免再次注入等之情況。即便於產生如上所述之注入不良之情形時,只要可藉由其後之操作將未注入至孔中之殘留試劑注入至所需之孔中,則亦可避免試劑損失,因此有益。 本發明係鑒於上述先前之情況而完成者,目的在於提供一種附剝離襯墊之黏著片,其係用以分析樣本之試驗片用之黏著片,並且可防止試驗片製造時之試劑損失。 [解決問題之技術手段] 根據本發明,提供一種用於製造用以分析樣本之試驗片之附剝離襯墊之黏著片。該附剝離襯墊之黏著片具備具有黏著劑層之雙面接著性之黏著片、覆蓋該黏著片之第1黏著面之第1剝離襯墊、及覆蓋該黏著片之第2黏著面之第2剝離襯墊。又,上述第1剝離襯墊之背面及上述第2剝離襯墊之背面中之一個背面之水接觸角為70°以上。 根據上述構成,雙面黏著片係藉由2片剝離襯墊分別覆蓋其兩個黏著面,因此可在附剝離襯墊之黏著片之狀態下容易地形成貫通剝離襯墊(例如第2剝離襯墊)與黏著片之孔。並且,於製造用以分析樣本之試驗片(以下,亦簡稱為「試驗片」)時,可自上述雙面黏著片將保護其第1黏著面之第1剝離襯墊剝離,將露出之第1黏著面貼合於基板後,自保護第2黏著面之第2剝離襯墊之背面(外表面)側將試劑注入至於該背面開口之孔。並且,進而,即便於該試劑注入時無法將試劑高精度地注入至孔中而產生試劑之至少一部分殘留於第2剝離襯墊之背面之注入不良,藉由將第2剝離襯墊背面之水接觸角設為70°以上,未注入試劑亦毫無損失地殘留於第2剝離襯墊背面上。藉由利用適當之方法誘導該第2剝離襯墊背面上之未注入試劑進入至孔中,可不浪費地利用試劑。與上述相反,於首先將第2黏著面貼合於被黏著體之情形時,藉由將第1剝離襯墊背面之水接觸角設為70°以上,可獲得與上述相同之效果。因此,藉由使用本發明之附剝離襯墊之黏著片,可防止試驗片製造時之試劑損失。 於此處所揭示之技術(包含附剝離襯墊之黏著片、具備該黏著片之試驗片、該試驗片之製造方法,以下相同)之較佳之一態樣中,上述黏著劑層之凝膠分率為25%~55%。上述凝膠分率為特定值以下之黏著片之試劑保持性優異。具體而言,藉由使黏著劑層之凝膠分率為特定值以下,可較佳地防止收容於雙面黏著片內之試劑自黏著片之黏著面漏出之現象。又,上述凝膠分率為特定值以上之黏著片於沖裁加工等加工後不存在糊劑之溢出,因此加工性優異。進而,藉由使用具有上述範圍之凝膠分率之黏著劑層,亦可改善耐彎曲性。 於此處所揭示之技術之較佳之一態樣中,上述黏著片之黏著面(典型而言為第1黏著面及第2黏著面之兩者)顯示出7 N/20 mm以上之180度剝離強度。顯示出上述剝離強度之黏著片即便尺寸較小,亦可發揮充分之接合強度,因此可較佳地用作接著面積容易受到限制之試驗片用之黏著片。 於此處所揭示之技術之較佳之一態樣中,上述黏著片係具備基材、設置於該基材之一面之第1黏著劑層、及設置於該基材之另一面之第2黏著劑層的附基材之雙面黏著片。藉由使用具有基材之黏著片,黏著片之加工性提高,從而可更容易地製造形狀精度較高之試驗片。 於此處所揭示之技術之較佳之一態樣中,上述黏著劑層係包含丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑層。藉由使用丙烯酸系黏著劑作為黏著劑,可較佳地實現具有適於試驗片用途之黏著特性之黏著片。 於此處所揭示之技術之較佳之一態樣中,上述黏著劑層包含相對於上述丙烯酸系聚合物100重量份為20~60重量份之黏著賦予樹脂。藉由於丙烯酸系黏著劑中調配特定量之黏著賦予樹脂,可較佳地實現具有適於試驗片用途之特性(例如黏著力或試劑保持性)之黏著片。 於此處所揭示之技術之較佳之一態樣中,上述黏著片之厚度為50 μm以下。此種較薄之黏著片可較佳地發揮作為基板與蓋之間之間隔片之功能。 於此處所揭示之技術之較佳之一態樣中,上述試驗片係裝卸自如地連接於生物樣本測定設備之生物感測器。於如上所述之生物感測器中,樣本測定所使用之試劑相對昂貴。藉由使用此處所揭示之黏著片作為此種生物感測器用之黏著片,可有效地享受防止試劑損失之優勢。又,以生物感測器為代表之生物樣本測定設備等樣本測定設備之分析精度逐年提高,隨之,有要求更高品質之試驗片之傾向。藉由將此處所揭示之較佳之一態樣之黏著片用於此種用途,可提高試驗片之強度等(典型而言為構件間之接合強度等),從而可創造出更高品質之試驗片(典型而言為生物感測器)。 又,根據本說明書,可提供一種用以分析樣本之試驗片之製造方法。該製造方法包括:準備附剝離襯墊之黏著片之步驟,該附剝離襯墊之黏著片具備具有黏著劑層之雙面接著性之黏著片、覆蓋該黏著片之第1黏著面之第1剝離襯墊、及覆蓋該黏著片之第2黏著面之第2剝離襯墊;設置將上述附剝離襯墊之黏著片中之至少上述第2剝離襯墊與上述黏著片貫通之孔之步驟;自上述附剝離襯墊之黏著片剝離上述第1剝離襯墊,並將上述黏著片之第1黏著面貼合於試驗片構件A(例如基板)之步驟;及將試劑注入至於上述第2剝離襯墊之背面開口之上述孔之步驟。又,典型而言,上述製造方法可進而包括:自上述附剝離襯墊之黏著片剝離上述第2剝離襯墊,並將上述黏著片之第2黏著面貼合於試驗片構件B(例如被覆層)之步驟。於上述製造方法中,上述第2剝離襯墊之背面之水接觸角較佳為70°以上。根據上述製造方法,可防止試劑損失。The test piece includes, for example, a plurality of members such as a substrate, a spacer, and a cover (for example, a hydrophilic film). In order to bond the substrate to the cover, a double-sided adhesive sheet (double-sided adhesive sheet) is preferably used. The double-sided adhesive sheet also functions as a spacer between the substrate and the cover, and has a path (also referred to as a capillary) for guiding the sample to the electrode. In addition, a hole is provided in the double-sided adhesive sheet for injecting a reagent reacting with a sample such as blood, and after one of the double-sided adhesive sheets is adhered to a substrate, the reagent is injected into the double-sided adhesive sheet. hole. After that, a test piece is manufactured by attaching the cover to the other adhesive surface of the double-sided adhesive sheet and joining the substrate and the cover. In the manufacture of the test piece as described above, the accuracy of injecting the reagent into the hole provided in the above-mentioned adhesive sheet may not be able to inject at least a part of the reagent into the hole, resulting in poor injection. In this case, the test piece can be effectively used by re-injecting the reagent to the test piece having a poor injection. However, for example, reagents used for blood glucose concentration measurement often include enzymes and are expensive, so there are cases where it is necessary to avoid reinjection. That is, when it is convenient to cause the injection failure as described above, as long as the remaining reagents that have not been injected into the wells can be injected into the required wells through subsequent operations, the loss of reagents can also be avoided, which is beneficial. The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide an adhesive sheet with a release liner, which is an adhesive sheet for a test piece for analyzing a sample, and can prevent loss of reagents during the manufacture of the test piece. [Technical means to solve the problem] According to the present invention, there is provided an adhesive sheet with a release liner for producing a test piece for analyzing a sample. The adhesive sheet with a release liner includes a double-sided adhesive sheet having an adhesive layer, a first release liner covering a first adhesive surface of the adhesive sheet, and a second adhesive sheet covering a second adhesive surface of the adhesive sheet. 2 Release liner. The water contact angle of one of the back surface of the first release liner and the back surface of the second release liner is 70 ° or more. According to the above configuration, the double-sided adhesive sheet covers its two adhesive surfaces with two release liners, respectively. Therefore, it is possible to easily form a through release liner (for example, a second release liner) in a state of an adhesive sheet with a release liner. Pad) and the hole of the adhesive sheet. In addition, when a test piece (hereinafter, also referred to as a "test piece") for analyzing a sample is manufactured, the first release liner protecting the first adhesive surface of the double-sided adhesive sheet can be peeled off, and the exposed first 1 After the adhesive surface is bonded to the substrate, the reagent is injected into the hole opened in the rear surface from the back (outer surface) side of the second release liner that protects the second adhesive surface. In addition, even if the reagent cannot be injected into the hole with high accuracy during the injection of the reagent, at least a part of the reagent is left on the back surface of the second release liner and injection failure occurs. The contact angle was set to 70 ° or more, and it remained on the back surface of the second release liner without injecting any reagent. By inducing an uninjected reagent on the back surface of the second release liner into the well by an appropriate method, the reagent can be used without waste. In contrast to the above, when the second adhesive surface is first attached to the adherend, the same effect as described above can be obtained by setting the water contact angle on the back surface of the first release liner to 70 ° or more. Therefore, by using the adhesive sheet with a release liner of the present invention, it is possible to prevent loss of reagents during the production of the test piece. In a preferred aspect of the technology disclosed here (including an adhesive sheet with a release liner, a test piece provided with the adhesive sheet, and a method for manufacturing the test piece, the same below), the gel fraction of the above-mentioned adhesive layer is The rate is 25% to 55%. The above-mentioned gel fraction is excellent in the reagent holding property of an adhesive sheet having a specific value or less. Specifically, by reducing the gel fraction of the adhesive layer to a specific value or less, it is possible to better prevent the reagent contained in the double-sided adhesive sheet from leaking from the adhesive surface of the adhesive sheet. In addition, since the adhesive sheet having the gel fraction above a specific value has no paste overflow after processing such as punching, the processability is excellent. Furthermore, by using an adhesive layer having a gel fraction in the above range, the bending resistance can be improved. In a preferred aspect of the technology disclosed herein, the adhesive surface of the above-mentioned adhesive sheet (typically, both the first adhesive surface and the second adhesive surface) shows a 180-degree peel of 7 N / 20 mm or more strength. The adhesive sheet exhibiting the above-mentioned peel strength can exhibit sufficient bonding strength even if the size is small, and therefore, it can be suitably used as an adhesive sheet for a test sheet where the area of the adhesive is easily limited. In a preferred aspect of the technology disclosed herein, the adhesive sheet is provided with a substrate, a first adhesive layer provided on one side of the substrate, and a second adhesive provided on the other side of the substrate. Double-sided adhesive sheet with substrate. By using an adhesive sheet having a base material, the workability of the adhesive sheet is improved, so that it is easier to manufacture a test piece having a higher shape accuracy. In a preferred aspect of the technology disclosed herein, the above-mentioned adhesive layer is an acrylic adhesive layer including an acrylic polymer as a base polymer. By using an acrylic adhesive as the adhesive, an adhesive sheet having adhesive properties suitable for the use of a test piece can be better realized. In a preferred aspect of the technology disclosed herein, the adhesive layer includes an adhesion-imparting resin in an amount of 20 to 60 parts by weight based on 100 parts by weight of the acrylic polymer. By formulating a specific amount of the adhesion-imparting resin in the acrylic pressure-sensitive adhesive, an adhesive sheet having characteristics suitable for the use of the test piece (such as adhesion or reagent retention) can be preferably realized. In a preferred aspect of the technology disclosed herein, the thickness of the adhesive sheet is 50 μm or less. Such a thin adhesive sheet can better function as a spacer between the substrate and the cover. In a preferred aspect of the technology disclosed herein, the test strip is a biosensor that is detachably connected to a biological sample measurement device. In the biosensors described above, the reagents used for sample measurement are relatively expensive. By using the adhesive sheet disclosed herein as an adhesive sheet for such a biosensor, the advantage of preventing loss of reagents can be effectively enjoyed. In addition, the analysis accuracy of sample measurement equipment such as biological sample measurement equipment represented by biosensors has been increasing year by year, and as a result, there has been a tendency to require higher quality test pieces. By using one of the preferred aspects of the adhesive sheet disclosed herein for this purpose, the strength of the test piece (typically, the bonding strength between members, etc.) can be increased, thereby creating a higher quality test Film (typically a biosensor). In addition, according to the present specification, a method for manufacturing a test piece for analyzing a sample can be provided. The manufacturing method includes the steps of preparing an adhesive sheet with a release liner, the adhesive sheet with a release liner having a double-sided adhesive sheet with an adhesive layer, and a first sheet covering a first adhesive surface of the adhesive sheet. A release liner and a second release liner covering the second adhesive surface of the adhesive sheet; a step of providing a hole penetrating at least the second release liner and the adhesive sheet in the adhesive sheet with the release liner; A step of peeling the first release liner from the adhesive sheet with a release liner, and bonding the first adhesive surface of the adhesive sheet to a test piece member A (for example, a substrate); and injecting a reagent into the second peeling The step of opening the above hole on the back of the pad. Further, typically, the manufacturing method may further include peeling the second release liner from the adhesive sheet with a release liner, and bonding the second adhesive surface of the adhesive sheet to the test piece member B (for example, coating Layer). In the above manufacturing method, the water contact angle of the back surface of the second release liner is preferably 70 ° or more. According to the above manufacturing method, loss of reagents can be prevented.

以下,對本發明之較佳之實施形態進行說明。再者,業者可基於本說明書所記載之有關發明之實施之教示與申請時之技術常識理解本說明書中特別提及之事項以外之本發明之實施所必需之內容。本發明可基於本說明書所揭示之內容與該領域中之技術常識而實施。又,於以下之圖式中,存在對發揮相同作用之構件、部位標註相同符號進行說明,且將重複之說明省略或簡略化之情況。又,圖式所記載之實施形態係模式化以清楚地說明本發明,並未正確地表示作為製品所實際提供之黏著片或試驗片之尺寸或縮小比例。 於本說明書中,所謂「黏著劑」,係指具有於室溫附近之溫度區域下呈柔軟之固體(黏彈性體)之狀態,且藉由壓力而簡單地接著於被黏著體之性質之材料。此處所言之黏著劑如「C. A. Dahlquist, “Adhesion : Fundamental and Practice”, McLaren & Sons, (1966) P. 143」所定義,通常可為具有滿足複拉伸彈性模數E (1 Hz)<107 dyne/cm2 之性質之材料(典型而言為於25℃下具有上述性質之材料)。 <附剝離襯墊之黏著片之結構例> 此處所揭示之附剝離襯墊之黏著片例如具有圖1所示之剖面結構。該附剝離襯墊之黏著片1具備雙面接著性之黏著片(雙面黏著片)11。該雙面黏著片11具備作為基材15之塑膠膜及分別由該基材15之雙面支持之第1黏著劑層21及第2黏著劑層22。更詳細而言,於基材15之第1面15A及第2面15B(均為非剝離性)分別設置有第1黏著劑層21及第2黏著劑層22。 又,附剝離襯墊之黏著片1具備覆蓋雙面黏著片11之第1黏著面(第1黏著劑層21之黏著面,位於與基材15側相反之側之表面)21A之第1剝離襯墊31、及覆蓋雙面黏著片11之第2黏著面(第2黏著劑層22之黏著面,位於與基材15側相反之側之表面)22A之第2剝離襯墊32。使用前(貼附於被黏著體之前)之雙面黏著片11中,第1黏著劑層21之第1黏著面21A係由該第1黏著面21A側之表面(正面)31A成為剝離面之第1剝離襯墊31保護。又,第2黏著劑層22之第2黏著面22A係由該第2黏著面22A側之表面(正面)32A成為剝離面之第2剝離襯墊32保護。第1剝離襯墊31之背面(與正面31A相反之側之表面)31B於附剝離襯墊之黏著片1中構成外表面。又,第2剝離襯墊32之背面(與正面32A相反之側之表面)32B亦與第1剝離襯墊31之背面31B同樣地,於附剝離襯墊之黏著片1中構成外表面。 此處所揭示之技術可較佳地應用於圖1所示之附基材之雙面黏著片,此外,亦可應用於圖2所示之無基材之(即不具有基材)雙面黏著片12。使用前之雙面黏著片12例如如圖2所示,為附剝離襯墊之黏著片2之形態,具有無基材之黏著劑層20,且具備覆蓋其第1黏著面(黏著劑層20之一黏著面)20A之第1剝離襯墊31及覆蓋其第2黏著面(黏著劑層20之另一黏著面,位於與第1黏著面20A相反之側之黏著面)20B之第2剝離襯墊32。由無基材之黏著劑層20構成之雙面黏著片12之第1黏著面20A係由該第1黏著面20A側之表面(正面)31A成為剝離面之第1剝離襯墊31保護。又,雙面黏著片12之第2黏著面20B係由該第2黏著面20B側之表面(正面)32A成為剝離面之第2剝離襯墊32保護。 <第1剝離襯墊及第2剝離襯墊> 此處所揭示之技術之特徵在於:第1剝離襯墊及第2剝離襯墊(以下,有時彙總簡稱為「剝離襯墊」)之任一者之背面(與黏著劑層側表面(正面)相反之側之表面)之水接觸角為70°以上。藉此,於製造試驗片時,即便欲將試劑注入至於第1剝離襯墊或第2剝離襯墊之背面開口之孔中而未能將該試劑之至少一部分注入至孔中之情形時,未注入之試劑亦不會潤濕擴散或被吸收而以液滴之形式殘留於上述剝離襯墊背面上。例如藉由使剝離襯墊傾斜或使用滴管等誘導機構轉移液滴,將殘留於該剝離襯墊背面上之未注入試劑(液滴)導入至孔中,可防止試劑損失。有時將此種對未於注入操作中注入而殘留之試劑進行回收並裝入至所需之孔中之操作稱為回收注入以與將新的試劑液滴注入至相同之孔中之再次注入加以區別。又,有時將如上所述以水接觸角成為70°以上之撥水性之方式調節之剝離襯墊之背面稱為撥水性背面以與水接觸角未達70°之剝離襯墊背面(非撥水性背面)加以區別。上述水接觸角可藉由構成剝離襯墊背面之材料之選擇或表面處理等進行調節。剝離襯墊背面(撥水性背面)之水接觸角係利用下述實施例所記載之方法進行測定。 第1剝離襯墊背面及第2剝離襯墊背面中之一背面(撥水性背面)之水接觸角較佳為90°以上(典型而言超過90°),更佳為100°以上,進而較佳為120°以上(例如130°以上)。若上述水接觸角過大,則存在液滴過於容易於第1剝離襯墊背面上移動而自該背面脫落之情況,因此上述水接觸角較適合為160°以下(例如150°以下)左右。再者,第1剝離襯墊背面及第2剝離襯墊背面中之另一背面之水接觸角可未達70°,亦可為70°以上。 此處所揭示之第1剝離襯墊背面及第2剝離襯墊背面中之一背面(撥水性背面)之表面自由能較佳為未達40 mJ/m2 。藉此,容易防止試劑損失。上述表面自由能較佳為30 mJ/m2 以下,更佳為20 mJ/m2 以下(例如15 mJ/m2 以下)。就試劑回收性之觀點而言,上述表面自由能較合適為7 mJ/m2 以上(例如10 mJ/m2 以上)。再者,第1剝離襯墊背面及第2剝離襯墊背面中之另一背面之表面自由能可未達40 mJ/m2 ,亦可為40 mJ/m2 以上。剝離襯墊背面(撥水性背面)之表面自由能係利用下述實施例所記載之方法而求出。 作為第1剝離襯墊及第2剝離襯墊中具有撥水性背面之剝離襯墊,典型而言,使用具有作為剝離面之正面及作為撥水面之背面之剝離襯墊。作為此種剝離襯墊之較佳例,可列舉對剝離襯墊基材實施過剝離處理及撥水處理者。上述剝離襯墊可為對剝離襯墊基材之一表面實施過剝離處理,對另一表面實施過撥水處理者。於典型之一態樣中,上述具有撥水性背面之剝離襯墊具備成為支持體之剝離襯墊基材(剝離處理對象且撥水處理對象)、設置於該基材之一表面之剝離處理層、及設置於該基材之另一表面之撥水處理層。 此處所揭示之剝離襯墊基材之材料並無特別限定。例如可使用由塑膠類、紙類、各種纖維類等形成之單層體(例如塑膠膜)或者積層體。再者,於本說明書中,所謂「塑膠膜」,典型而言為非多孔質之膜,並且係與所謂之不織布或織布區別之概念。 作為上述塑膠膜,例如可使用包含聚乙烯(PE)、聚丙烯(PP)等聚烯烴;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)等聚酯;聚醯胺(所謂之尼龍);纖維素(所謂之塞璐芬)等之膜。塑膠膜類可為非延伸型,亦可為延伸型(單軸延伸型或雙軸延伸型)。 作為上述紙基材,例如可使用日本紙、洋紙、道林紙、玻璃紙、牛皮紙、伸性紙、皺紋紙、白土塗佈紙(clay coated paper)、面漆紙、合成紙等。紙基材之基重並無特別限定,通常適宜為使用50~100 g/m2 左右者。 作為各種纖維基材,可列舉由各種纖維狀物質(可為天然纖維、半合成纖維或合成纖維之任一者,例如棉纖維、人造短纖維、馬尼拉麻、紙漿、嫘縈、乙酸纖維、聚酯纖維、聚乙烯醇纖維、聚醯胺纖維、聚烯烴纖維等)單獨或混紡等所得之織布或不織布等。 作為包含其他素材之基材,可列舉:包含天然橡膠、丁基橡膠等之橡膠片材類;包含發泡聚胺基甲酸酯、發泡聚氯丁二烯橡膠等發泡體之發泡體片材類;鋁箔、銅箔等金屬箔;該等之複合體等。 作為積層體,例如可列舉於雙面層壓有塑膠膜(例如PE樹脂)之紙(例如道林紙)。 作為上述中之較佳之剝離襯墊基材,可列舉聚酯膜,其中更佳為PET膜。 針對上述剝離襯墊基材,亦可視需要對設置剝離處理層或撥水處理層之表面實施電暈放電處理、電漿處理、底塗劑之塗佈等各種表面改質處理或壓紋加工等各種表面加工。又,亦可視需要調配填充劑(無機填充劑、有機填充劑等)、抗老化劑、抗氧化劑、紫外線吸收劑、抗靜電劑、潤滑劑、塑化劑、著色劑(顏料、染料等)等各種添加劑。 此處所揭示之剝離襯墊之撥水性背面可使用聚矽氧系撥水處理劑、氟系撥水處理劑、長鏈烷基系撥水處理劑等撥水處理劑形成。作為該等撥水處理劑,能夠自可用作剝離處理劑者基於技術常識選擇水接觸角滿足70°以上者使用。其中,較佳為聚矽氧系撥水處理劑。或者,藉由自剝離襯墊基材之材料基於技術常識選擇表面之水接觸角成為70°以上之材料使用,亦可獲得撥水性背面。例如,亦能夠將由烯烴系樹脂(例如PE、PP、乙烯-丙烯共聚物、PE/PP混合物)、氟系聚合物(例如聚四氟乙烯、聚偏二氟乙烯)、矽橡膠等形成之剝離襯墊基材用作剝離襯墊而不對該基材之表面實施撥水處理。於該情形時,該剝離襯墊之背面即便不進行撥水處理亦能夠成為撥水性背面。 作為於較佳之一態樣中使用之聚矽氧系撥水處理劑,並無特別限制,可使用可實現70°以上之水接觸角之各種聚矽氧系材料。例如,可列舉於塗佈後藉由賦予熱或游離輻射(紫外線、α射線、β射線、γ射線、中子射線、電子束等)而硬化之熱硬化性(典型而言為熱硬化性加成型)聚矽氧系撥水處理劑、游離輻射硬化性(典型而言為UV(ultraviolet,紫外線)硬化性)聚矽氧系撥水處理劑等。該等可單獨使用1種,或者可將2種以上組合使用。就經濟性、塗佈所需之裝置之簡便性等觀點而言,可較佳地使用熱硬化性(典型而言為熱硬化性加成型)聚矽氧系撥水處理劑。又,該等撥水處理劑可為不含溶劑之無溶劑型、溶解或分散於有機溶劑中之溶劑型之任一者。又,亦可使用於將表面張力相對較低之溶劑適量混合於無溶劑型撥水處理劑中並以容易賦予(典型而言塗佈)之方式調節黏度而成者。進而,可於如上所述之熱硬化性等之聚矽氧系撥水處理劑中添加用於提高反應性之鉑系觸媒等觸媒。就撥水處理層形成時之環境衛生或減少VOC(volatile organic compounds,揮發性有機物)之觀點而言,較佳為使用實質上不含有機溶劑並可於該狀態下直接塗佈之無溶劑型。如上所述之聚矽氧系撥水處理劑例如可自信越化學工業公司等獲取。 作為於此處所揭示之剝離襯墊形成撥水處理層之方法,例如可列舉使用各種塗佈機於剝離襯墊基材塗佈聚矽氧系撥水處理劑等撥水處理劑並進行乾燥而形成撥水處理層之方法。作為上述塗佈機,例如可自直接凹版塗佈機、膠版凹版塗佈機、輥式塗佈機、棒式塗佈機、模嘴塗佈機等適當選擇。作為乾燥條件,並無特別限制,可適當選擇適於所使用之撥水處理劑之乾燥條件。通常較合適為溫度80~150℃左右之乾燥溫度。 於此處所揭示之剝離襯墊具有撥水處理層之情形時,撥水處理層之厚度並無特別限制。就充分地獲得撥水性之觀點而言,撥水處理層之厚度例如較合適為大約0.03 μm以上,較佳為大約0.05 μm以上。又,就膜形成性或成本等觀點而言,上述厚度例如為5 μm以下(典型而言為3 μm以下)左右。 作為撥水處理劑之塗佈量,可根據所使用之剝離襯墊基材之種類、撥水處理劑之種類等適當選擇。例如,較合適為以固形物成分換算計為0.01 g/m2 以上,較佳為0.05 g/m2 以上,更佳為0.1 g/m2 以上,進而較佳為0.5 g/m2 以上,又,較合適為大約10 g/m2 以下,較佳為7 g/m2 以下,更佳為5 g/m2 以下,進而較佳為4 g/m2 以下。 此處所揭示之剝離襯墊之剝離面可使用公知或慣用之剝離處理劑(例如聚矽氧系、氟系、長鏈烷基系等之剝離處理劑)並藉由常規方法形成。例如,可較佳地採用層壓有PE樹脂之道林紙之PE樹脂面或利用聚矽氧系剝離處理劑對聚酯製剝離襯墊基材之表面進行剝離處理而成之剝離面。又,例如亦能夠將由烯烴系樹脂(例如PE、PP、乙烯-丙烯共聚物、PE/PP混合物)、氟系聚合物(例如聚四氟乙烯、聚偏二氟乙烯)、矽橡膠等形成之剝離襯墊基材用作剝離襯墊而不對該基材之表面實施剝離處理。於該情形時,該剝離襯墊之表面(典型而言為正面)即便不進行剝離處理亦能夠成為剝離面。 作為於此處所揭示之剝離襯墊形成剝離處理層之方法,可採用先前公知之方法。例如可使用各種塗佈機於剝離襯墊基材塗佈如上所述之剝離處理劑(例如聚矽氧系剝離處理劑)並進行乾燥而形成剝離處理層。作為上述塗佈機,可適當選擇作為可於撥水處理層之形成中採用之塗佈機而例示者。關於乾燥條件,亦並無特別限制,可適當選擇適於所使用之剝離處理劑之乾燥條件。 於此處所揭示之剝離襯墊具有剝離處理層之情形時,剝離處理層之厚度並無特別限制。就充分地獲得剝離性之觀點而言,剝離處理層之厚度例如較合適為大約0.03 μm以上,較佳為大約0.05 μm以上。又,就膜形成性或成本等觀點而言,上述厚度例如為5 μm以下(典型而言為3 μm以下)左右。 就作業性等觀點而言,此處所揭示之剝離襯墊之厚度較合適為設為大約20 μm以上,較佳為30 μm以上(例如50 μm以上,進而60 μm以上),又,上述厚度較合適為設為大約200 μm以下,較佳為160 μm以下(例如100 μm以下)。第1剝離襯墊與第2剝離襯墊之厚度可相同,亦可不同。於按照第1剝離襯墊、第2剝離襯墊之順序將剝離襯墊剝離而使用黏著片之態樣中,較佳為將第1剝離襯墊之厚度設為薄於第2剝離襯墊。藉此,第1剝離襯墊之剝離作業性、以及黏著片之貼附作業性提高。又,藉由使第2剝離襯墊具有厚度,提高剛性,而於第1剝離襯墊剝離後容易利用第2剝離襯墊支持黏著片。 <黏著劑層> 此處所揭示之黏著劑層(於附基材之雙面黏著片之情形時,包含第1黏著劑層及第2黏著劑層,以下相同)可包含黏著劑之領域中公知之丙烯酸系聚合物、橡膠系聚合物、聚酯系聚合物、胺基甲酸酯系聚合物、聚醚系聚合物、聚矽氧系聚合物、聚醯胺系聚合物、氟系聚合物等各種橡膠狀聚合物之1種或2種以上作為基礎聚合物。詳細內容將於下文中進行敍述,此處所揭示之黏著劑層較佳為包含丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑層或包含橡膠系聚合物作為基礎聚合物之橡膠系黏著劑層。或者,亦可為將丙烯酸系聚合物與橡膠系聚合物併用作基礎聚合物之黏著劑層。 (丙烯酸系黏著劑層) 於較佳之一態樣中,上述黏著劑層就特性(典型而言為黏著力或耐彎曲性、試劑保持性等)或分子設計、經時穩定性等觀點而言,係包含丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑層。再者,於本說明書中,所謂黏著劑之「基礎聚合物」,係指該黏著劑所包含之聚合物成分之主成分(典型而言為包含超過50重量%之成分)。 (丙烯酸系聚合物) 作為上述丙烯酸系聚合物,例如較佳為包含(甲基)丙烯酸烷基酯作為主單體且可進而包含與該主單體具有共聚性之副單體之單體原料之聚合物。此處,所謂主單體,係指上述單體原料中占總單體成分超過50重量%之成分。 作為(甲基)丙烯酸烷基酯,例如可較佳地使用下述式(1)所表示之化合物。 CH2 =C(R1 )COOR2 (1) 此處,上述式(1)中之R1 為氫原子或甲基。又,R2 為碳原子數1~20之鏈狀烷基(以下,有時將此種碳原子數之範圍表示為「C1-20 」)。就黏著劑之儲存模數等觀點而言,較佳為R2 為C1-14 (例如C2-10 ,典型而言為C4-8 )之鏈狀烷基之(甲基)丙烯酸烷基酯,更佳為R1 為氫原子且R2 為C4-8 之鏈狀烷基之丙烯酸烷基酯。上述R2 為C1-20 之鏈狀烷基之(甲基)丙烯酸烷基酯可單獨使用1種,或可將2種以上組合使用。作為較佳之(甲基)丙烯酸烷基酯,可列舉丙烯酸正丁酯(BA)及丙烯酸2-乙基己酯(2EHA)。就黏著特性或加工性等觀點而言,更佳為BA。 總單體成分中之主單體之調配比率較佳為70重量%以上(例如85重量%以上,典型而言為90重量%以上)。主單體之調配比率之上限並無特別限定,較佳為設為99.5重量%以下(例如95重量%以下)。 與作為主單體之(甲基)丙烯酸烷基酯具有共聚性之副單體可發揮用於將交聯點導入至丙烯酸系聚合物或提高丙烯酸系聚合物之凝聚力之作用。作為副單體,例如可使用含羧基單體、含羥基單體、含酸酐基單體、含醯胺基單體、含胺基單體、含酮基單體、具有含氮原子環之單體、含烷氧基矽烷基單體、含醯亞胺基單體、含環氧基單體等含官能基單體之1種或2種以上。例如,就提高凝聚力之觀點而言,較佳為使含羧基單體及/或含羥基單體作為上述副單體共聚而成之丙烯酸系聚合物。作為上述含羧基單體之較佳例,可例示丙烯酸(AA)、甲基丙烯酸(MAA)等。作為上述含羥基單體,可列舉(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯類或不飽和醇類等。其中,較佳為(甲基)丙烯酸羥基烷基酯,更佳為丙烯酸2-羥基乙酯(HEA)、丙烯酸4-羥基丁酯(4HBA)。 上述副單體之量只要以實現所需之凝聚力之方式適當選擇即可,並無特別限定。通常,就平衡性良好地兼顧黏著力與凝聚力之觀點而言,副單體之量較合適為設為丙烯酸系聚合物之總單體成分中之0.5重量%以上,較佳為1重量%以上。又,副單體之量較合適為總單體成分中之30重量%以下,較佳為10重量%以下(例如5重量%以下)。於丙烯酸系聚合物中共聚有含羧基單體之情形時,含羧基單體之含量於丙烯酸系聚合物之合成所使用之總單體成分中,較合適為設為大約0.1重量%以上,較佳為0.5重量%以上,更佳為1重量%以上,又,較合適為設為大約15重量%以下,較佳為8重量%以下,更佳為5重量%以下。於丙烯酸系聚合物中共聚有含羥基單體之情形時,含羥基單體之含量於丙烯酸系聚合物之合成所使用之總單體成分中,較合適為設為大約0.001重量%以上,較佳為0.01重量%以上,更佳為0.05重量%以上,又,較合適為設為大約10重量%以下,較佳為5重量%以下,更佳為2重量%以下。藉此,可實現黏著力與凝聚力以更高之等級平衡之黏著劑。 亦可於此處所揭示之丙烯酸系聚合物中共聚上述以外之單體(其他單體)。上述其他單體例如可用於丙烯酸系聚合物之玻璃轉移溫度之調整、黏著性能(例如剝離性)之調整等目的。例如,作為可提高黏著劑之凝聚力之單體,可列舉含磺酸基單體、含磷酸基單體、含氰基單體、乙烯酯類、芳香族乙烯系化合物等。上述其他單體可單獨使用1種,亦可將2種以上組合使用。其中,可列舉乙烯酯類作為較佳例。作為乙烯酯類,具體而言,可例示乙酸乙烯酯(VAc)、丙酸乙烯酯、月桂酸乙烯酯等。其中,較佳為VAc。上述其他單體之含量於丙烯酸系聚合物之合成所使用之總單體成分中,較合適為設為大約30重量%以下,較佳為設為10重量%以下,又,較合適為設為0.01重量%以上(例如0.1重量%以上)。 上述丙烯酸系聚合物之共聚組成較合適為以該聚合物之玻璃轉移溫度(Tg)成為-15℃以下(典型而言為-70℃以上且-15℃以下)之方式設計,較佳為-25℃以下(例如-60℃以上且-25℃以下),更佳為-40℃以下(例如-60℃以上且-40℃以下)。就黏著力等觀點而言,較佳為將丙烯酸系聚合物之Tg設為上述上限值以下。 丙烯酸系聚合物之Tg可藉由適當改變單體組成(即該聚合物之合成所使用之單體之種類或使用量比)而進行調整。此處,所謂丙烯酸系聚合物之Tg,係指基於構成該聚合物之各單體之均聚物(homopolymer)之Tg及該單體之重量分率(重量基準之共聚比率)並根據福克斯(Fox)之式而求出之值。所謂福克斯之式,如以下所示,係共聚物之Tg與將構成該共聚物之單體之各者均聚而成之均聚物之玻璃轉移溫度Tgi之關係式。 1/Tg=Σ(Wi/Tgi) 再者,於上述福克斯之式中,Tg表示共聚物之玻璃轉移溫度(單位:K),Wi表示該共聚物中之單體i之重量分率(重量基準之共聚比率),Tgi表示單體i之均聚物之玻璃轉移溫度(單位:K)。作為均聚物之Tg,亦採用公知資料所記載之值。 於此處所揭示之技術中,作為上述均聚物之Tg,具體而言,使用以下之值。 丙烯酸2-乙基己酯 -70℃ 丙烯酸丁酯 -55℃ 乙酸乙烯酯 32℃ 丙烯酸 106℃ 甲基丙烯酸 228℃ 丙烯酸2-羥基乙酯 -15℃ 丙烯酸4-羥基丁酯 -40℃ 關於除上述所例示以外之均聚物之Tg,使用「Polymer Handbook」(第3版,John Wiley & Sons, Inc., 1989)所記載之數值。於上述Polymer Handbook中亦未記載之情形時,使用藉由日本專利特開2007-51271號公報所記載之測定方法所得之值。 獲得丙烯酸系聚合物之方法並無特別限定,可適當採用溶液聚合法、乳化聚合法、塊狀聚合法、懸浮聚合法等作為丙烯酸系聚合物之合成方法所已知之各種聚合方法。例如,可較佳地使用溶液聚合法。作為進行溶液聚合時之單體供給方法,可適當採用一次供給所有單體原料之一次添加方式、連續供給(滴加)方式、分批供給(滴加)方式等。聚合溫度可根據所使用之單體及溶劑之種類、聚合起始劑之種類等適當選擇,例如可設為20℃~170℃(典型而言為40℃~140℃)左右。或者,亦可採用照射UV等光而進行之光聚合(典型而言,於光聚合起始劑之存在下進行)或照射β射線、γ射線等放射線而進行之放射線聚合等活性能量線照射聚合。 溶液聚合所使用之溶劑(聚合溶劑)可自先前公知之有機溶劑中適當選擇。例如,可較佳地使用:甲苯等芳香族化合物類(典型而言為芳香族烴類);或乙酸乙酯、乙酸丁酯等乙酸酯類;己烷、環己烷、甲基環己烷等脂肪族或脂環式烴類等。 聚合所使用之起始劑可根據聚合方法之種類自先前公知之聚合起始劑適當選擇。例如可較佳地使用2,2'-偶氮雙異丁腈(AIBN)等偶氮系聚合起始劑之1種或2種以上。作為聚合起始劑之另一例,可列舉:過硫酸鉀等過硫酸鹽;過氧化苯甲醯、過氧化氫等過氧化物系起始劑;苯基取代乙烷等取代乙烷系起始劑;芳香族羰基化合物等。作為聚合起始劑之進而其他例,可列舉基於過氧化物與還原劑之組合之氧化還原系起始劑。此種聚合起始劑可單獨使用1種,或可將2種以上組合使用。聚合起始劑之使用量為通常之使用量即可,例如可自相對於總單體成分100重量份為0.005~1重量份(典型而言為0.01~1重量份)左右之範圍內選擇。 此處所揭示之基礎聚合物(較佳為丙烯酸系聚合物)之重量平均分子量(Mw)並無特別限定。就使凝聚力與黏著力以高等級平衡之觀點而言,基礎聚合物(較佳為丙烯酸系聚合物)之Mw較佳為10×104 以上,更佳為20×104 以上,進而較佳為35×104 以上。又,上述Mw較佳為500×104 以下,更佳為110×104 以下(例如75×104 以下),進而較佳為90×104 以下(例如65×104 以下)。此處,所謂Mw,係指藉由凝膠滲透層析法(GPC)所獲得之標準聚苯乙烯換算之值。作為GPC裝置,例如使用機型名「HLC-8320GPC」(管柱:TSKgel GMH-H(S),Tosoh公司製造)即可。於下述實施例中亦相同。 (橡膠系聚合物) 於另一較佳之一態樣中,上述黏著劑層係由橡膠系黏著劑構成。此處,所謂橡膠系黏著劑,係指含有橡膠系聚合物作為基礎聚合物之黏著劑。作為橡膠系聚合物,可列舉天然橡膠、苯乙烯丁二烯橡膠(SBR)、丙烯腈丁二烯橡膠(NBR)、異戊二烯橡膠、氯丁二烯橡膠、聚異丁烯、丁基橡膠、再生橡膠等。該等可單獨使用1種,或可將2種以上組合使用。 較佳之一態樣之橡膠系黏著劑含有單乙烯基取代芳香族化合物與共軛二烯化合物之嵌段共聚物作為基礎聚合物。所謂上述單乙烯基取代芳香族化合物,係指於芳香環鍵結有1個具有乙烯基之官能基之化合物。作為上述芳香環之代表例,可列舉苯環(可為經不具有乙烯基之官能基(例如烷基)取代之苯環)。作為上述單乙烯基取代芳香族化合物之具體例,可列舉苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙烯基二甲苯等。作為上述共軛二烯化合物之具體例,可列舉1,3-丁二烯、異戊二烯等。此種嵌段共聚物可單獨使用1種,或可將2種以上併用而用於基礎聚合物。 上述嵌段共聚物中之A鏈段(硬鏈段)較佳為上述單乙烯基取代芳香族化合物(可將2種以上併用)之共聚比率為70重量%以上(更佳為90重量%以上,亦可實質為100重量%)。上述嵌段共聚物中之B鏈段(軟鏈段)較佳為上述共軛二烯化合物(可將2種以上併用)之共聚比率為70重量%以上(更佳為90重量%以上,亦可實質為100重量%)。根據該嵌段共聚物,可實現更高性能之黏著片。 上述嵌段共聚物可為二嵌段體、三嵌段體、放射狀(radial)體、該等之混合物等形態。於三嵌段體及放射狀體中,較佳為於聚合物鏈之末端配置有A鏈段(例如苯乙烯嵌段)。其原因在於配置於聚合物鏈之末端之A鏈段容易聚集而形成域,藉此形成近似交聯結構而提高黏著劑之凝聚性。作為此處所揭示之技術中之嵌段共聚物,就對被黏著體之黏著力(剝離強度)或耐彎曲性之觀點而言,例如可較佳地使用二嵌段體比率為30重量%以上(更佳為40重量%以上,進而較佳為50重量%以上,尤佳為60重量%以上,典型而言為65重量%以上,例如70重量%以上)者。又,就對持續施加之應力之耐受性之觀點而言,可較佳地使用二嵌段體比率為90重量%以下(更佳為85重量%以下,例如80重量%以下)者。例如,較佳為使用二嵌段體比率為60~85重量%之嵌段共聚物。 (苯乙烯系嵌段共聚物) 於此處所揭示之技術之較佳之一態樣中,上述基礎聚合物係苯乙烯系嵌段共聚物。例如能夠以上述基礎聚合物包含苯乙烯異戊二烯嵌段共聚物及苯乙烯丁二烯嵌段共聚物之至少一者之態樣較佳地實施。較佳為黏著劑所包含之苯乙烯系嵌段共聚物中,苯乙烯異戊二烯嵌段共聚物之比率為70重量%以上,或苯乙烯丁二烯嵌段共聚物之比率為70重量%以上,或者苯乙烯異戊二烯嵌段共聚物與苯乙烯丁二烯嵌段共聚物之合計比率為70重量%以上。於較佳之一態樣中,上述苯乙烯系嵌段共聚物之實質全部(例如95~100重量%)係苯乙烯異戊二烯嵌段共聚物。於另一較佳之一態樣中,上述苯乙烯系嵌段共聚物之實質全部(例如95~100重量%)係苯乙烯丁二烯嵌段共聚物。根據此種組成,可更良好地發揮應用此處所揭示之技術之效果。 上述苯乙烯系嵌段共聚物可為二嵌段體、三嵌段體、放射狀(radial)體、該等之混合物等形態。於三嵌段體及放射狀體中,較佳為於聚合物鏈之末端配置有苯乙烯嵌段。其原因在於配置於聚合物鏈之末端之苯乙烯嵌段容易聚集而形成苯乙烯域,藉此形成近似交聯結構而提高黏著劑之凝聚性。作為於此處所揭示之技術中使用之苯乙烯系嵌段共聚物,就對被黏著體之黏著力(剝離強度)或耐彎曲性之觀點而言,例如可較佳地使用二嵌段體比率為30重量%以上(更佳為40重量%以上,進而較佳為50重量%以上,尤佳為60重量%以上,典型而言為65重量%以上)者。亦可為二嵌段體比率為70重量%以上(例如75重量%以上)之苯乙烯系嵌段共聚物。又,就保持力等觀點而言,可較佳地使用二嵌段體比率為90重量%以下(更佳為85重量%以下,例如80重量%以下)之苯乙烯系嵌段共聚物。例如,可較佳地採用二嵌段體比率為60~85重量%之苯乙烯系嵌段共聚物。 上述苯乙烯系嵌段共聚物之苯乙烯含量例如可為5~40重量%。就耐彎曲性或保持力等觀點而言,通常較佳為苯乙烯含量為10重量%以上(更佳為大於10重量%,例如12重量%以上)之苯乙烯系嵌段共聚物。又,就對被黏著體之黏著力之觀點而言,較佳為苯乙烯含量為35重量%以下(典型而言為30重量%以下,更佳為25重量%以下,例如未達20重量%)之苯乙烯系嵌段共聚物。例如,可較佳地採用苯乙烯含量為12重量%以上且未達20重量%之苯乙烯系嵌段共聚物。 (黏著賦予劑) 此處所揭示之黏著劑層可為包含黏著賦予劑之組成。作為黏著賦予劑,並無特別限制,例如可使用松香系黏著賦予樹脂、萜烯系黏著賦予樹脂、烴系黏著賦予樹脂、環氧系黏著賦予樹脂、聚醯胺系黏著賦予樹脂、彈性體系黏著賦予樹脂、酚系黏著賦予樹脂、酮系黏著賦予樹脂等各種黏著賦予樹脂。此種黏著賦予樹脂可單獨使用1種,或可將2種以上組合使用。 作為松香系黏著賦予樹脂之具體例,可列舉:松脂膠、木松香、妥爾油松香等未改性松香(生松香);藉由氫化、歧化、聚合等而將該等未改性松香改性而成之改性松香(氫化松香、歧化松香、聚合松香、其他經化學修飾之松香等,以下相同);其他各種松香衍生物等。作為上述松香衍生物之例,可列舉:藉由醇類使未改性松香酯化而成者(即松香之酯化物)、藉由醇類使改性松香酯化而成者(即改性松香之酯化物)等松香酯類;利用不飽和脂肪酸使未改性松香或改性松香改性而成之不飽和脂肪酸改性松香類;利用不飽和脂肪酸使松香酯類改性而成之不飽和脂肪酸改性松香酯類;對未改性松香、改性松香、不飽和脂肪酸改性松香類或不飽和脂肪酸改性松香酯類中之羧基進行還原處理而成之松香醇類;未改性松香、改性松香、各種松香衍生物等松香類(尤其是松香酯類)之金屬鹽;藉由利用酸觸媒使苯酚與松香類(未改性松香、改性松香、各種松香衍生物等)加成並進行熱聚合而獲得之松香酚樹脂等。於採用丙烯酸系聚合物作為基礎聚合物之情形時,較佳為使用松香系黏著賦予樹脂。就提高黏著力等黏著特性之觀點而言,更佳為自上述松香系黏著賦予樹脂中併用種類、特性(例如軟化點)等不同之2種或3種以上。 作為萜烯系黏著賦予樹脂之例,可列舉:α-蒎烯聚合物、β-蒎烯聚合物、雙戊烯聚合物等萜烯樹脂;使該等萜烯樹脂改性(苯酚改性、芳香族改性、氫化改性、烴改性等)而成之改性萜烯樹脂等。作為上述改性萜烯樹脂之例,可列舉萜烯改性苯酚樹脂、苯乙烯改性萜烯樹脂、芳香族改性萜烯樹脂、氫化萜烯樹脂等。於採用丙烯酸系聚合物作為基礎聚合物之情形時,較佳為使用萜烯系黏著賦予樹脂(例如萜烯改性苯酚樹脂)。尤其是就提高黏著力等黏著特性之觀點而言,較佳為自上述萜烯系黏著賦予樹脂(例如萜烯改性苯酚樹脂)中併用種類、特性(例如軟化點)等不同之1種或2種以上。 作為烴系黏著賦予樹脂之例,可列舉脂肪族系烴樹脂、芳香族系烴樹脂、脂肪族系環狀烴樹脂、脂肪族-芳香族系石油樹脂(苯乙烯-烯烴系共聚物等)、脂肪族-脂環族系石油樹脂、氫化烴樹脂、薰草咔系樹脂、薰草咔-茚系樹脂等各種烴系之樹脂。 於此處所揭示之技術中,作為上述黏著賦予樹脂,可較佳地使用軟化點(軟化溫度)大約為70℃以上(較佳為大約為100℃以上,更佳為大約110℃以上)者。根據包含具有上述下限值以上之軟化點之黏著賦予樹脂之黏著劑,可實現黏著力更優異之黏著片。可較佳地使用上述所例示之黏著賦予樹脂中具有上述軟化點之萜烯系黏著賦予樹脂(例如萜烯改性苯酚樹脂)、松香系黏著賦予樹脂(例如聚合松香之酯化物)等。黏著賦予樹脂之軟化點之上限並無特別限制,例如可設為大約200℃以下(典型而言為大約180℃以下)。再者,此處所言之黏著賦予樹脂之軟化點定義為藉由JIS K 5902及JIS K 2207之任一者所規定之軟化點試驗方法(環球法)所測得之值。 黏著賦予劑之使用量並無特別限制,可根據目標性能(黏著力或試劑保持性等)適當設定。例如,以固形物成分基準計,相對於基礎聚合物(例如丙烯酸系聚合物)100重量份,較合適為將黏著賦予劑設為大約10重量份以上,較佳為20重量份以上,更佳為30重量份以上,又,較合適為設為大約100重量份以下,較佳為80重量份以下,更佳為60重量份以下,進而較佳為50重量份以下。 (丙烯酸系低聚物) 此處所揭示之黏著劑組合物亦可包含丙烯酸系低聚物。藉由採用丙烯酸系低聚物,可平衡性良好地改善黏著力與耐彎曲性。又,於藉由活性能量線照射(例如UV照射)使黏著劑組合物硬化之態樣之情形時,丙烯酸系低聚物與例如松香系或萜烯系等黏著賦予樹脂相比,具有不易產生硬化阻礙(例如未反應單體之聚合阻礙)之優勢。再者,丙烯酸系低聚物係包含丙烯酸系單體作為其構成單體成分之聚合物,定義為Mw小於上述丙烯酸系聚合物之聚合物。 丙烯酸系低聚物之Mw並無特別限定,典型而言為0.1×104 ~3×104 左右。就提高黏著特性(例如黏著力或耐彎曲性)之觀點而言,丙烯酸系低聚物之Mw較佳為1.5×104 以下,更佳為1×104 以下,進而較佳為0.8×104 以下(例如0.6×104 以下)。又,就黏著劑之凝聚性等觀點而言,上述Mw較佳為0.2×104 以上(例如0.3×104 以上)。丙烯酸系低聚物之分子量可於聚合時視需要使用鏈轉移劑等進行調節。 於此處所揭示之黏著劑組合物包含丙烯酸系低聚物之情形時,丙烯酸系低聚物之含量較合適為相對於基礎聚合物(典型而言為丙烯酸系聚合物)100重量份設為例如0.5重量份以上。就使丙烯酸系低聚物之效果更良好地發揮之觀點而言,上述丙烯酸系低聚物之含量較佳為設為1重量份以上(例如5重量份以上,典型而言為10重量份以上)。又,就黏著劑組合物之硬化性或與基礎聚合物(典型而言為丙烯酸系聚合物)之相溶性等觀點而言,上述丙烯酸系低聚物之含量較合適為設為未達50重量份(例如未達30重量份),較佳為設為未達20重量份(例如未達15重量份)。 (交聯劑) 用於形成黏著劑層之黏著劑組合物較佳為包含交聯劑。交聯劑之種類並無特別限制,可自先前公知之交聯劑中適當選擇使用。作為此種交聯劑,例如可列舉異氰酸酯系交聯劑、環氧系交聯劑、㗁唑啉系交聯劑、氮丙啶系交聯劑、三聚氰胺系交聯劑、碳二醯亞胺系交聯劑、胺系交聯劑、過氧化物系交聯劑、金屬螯合物系交聯劑、金屬烷氧化物系交聯劑、金屬鹽系交聯劑等。交聯劑可單獨使用1種,或可將2種以上組合使用。就防止糊劑溢出或耐彎曲性之觀點而言,較佳為異氰酸酯系交聯劑、環氧系交聯劑、三聚氰胺系交聯劑,更佳為異氰酸酯系交聯劑、環氧系交聯劑,尤佳為併用異氰酸酯系交聯劑與環氧系交聯劑。 作為異氰酸酯系交聯劑之例,可列舉:甲苯二異氰酸酯、二甲苯二異氰酸酯等芳香族異氰酸酯;異佛酮二異氰酸酯等脂環族異氰酸酯;六亞甲基二異氰酸酯等脂肪族異氰酸酯等。更具體而言,可例示三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物(商品名「Coronate L」,Tosoh公司製造)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物(商品名「Coronate HL」,Tosoh公司製造)、六亞甲基二異氰酸酯之異氰尿酸酯體(商品名「Coronate HX」,Tosoh公司製造)等異氰酸酯加成物等。該等可單獨使用1種,或可將2種以上組合使用。 作為環氧系交聯劑之例,可列舉N,N,N',N'-四縮水甘油基間苯二甲胺(商品名「TETRAD-X」,三菱瓦斯化學公司製造)、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷(商品名「TETRAD-C」,三菱瓦斯化學公司製造)等。 作為三聚氰胺系交聯劑之例,可列舉六羥甲基三聚氰胺、丁基化三聚氰胺樹脂(商品名「SUPER BECKAMINE J-820-60N」,DIC公司製造)等。 上述黏著劑組合物所包含之交聯劑之量並無特別限定,就兼顧黏著力與凝聚力之觀點等而言,通常較合適為相對於基礎聚合物(典型而言為丙烯酸系聚合物)100重量份設為大約0.01重量份以上,較佳為0.02重量份以上(例如0.1重量份以上)。又,相對於基礎聚合物(典型而言為丙烯酸系聚合物)100重量份,通常較合適為設為大約10重量份以下,較佳為5重量份以下(例如3重量份以下)。於上述黏著劑組合物包含異氰酸酯系交聯劑作為交聯劑之情形時,異氰酸酯系交聯劑之含量較合適為相對於基礎聚合物(典型而言為丙烯酸系聚合物)100重量份設為0.1重量份以上,較佳為0.3重量份以上,更佳為0.5重量份以上。又,上述異氰酸酯系交聯劑之含量較合適為設為大約10重量份以下,較佳為5重量份以下,更佳為3重量份以下。於上述黏著劑組合物包含環氧系交聯劑作為交聯劑之情形時,環氧系交聯劑之含量較合適為相對於基礎聚合物(典型而言為丙烯酸系聚合物)100重量份設為0.0001重量份以上,較佳為0.001重量份以上,更佳為0.01重量份以上。又,上述環氧系交聯劑之含量較合適為設為大約1重量份以下,較佳為0.5重量份以下,更佳為0.1重量份以下。 (其他添加成分) 上述黏著劑組合物可視需要含有調平劑、交聯助劑、塑化劑、軟化劑、填充劑、著色劑(染料、顏料)、抗靜電劑、抗老化劑、紫外線吸收劑、抗氧化劑、光穩定劑等黏著劑組合物之領域中通常之各種添加劑。關於此種各種添加劑,可藉由常規方法使用先前公知者,由於並非為特別對本發明賦予特徵者,因此省略詳細之說明。 (黏著劑層之形成方法) 此處所揭示之黏著劑層可藉由先前公知之方法形成。例如,可採用藉由對具有剝離性之表面(剝離面)賦予黏著劑組合物並使之乾燥而形成黏著劑層之方法。或者,可採用藉由直接對膜狀基材賦予(典型而言塗佈)黏著劑組合物並使之乾燥而形成黏著劑層之方法(直接法)。又,亦可採用藉由對具有剝離性之表面(剝離面)賦予黏著劑組合物並使之乾燥而於該表面上形成黏著劑層,並將該黏著劑層轉印至膜狀基材之方法(轉印法)。作為上述剝離面,可利用剝離襯墊之表面。再者,此處所揭示之黏著劑層典型而言係連續地形成,但並不限定於此種形態,例如亦可為形成為點狀、條紋狀等規律或者無規之圖案之黏著劑層。 此處所揭示之黏著劑組合物之形態並無特別限定,例如可為有機溶劑中包含如上所述之組成之黏著劑(黏著成分)之形態(溶劑型)之黏著劑組合物、黏著劑分散於水性溶劑中之形態(水分散型,典型而言為水性乳膠型)之黏著劑組合物、熱熔型之黏著劑組合物、活性能量線硬化型之黏著劑組合物等。就容易實現較佳之黏著力或試劑保持性、耐彎曲性等之觀點而言,可較佳地採用溶劑型或水分散型之黏著劑組合物。就實現更高之黏著性能之觀點而言,尤佳為溶劑型之黏著劑組合物。典型而言,該溶劑型黏著劑組合物係製備成有機溶劑中包含上述各成分之溶液之形態。上述有機溶劑可自公知或慣用之有機溶劑中適當選擇。例如可使用選自甲苯、二甲苯等芳香族化合物類(典型而言為芳香族烴類);乙酸乙酯、乙酸丁酯等乙酸酯類;己烷、環己烷、甲基環己烷等脂肪族或脂環式烴類;1,2-二氯乙烷等鹵化烷烴類;甲基乙基酮、乙醯丙酮等酮類等之任1種溶劑或2種以上之混合溶劑。雖並無特別限定,但通常較合適為將上述溶劑型黏著劑組合物製備成固形物成分(NV)20~65重量%(例如25~55重量%)。若NV過低則存在製造成本容易增高之情況,若NV過高則存在塗佈性等操作性降低之情況。 黏著劑組合物之塗佈例如可使用凹版輥式塗佈機、模嘴塗佈機、棒式塗佈機等先前公知之塗佈機進行。或者,亦可藉由含浸或淋幕式塗佈法等塗佈黏著劑組合物。又,就促進交聯反應、提高製造效率等觀點而言,黏著劑組合物之乾燥較佳為於加熱下進行。乾燥溫度例如可設為40~150℃左右(較佳為60~130℃左右)。於使黏著劑組合物乾燥後,亦可以黏著劑層內之成分移動之調整、交聯反應之進行、可能存在於基材或黏著劑層內之變形之緩和等為目的而進行熟化。 於較佳之一態樣中,黏著劑層之凝膠分率為23%以上,更佳為25%以上。上述凝膠分率為特定值以上之黏著片於沖裁加工等加工後不存在糊劑之溢出,因此加工性優異。亦無損所切取之試驗片之外觀。又,不存在糊劑之溢出可於進行孔或毛細管形成等加工之試驗片用黏著片中成為有利之特徵。就試劑保持性之觀點而言,上述凝膠分率較合適為大約65%以下,較佳為55%以下,更佳為45%以下,進而較佳為35%以下(例如30%以下)。藉由使黏著劑層之凝膠分率為特定值以下,可較佳地防止收容於雙面黏著片內之試劑自黏著片之黏著面漏出之現象。進而,藉由使用具有上述範圍之凝膠分率之黏著劑層,耐彎曲性亦得以改善。黏著劑層之凝膠分率係利用下述實施例所記載之方法進行測定。 此處所揭示之黏著劑層之厚度並無特別限定,可根據目的適當選擇。通常,就黏著性能等觀點而言,黏著劑層之厚度較合適為大約1 μm以上,較佳為3 μm以上,更佳為5 μm以上,進而較佳為10 μm以上。又,就乾燥效率等生產性或試驗片尺寸等觀點而言,黏著劑層之厚度較合適為大約200 μm以下,較佳為100 μm以下,更佳為50 μm以下,進而較佳為30 μm以下(例如20 μm以下)。於基材之雙面具備黏著劑層之雙面黏著片之情形時,各黏著劑層之厚度可相同,亦可不同。 <基材> 於將此處所揭示之技術應用於附基材之雙面黏著片之情形時,作為基材,例如可適當選擇使用:PE膜、PP膜、乙烯-丙烯共聚物膜等聚烯烴系膜、PET膜等聚酯膜、聚氯乙烯膜等塑膠膜;包含聚胺基甲酸酯發泡體、PE發泡體、聚氯丁二烯發泡體等發泡體之發泡體片材;由各種纖維狀物質(可為麻、棉等天然纖維、聚酯、維尼綸等合成纖維、乙酸酯等半合成纖維等)之單獨或混紡等所得之織布及不織布(為包含日本紙、道林紙等紙類之概念);鋁箔、銅箔等金屬箔等。亦可使用包含羧甲基纖維素(CMC)等之親水性聚合物膜作為基材。作為上述塑膠膜,非延伸膜及延伸(單軸延伸或雙軸延伸)膜之任一者均可使用。其中,就尺寸穩定性、厚度精度、經濟性(成本)、沖裁加工等之加工性、拉伸強度等觀點而言,較佳為塑膠膜。塑膠膜之中,尤佳為聚酯膜。亦可對基材之表面實施底塗劑之塗佈、電暈放電處理等表面處理。 又,於較佳之一態樣中,基材可為著色成白色者。藉由使用白色基材,可成為容易確認有無污漬等附著物、清潔感優異、於衛生方面亦較佳者。具備白色基材之黏著片可較佳地用於以醫療目的使用之試驗片。又,白色基材具有容易視認採樣至試驗片之樣本之優勢。於樣本為血液樣本之情形時,樣本之視認性尤其優異。白色之程度(白度)以L*a*b*表色系統所規定之L*(明度)計,較佳為87以上(例如87~100),更佳為90以上(例如90~100)。L*a*b*表色系統所規定之a*或b*可分別根據L*之值適當選擇。作為a*或b*,例如較佳為兩者均為-10~10(更佳為-5~5,進而較佳為‑2.5~2.5)之範圍。再者,於本說明書中,L*a*b*表色系統所規定之L*、a*、b*係藉由使用色彩色差計(例如,美能達公司製造之色彩色差計,商品名「CR-200」)進行測定而求出。再者,L*a*b*表色系統係國際照明委員會(CIE)於1976年推薦且稱為CIE1976(L*a*b*)表色系統之顏色空間。又,L*a*b*表色系統於日本工業標準中係由JIS Z 8729規定。 作為將基材著色成白色時所使用之白色著色劑,例如可列舉:氧化鈦(金紅石型二氧化鈦、銳鈦礦型二氧化鈦等二氧化鈦)、氧化鋅、氧化鋁、氧化矽、氧化鋯、氧化鎂、氧化鈣、氧化錫、氧化鋇、氧化銫、氧化釔、碳酸鎂、碳酸鈣(輕質碳酸鈣、重質碳酸鈣等)、碳酸鋇、碳酸鋅、氫氧化鋁、氫氧化鈣、氫氧化鎂、氫氧化鋅、矽酸鋁、矽酸鎂、矽酸鈣、硫酸鋇、硫酸鈣、硬脂酸鋇、鋅白、硫化鋅、滑石、黏土、高嶺土、磷酸鈦、雲母、石膏、白碳、矽藻土、膨潤土、鋅鋇白、沸石、絹雲母、多水高嶺土等無機系白色著色劑,或丙烯酸系樹脂粒子、聚苯乙烯系樹脂粒子、聚胺基甲酸酯系樹脂粒子、醯胺系樹脂粒子、聚碳酸酯系樹脂粒子、聚矽氧系樹脂粒子、脲-福馬林系樹脂粒子、三聚氰胺系樹脂粒子等有機系白色著色劑等。白色著色劑之使用量並無特別限定,設為以可賦予所需之光學特性(典型而言為白度)之方式適當調整之量即可。 基材之厚度可根據目的適當選擇,一般而言,較合適為大致1 μm以上,就強度或加工性之觀點而言,較佳為2 μm以上,更佳為3 μm以上。又,基材之厚度通常較合適為設為500 μm以下(典型而言為200 μm以下)。於將此處所揭示之附基材之黏著片用於可攜帶之小尺寸之試驗片之情形時,基材之厚度較佳為100 μm以下,更佳為50 μm以下,進而較佳為30 μm以下(例如20 μm以下)。於較佳之一態樣中,附基材之雙面黏著片中之基材之厚度為15 μm以下(例如10 μm以下,典型而言為7 μm以下)。具備此種較薄之基材之黏著片可尤佳地利用於較薄之試驗片。 <雙面黏著片之總厚> 此處所揭示之技術中之雙面黏著片之總厚(不含剝離襯墊之雙面黏著片之厚度)並無特別限定。例如,可使用具有大約10 μm以上之厚度之雙面黏著片。就發揮良好之黏著特性(黏著力等)之觀點而言,雙面黏著片之厚度較佳為15 μm以上(典型而言為25 μm以上)。又,雙面黏著片之厚度通常大約為300 μm以下(例如200 μm以下)左右。於將此處所揭示之雙面黏著片用於可攜帶之小尺寸之試驗片之情形時,雙面黏著片之總厚較佳為100 μm以下,更佳為70 μm以下,進而較佳為50 μm以下(例如40 μm以下)。具有上述總厚之雙面黏著片例如尤其適合用作發揮作為規定樣本向試驗片之採樣量之間隔片之功能的雙面黏著片。可成為良好地應對分析精度之提高所伴隨之樣本採樣量之降低者。 <附剝離襯墊之雙面黏著片之特性> 此處所揭示之雙面黏著片較佳為該雙面黏著片之第1黏著面及/或第2黏著面(較佳為第1黏著面及第2黏著面之兩者)顯示出4 N/20 mm以上之180度剝離強度(亦簡稱為「黏著力」)。具有上述黏著力之雙面黏著片作為接著面積較小之試驗片用黏著片可發揮良好之接合強度。上述黏著力更佳為6 N/20 mm以上,進而較佳為7 N/20 mm以上,尤佳為8 N/20 mm以上(例如8.5 N/20 mm以上)。上述180度剝離強度係使用不鏽鋼板作為被黏著體,使2 kg之輥往返1次而將黏著片之黏著面壓接於該被黏著體表面,放置30分鐘後,依據JIS Z 0237於剝離角度180度、拉伸速度300 mm/min之條件下測定。更詳細而言,係利用下述實施例所記載之方法測定。 於較佳之一態樣中,雙面黏著片之第1黏著面之襯墊剝離力(對第1剝離襯墊之剝離強度)可未達1 N/50 mm(例如0.5 N/50 mm以下,典型而言為0.4 N/50 mm以下)。同樣地,上述雙面黏著片之第2黏著面之襯墊剝離力(對第2剝離襯墊之剝離強度)較佳為未達1 N/50 mm(例如0.5 N/50 mm以下,典型而言為0.4 N/50 mm以下)。襯墊剝離力被限制為特定值以下之雙面黏著片容易去除剝離襯墊,故而貼附時之作業性優異。又,考慮到若上述襯墊剝離力過小則存在作業性降低之情況,雙面黏著片之第1黏著面之襯墊剝離力及/或第2黏著面之襯墊剝離力較佳為大約0.01 N/50 mm以上。進而,為了防止於將一剝離襯墊去除時連另一剝離襯墊亦被去除之現象,較佳為使第1黏著面之襯墊剝離力與第2黏著面之襯墊剝離力不同。於按照第1剝離襯墊、第2剝離襯墊之順序將剝離襯墊剝離而使用黏著片之態樣中,較佳為將對第1剝離襯墊之剝離強度設定為低於對第2剝離襯墊之剝離強度。上述襯墊剝離力係於23℃、50%RH之環境下,依據JIS Z 0237於剝離角度180度、拉伸速度300 mm/min之條件下測定。更詳細而言,係利用下述實施例所記載之方法測定。 較佳之一態樣之雙面黏著片於利用下述方法而進行之耐彎曲性評價試驗中,端部浮升距離(高度)未達3 mm(更佳為未達1 mm)。尤佳為於上述耐彎曲性評價試驗中端部未浮升。又,較佳之一態樣之雙面黏著片於利用下述方法進行之糊劑溢出防止性評價試驗中,糊劑之溢出量未達0.1 mm(更佳為0.09 mm以下,進而較佳為0.06 mm以下)。 此處所揭示之黏著片於較佳之一態樣中,於將黏著片於150℃下保持30分鐘時,自該片材散發之甲苯之量(甲苯散發量)可為該黏著劑層每1 g為20 μg以下。甲苯散發量被抑制為特定值以下之黏著片由於釋氣量被抑制,故而不存在令人不愉快之臭味而可舒適地使用。此種黏著片例如可尤佳地用於以醫療用或健康促進為目的之生物樣本(例如血液樣本)分析用試驗片。上述甲苯散發量更佳為黏著劑層每1 g為10 μg以下,進而較佳為3 μg以下(例如1 μg以下,典型而言為0.3 μg以下)。作為上述甲苯散發量,只要採用利用下述方法所測得之值即可。 [甲苯散發量測定] 將黏著片切成1 cm×1 cm之大小並將剝離襯墊剝離而使黏著面露出後,將使該黏著面貼合於鋁箔而成者作為樣本。於將該樣本放入至20 mL之小玻璃瓶中並拴緊後,將該小玻璃瓶以150℃加熱30分鐘,藉由頂空自動取樣器將加熱狀態之氣體1.0 mL注入至氣相層析(GC)測定裝置中並測定甲苯之量,算出上述樣本所包含之黏著劑層每1 g之甲苯散發量(μg/g)。 此時,氣相層析條件係設為如下所述。 ・載氣:氦氣 ・管柱:無極性毛細管柱 ・管柱溫度:升溫速度10℃/min 升溫後維持之溫度(低溫)40~300℃ ・管柱頭壓:113 kPa(40℃) ・檢測器:FID(flame ionization detector,火焰游離偵測器)(溫度250℃) 再者,定量只要使用氣體量已知之含甲苯之氣體製作校準曲線,並基於該校準曲線算出即可。具體而言,只要基於甲苯換算之校準曲線將升溫開始後至經過20分鐘所出現之各波峰之總面積換算成重量而定量甲苯氣體之散發量即可。 <雙面黏著片之用途> 此處所揭示之雙面黏著片可用於用以分析樣本之試驗片(樣本分析用試驗片)。於本說明書中,所謂「試驗片」係定義為用於分析樣本者(亦稱為測試條)。例如,可為具有對樣本進行採樣(典型而言,收集及/或保持)之功能者。典型而言,此處所揭示之試驗片係可放置於具有分析功能之各種樣本測定設備之構件(與測定設備一併使用之構件),藉此進行樣本之分析。試驗片較佳可為具有分析樣本之功能(例如,利用化學反應等而使來自樣本之資訊(例如成分濃度)成為可檢測之狀態之功能)之感測器。此處,成為分析對象之樣本並無特別限定,例如可列舉全血、血漿、血清、唾液、尿、腦脊液等生物樣本。又,樣本亦可為各種食品類或飲料水、排水、雨水等。樣本之形態並無特別限定,較佳為於常溫下呈液狀之樣本。又,分析目的亦並無特別限定,例如可為血液中之葡萄糖濃度等樣本中之特定成分之濃度測定等。於樣本為血液樣本之情形時,作為分析對象物,除上述葡萄糖以外,亦可列舉白蛋白或乳酸、膽紅素、膽固醇等成分。此處所揭示之技術中之黏著片可較佳地用於用以分析生物樣本(較佳為血液樣本)之試驗片(以下,亦稱為生物感測器)。 使用試驗片之樣本分析例如可藉由將保持有樣本之試驗片放置於樣本測定設備而進行。此種樣本測定設備例如可為以醫療或健康促進為目的之可攜帶之小尺寸測定設備(例如生物樣本測定設備)。此處所揭示之試驗片(例如醫療用試驗片)可為具有裝卸自如地連接於如上所述之生物樣本測定設備之結構(形狀、尺寸等)者。典型而言,此種試驗片可為拋棄式試驗片(典型而言,亦稱為條(stripe)或片(chip))。作為上述試驗片之使用態樣之一例,可列舉如下所述之使用態樣:攜帶收容有複數個試驗片之盒體與上述測定設備,於適當之時間點進行樣本分析,並廢棄使用過之試驗片。以下,參照圖式,對作為此處所揭示之雙面黏著片之適當之使用對象的血糖濃度測定用之試驗片(生物感測器)及使用此處所揭示之附剝離襯墊之黏著片的上述試驗片之製造方法進行說明,但此處所揭示之技術並不限定於此。 如圖3所示,試驗片100具備基板110、被覆層120、及配置於基板110與被覆層120之間之雙面黏著片11。試驗片100之形狀可表現為長條平板狀。於該實施形態中,基板110為樹脂製之基板,且具有樹脂板與絕緣層之積層結構。基板只要形成下述電極之面由具有絕緣性之材料構成即可,亦可整體由絕緣材料構成。作為構成基板之材料,可例示PET等聚酯、PE或PP等聚烯烴、尼龍等聚醯胺、聚碳酸酯、聚醯亞胺、聚苯乙烯、聚甲基丙烯酸甲酯、丙烯腈-丁二烯-苯乙烯樹脂(ABS樹脂)、氟樹脂等有機材料(典型而言為樹脂)、玻璃等無機材料。該等可單獨使用1種,或可將2種以上組合使用。 於基板110之表面,帶狀之電極116以具有特定間隔之方式配置成條紋狀,藉此於基板110之表面形成電極圖案。該等電極116係用於檢測藉由分析對象物與試劑之反應而產生之電流者。電極之材質只要為導電性材料即可,例如可較佳地使用碳電極。由於如上所述在基板110之表面形成有電極圖案,故而基板110之表面具有凹凸。 雙面黏著片11具有附基材之雙面黏著片之形態,將基板110與被覆層120接合,並且亦發揮作為基板110與被覆層120之間之間隔片之功能。又,於雙面黏著片11,於試驗片100之長度方向之一端設置有コ字狀之缺口。由該缺口形成之空間(換言之,由位於上述缺口之周圍之雙面黏著片11與覆蓋其上下之基板110及被覆層120所包圍之空間)係發揮作為於試驗片100之長度方向之一端具有開口(樣本導入口)152之毛細管部150之功能。於該毛細管部150內保持自開口152導入之血液樣本。再者,於該實施形態中,毛細管部150之寬度(亦可為缺口之寬度)大約為1 mm左右,毛細管部150之深度大約為5 mm左右。 被覆層120之材質並無特別限定,自作為可用於基板110之材料而例示者中選擇適當者使用即可。或者,就提高分析精度之觀點而言,亦可使用由CMC等親水性聚合物構成之親水性膜。 簡明而言,試驗片100例如係以如下方式用於樣本之分析。即,自位於試驗片100之一端之開口152藉由毛細現象,將作為分析對象之血液樣本導入至毛細管部150內。於試驗片100之內部,於與毛細管部150連通之部位配置有試劑180。試劑180於該實施形態中,收容於形成於雙面黏著片11之孔160。試劑180於收容於試驗片100時,於常溫(例如25℃)下為液狀,藉由其後之處理等而以凝膠狀、將該液狀物乾燥擔載之狀態或包含於層狀構件等之狀態等各種形態配置於試驗片100內。該試劑180藉由與導入至毛細管部150內之血液樣本中之分析對象物(典型而言為葡萄糖)進行電化學反應而產生電流。將該狀態之試驗片100放置於測定設備之試驗片插入口,並於該設備內測定藉由上述反應而產生之電流值,藉此算出血液樣本中之葡萄糖濃度。 作為收容於試驗片之試劑,可根據分析對象物適當選擇與分析對象物進行電化學反應或者顯色反應等之公知或慣用者使用。例如,於如上所述測定血糖濃度之情形時,使用包含與葡萄糖反應之氧化還原酶及電子傳遞介質之試劑。作為可包含於試劑之氧化還原酶,並無特別限定,根據分析對象物,可例示NADH(nicotinamide adenine dinucleotide hydride,氫化菸醯胺腺嘌呤二核苷酸)氧化酶(例如黃遞酶)、乙醇氧化酶、葡萄糖氧化酶、葡萄糖脫氫酶、乳酸氧化酶、乳酸脫氫酶、膽固醇氧化酶、膽紅素氧化酶等。電子傳遞介質亦並無特別限定,可根據所使用之酶等使用鐵氰化鉀、對苯醌、啡&#134116;甲基硫酸鹽、二茂鐵衍生物等。試劑中亦可包含水溶性高分子、填充劑等任意之添加成分。典型而言,注入試驗片時之試劑包含溶劑,例如可為於溶劑中包含上述氧化還原酶、電子傳遞介質等成分之溶液之形態。作為試劑用之溶劑,並無特別限定,可列舉將水(蒸餾水、超純水等)設為主成分(包含最多之成分,典型而言為包含超過50重量%之成分)之水系溶劑或磷酸緩衝液等緩衝液、乙醇等醇類、二甲基亞碸、四氫呋喃等有機溶劑等。 上述試劑於製造試驗片時,典型而言,係利用下述方法收容於試驗片內部。具體而言,如圖4所示,準備兩黏著面經剝離襯墊覆蓋之雙面黏著片11,將一剝離襯墊(此處為第1剝離襯墊)剝離而使一黏著面(此處為第1黏著面)露出,將該露出之黏著面(第1黏著面)貼合於基板110。作為所使用之附剝離襯墊之黏著片,例如使用上述圖1所示之附剝離襯墊之黏著片1。於該附剝離襯墊之黏著片(例如圖1之附剝離襯墊之黏著片1)預先設置有至少貫通第2剝離襯墊32與雙面黏著片11之孔160,孔160於第2剝離襯墊32之背面32B開口。此時,貼附於基板110上之雙面黏著片11係其第2黏著面(上表面)經第2剝離襯墊32覆蓋之狀態。於該狀態下,自第2剝離襯墊32之背面32B將試劑180注入至試驗片1內部。具體而言,將試劑180注入至於第2剝離襯墊32之背面32B開口之孔160。典型而言,試劑180係以液體之狀態注入。即便於在該注入操作中未能高精度地將試劑180注入至孔160而試劑180附著於第2剝離襯墊32之背面32B上之情形時,由於第2剝離襯墊32之背面32B之水接觸角為70°以上,因此未注入試劑無損失地殘留於第2剝離襯墊32之背面32B上。可藉由利用滴管等進行誘導而將該殘留未注入試劑裝入至孔160。於將試劑180裝入至孔160內後,自雙面黏著片11剝離第2剝離襯墊32,並將被覆層貼合於雙面黏著片11之第2黏著面,藉此獲得如圖3所示之具有包含基板110、雙面黏著片11及被覆層120之積層結構之試驗片1。再者,於試驗片亦可在被覆層(典型而言為親水性膜)之上進而設置裝飾層或用以固定裝裝飾層之接著劑層(例如黏著劑層)。 此處所揭示之試驗片之大小並無特別限制,只要根據測定設備或根據所需之樣本量等適當設定即可。例如,可對於長度15~50 mm(例如20~40 mm)左右、寬度3~15 mm(例如4~10 mm)左右、最大厚度100~2000 μm(例如300~600 μm)左右之試驗片較佳地使用此處所揭示之雙面黏著片。又,影響毛細管部之容積之基板與被覆層之間隔(即間隔片之厚度)通常為200 μm以下左右,較佳為120 μm以下(例如70 μm以下,典型而言為50 μm以下)。間隔片之厚度例如於上述實施形態之構成中為雙面黏著片之總厚。 具有如上所述之構成之試驗片例如係藉由於片狀之基板之表面形成複數個電極圖案,經由雙面黏著片積層被覆層而獲得積層結構後,將該積層結構沖裁成複數個(例如10個以上)之試驗片形狀而製作。電極圖案可適當採用網版印刷等公知之方法形成。試劑向試驗片之注入可如上所述於被覆層之積層之前進行。又,沖裁加工係使用公知或慣用之加工機進行。試驗片所使用之雙面黏著片較佳為具有良好地密接於作為被黏著體之電極形成基板與被覆層而不會產生可能導致樣本漏出之剝落等不良情況之性能(典型而言為黏著力、試劑保持性等性能)。例如,較佳為具有下述程度之耐彎曲性:即便於在將採集有樣本之試驗片放置於測定設備之試驗片插入口時,試驗片卡在上述插入口附近而彎曲之情形時,亦良好地維持試驗片構成構件之接合狀態。進而,期待試驗片用之黏著片於上述沖裁加工時或將藉由沖裁加工而一體化之複數個試驗片逐個分離(典型而言切割)時,黏著劑不會自切斷端面溢出。 實施例 以下,對與本發明相關之若干實施例進行說明,但並不意圖將本發明限定於該實施例所示者。再者,於以下之說明中,只要無特別說明,則「份」及「%」為重量基準。 <評價方法> [水接觸角] 使用市售之接觸角測定裝置並依據JIS R 3257:1999於下述條件下測定剝離襯墊(第2剝離襯墊)背面之水接觸角。 (水接觸角測定條件) 測定裝置:接觸角測定器 FACE CA-X型(協和界面化學公司製造) 測定環境:23℃、50%RH 測定液體:蒸餾水 測定時間:滴落1500 ms後 [表面自由能] 表面自由能γ係由下述式:γ=γd +γp +γh 所表示之值。此處,上述式中之γd 、γp 及γh 分別表示表面自由能之分散成分、極性成分及氫鍵成分。剝離襯墊(第2剝離襯墊)背面之表面自由能γ係將水、二碘甲烷及1-溴萘用作探測液,根據各探測液之接觸角並依據北崎-畑式(日本接著協會志,Vol.8, No.3, 1972, pp.131-141)而求出。接觸角係使用市售之接觸角計而測定。 [180度剝離強度] 自各例之附剝離襯墊之雙面黏著片將一剝離襯墊剝離,使一黏著面露出,並將厚度25 μm之PET膜貼合於該露出之黏著面。將其切割成寬度20 mm、長度150 mm之尺寸而作為評價用樣品。自該評價用樣品將另一剝離襯墊剝離,使上述測定樣品之另一黏著面(測定對象黏著面)露出,於23℃、50%RH之環境下,使2 kg之輥往返1次而將該另一黏著面壓接於被黏著體之表面。將其於相同環境下放置30分鐘後,使用萬能拉伸壓縮試驗機(裝置名「TCM-1kNB」,Minebea公司製造)並依據JIS Z 0237以剝離角度180度、拉伸速度300 mm/min之條件測定剝離強度(N/20 mm寬)。使用不鏽鋼板(SUS304板)作為被黏著體。 [襯墊剝離力] 將各例之附剝離襯墊之雙面黏著片切割成寬度50 mm、長度150 mm之尺寸而作為評價用樣品。針對該評價用樣品,使用拉伸試驗機(裝置名「TCM-1kNB」,Minebea公司製造)於23℃、RH50%之環境下以剝離角度180度、拉伸速度300 mm/min之條件測定將剝離襯墊自雙面黏著片之黏著面剝離時之剝離強度,並將其最高值設為剝離強度(N/50 mm寬)。測定係針對第1黏著面(對第1剝離襯墊之剝離力)與第2黏著面(對第2剝離襯墊之剝離力)之雙面進行。 [黏著劑層之凝膠分率] 自各例之黏著片採集約0.1 g(重量W1)之黏著劑,利用平均孔徑0.2 μm之多孔質聚四氟乙烯(PTFE)膜(重量W2)包成荷包狀,並利用風箏線(重量W3)將口紮緊。將該捆包物浸漬於乙酸乙酯50 mL中,於室溫(典型而言為23℃)下保持7天而僅使黏著劑層中之凝膠成分溶出至上述膜外後,將上述捆包物取出並擦去附著於外表面之乙酸乙酯,使該捆包物以130℃乾燥1小時,測定該捆包物之重量(W4)。將各值代入以下之式,藉此求出黏著劑層之凝膠分率(%)。 凝膠分率(%)=[(W4-W2-W3)/W1]×100 作為上述多孔質PTFE膜,使用可自日東電工公司獲取之商品名「NITOFLON NTF1122」(平均孔徑0.2 μm、氣孔率75%、厚度85 μm)。 [液體回收性] 將各例之附剝離襯墊之雙面黏著片切割成寬度10 mm、長度100 mm之尺寸,將第1剝離襯墊剝離,並將不鏽鋼(SUS)板貼附於露出之第1黏著面。針對以如上方式獲得之評價用樣品,如圖5所示,以SUS板212側朝下之方式將評價用樣品200載置於30度傾斜面。評價用樣品200係以其長度方向成為傾斜面之上下方向(傾斜方向)之方式配置。於在評價用樣品200中配置於上方之第2剝離襯墊216之背面216B之上方側端部配置一滴(3~5 μL左右)純水220,使用滴管,一面使水滴附著於滴管之前端,一面向下方(圖5中之箭頭方向)直線狀地滑動移動50 mm。再者,於圖5中,符號214表示雙面黏著片。容易使水滴移動之背面成為容易使剝離襯墊背面上之試劑移動而容易進行試劑之回收注入之背面,因此於可使第2剝離襯墊216之背面216B上之水滴之總量移動之情形時評價為「○」,於未能使總量移動之情形時評價為「×」。 [液體保持性] 將各例之附剝離襯墊之雙面黏著片切割成寬度10 mm、長度40 mm之尺寸,並於其長度方向之一端側形成直徑2 mm之孔。繼而,自雙面黏著片剝離第1剝離襯墊,並將白色PET板貼附於露出之第1黏著面。自第2剝離襯墊背面之開口將著色成紅色之水(著色水)滴加一滴(3~5 μL左右)至以如上方式獲得之評價用樣品之孔中,並如圖6所示以第2剝離襯墊316側朝上之方式將評價用樣品300載置於30度傾斜面。評價用樣品300係以其長度方向成為傾斜面之上下方向(傾斜方向)之方式配置。於該狀態下放置1天後,對雙面黏著片314中之孔330內之著色水320之狀態進行觀察。於著色水320未自孔330漏出之情形時評價為「○」,於著色水320自孔330漏出之情形(即自PET板312與雙面黏著片314之間流出之情形)時評價為「×」。 [耐彎曲性] 將各例之附剝離襯墊之雙面黏著片切割成寬度10 mm、長度50 mm之尺寸,將切割成相同尺寸之厚度100 μm之PET板貼附(襯底)於剝離第2剝離襯墊而露出之第2黏著面,獲得評價用之PET襯底雙面黏著片。又,於厚度1 mm之樹脂板(PET板)之一表面貼合厚度50 μm之銅膜,並切割成寬度10 mm、長度70 mm之尺寸而獲得試驗用被黏著體(Cu樹脂積層板)。自試驗用之PET襯底雙面黏著片剝離第1剝離襯墊而使第1黏著面露出,於23℃、RH50%之環境下,使用層壓機將上述第1黏著面與試驗用被黏著體之銅膜面之長度方向之中心對準並將兩者壓接,將其作為試驗片。繼而,使用治具如圖7所示般以試驗片400之長度方向之弦長成為50 mm之方式使試驗片400彎曲成圓弧狀。試驗片400係以襯底PET板412側凸出之方式彎曲。將其於相同環境下保持1天,並對上述試驗片400之雙面黏著片414之端部之接著狀態進行觀察。於雙面黏著片414追隨試驗用被黏著體420之銅膜424表面之情形時評價為「○」,於雙面黏著片414之端部自試驗用被黏著體420鼓起而確認到剝落之情形時評價為「×」。再者,於圖7中,符號422表示試驗用被黏著體400之樹脂板。 [糊劑溢出防止性] 將各例之附剝離襯墊之雙面黏著片切割成10 mm×30 mm之尺寸,將一剝離襯墊剝離,將丙烯酸系樹脂板貼附於露出之黏著面,並以丙烯酸系樹脂板側成為下方之方式載置。另一剝離襯墊未剝離而直接殘留,將鋁板載置於該剝離襯墊之上,獲得如圖8所示自下依序積層丙烯酸系樹脂板512、雙面黏著片514、剝離襯墊516及鋁板520而成之評價用樣品500。針對該評價用樣品500,自上方賦予10 MPa之壓力(圖8中之箭頭方向)1分鐘,並自上方藉由顯微鏡觀察而測定剛釋放壓力後糊劑(雙面黏著片514之黏著劑)自剝離襯墊端面之溢出距離之最大值(mm)。若糊劑之溢出量(溢出距離之最大值)成為0.1 mm以上,則加工性降低,因此於糊劑之溢出量未達0.1 mm之情形時評價為「○」,於上述溢出量為0.1 mm以上之情形時評價為「×」。 <例1> (黏著劑組合物(A)之製備) 向具備攪拌機、溫度計、氮氣導入管、回流冷凝器、滴液漏斗之反應容器中添加BA 100份、VAc 5份、AA 3份、HEA 0.1份、作為聚合起始劑之AIBN 0.3份、及作為聚合溶劑之甲苯,於60℃下進行溶液聚合6小時而獲得丙烯酸系聚合物(A)之甲苯溶液。該丙烯酸系聚合物(A)之Mw為55×104 。 相對於上述甲苯溶液所包含之丙烯酸系聚合物(A)100份,以固形物成分基準計,添加聚合松香季戊四醇酯(商品名「HARITACK PCJ」,哈利瑪化成公司製造,軟化點118~128℃)10份、氫化松香甘油酯(商品名「HARITACK SE10」,哈利瑪化成公司製造,軟化點75~85℃)10份、氫化松香甲酯(商品名「Foralyn 5020F」,Eastman Chemical公司製造)5份、萜烯改性苯酚系樹脂(商品名「SUMILITE RESIN PR-12603N」,住友電木公司製造)15份作為黏著賦予樹脂,添加異氰酸酯系交聯劑(商品名「Coronate L」,Tosoh公司製造)2份及環氧系交聯劑(商品名「TETRAD-C」,三菱瓦斯化學公司製造)0.025份作為交聯劑,獲得丙烯酸系黏著劑組合物(A)。 (黏著片之製作) 準備單面經剝離處理而成為剝離面之厚度38 μm之聚酯製剝離膜(商品名「DIAFOIL MRF」,三菱聚酯公司製造)作為第1剝離襯墊。又,準備一面(正面)藉由聚矽氧系剝離處理劑(商品名「KS-3703T」,信越化學工業公司製造,熱硬化性加成型)經剝離處理而成為剝離面,另一面(背面)藉由聚矽氧系撥水處理劑(商品名「KS-847T」,信越化學工業公司製造,熱硬化性加成型)經撥水處理而成為撥水面之厚度75 μm之聚酯製剝離膜作為第2剝離襯墊。 於第1剝離襯墊之剝離面及第2剝離襯墊之剝離面之各者塗佈黏著劑組合物(A),以100℃乾燥2分鐘,而於各剝離襯墊上形成厚度13 μm之黏著劑層。將形成於上述2片剝離襯墊上之黏著劑層分別貼合於厚度5 μm之PET製基材膜(商品名「Lumirror」,Toray公司製造)之第1面及第2面,製作本例之附基材之雙面黏著片。該雙面黏著片係具備基材、設置於基材之第1面之第1黏著劑層、及設置於基材之第2面之第2黏著劑層的雙面黏著片,上述第1黏著劑層之黏著面(第1黏著面)由第1剝離襯墊保護,上述第2黏著劑層之黏著面(第2黏著面)由第2剝離襯墊保護。 <例2> 使用藤森工業公司製造之剝離膜(商品名「FILMBYNA NT」)作為第2剝離襯墊,並對正面側實施與例1相同之剝離處理,藉此獲得具有剝離面(正面)與撥水面(背面)之剝離膜。除此以外,以與例1相同之方式獲得本例之附剝離襯墊之雙面黏著片。 <例3> 使用東洋鋁公司製造之撥水性材料(商品名「TOYAL LOTUS」)作為第2剝離襯墊並設置撥水面,又,對正面側實施與例1相同之剝離處理,藉此獲得具有剝離面(正面)與撥水面(背面)之剝離膜。除此以外,以與例1相同之方式獲得本例之附剝離襯墊之雙面黏著片。 <例4> (黏著劑組合物(B)之製備) 向具備攪拌機、溫度計、氮氣導入管、回流冷凝器、滴液漏斗之反應容器中添加作為單體成分之BA 70份、2EHA 30份、AA 3份及4HBA 0.05份、作為聚合起始劑之AIBN 0.08份、及作為聚合溶劑之乙酸乙酯,並於氮氣氣流中於65℃下進行溶液聚合3.5小時而獲得丙烯酸系聚合物(B)之溶液。 於上述丙烯酸系聚合物(B)之溶液中,相對於丙烯酸系聚合物(B)100份,以固形物成分基準計,調配作為黏著賦予樹脂之聚合松香酯(商品名「PENSEL D125」,荒川化學工業公司製造,軟化點125℃)30份、異氰酸酯系交聯劑(商品名「Coronate L」,Tosoh公司製造)3份,製備丙烯酸系黏著劑組合物(B)。 (黏著片之製作) 準備單面經剝離處理而成為剝離面之厚度38 μm之聚酯製剝離膜(商品名「DIAFOIL MRF」,三菱聚酯公司製造)作為第1剝離襯墊。又,準備僅單面(正面)經剝離處理而成為剝離面之厚度75 μm之聚酯製剝離膜作為第2剝離襯墊。於第1剝離襯墊之剝離面及第2剝離襯墊之剝離面之各者塗佈黏著劑組合物(B),以100℃乾燥2分鐘,而於各剝離襯墊上形成厚度13 μm之黏著劑層。除此以外,以與例1相同之方式製作本例之附基材之雙面黏著片。 <例5> (黏著劑組合物(C)之製備) 向具備攪拌機、溫度計、氮氣導入管、回流冷凝器、滴液漏斗之反應容器中添加作為單體成分之BA 95份及AA 5份、作為聚合起始劑之AIBN 0.2份、及作為聚合溶劑之甲苯,於氮氣氣流中於60℃下進行溶液聚合6小時而獲得丙烯酸系聚合物(C)之溶液。 於上述丙烯酸系聚合物(C)之溶液中,相對於丙烯酸系聚合物(C)100份,以固形物成分基準計,添加丙烯酸系低聚物15份、異氰酸酯系交聯劑(商品名「Coronate L」,Tosoh公司製造)1份、環氧系交聯劑(商品名「TETRAD-C」,三菱瓦斯化學公司製造)0.075份,獲得丙烯酸系黏著劑組合物(C)。 作為丙烯酸系低聚物,使用以如下方法製備者。具體而言,向具備攪拌機、溫度計、氮氣導入管、回流冷凝器、滴液漏斗之反應容器中添加甲基丙烯酸環己酯95份、AA 5份及α-甲基苯乙烯二聚物(商品名「Nofmer MSD」,日油公司製造)10份、作為聚合起始劑之AIBN 10份、及作為聚合溶劑之甲苯,於氮氣氣流中攪拌1小時而將聚合體系內之氧去除後,升溫至85℃,反應5小時而獲得固形物成分濃度50%之丙烯酸系低聚物。所獲得之丙烯酸系低聚物之重量平均分子量為4300。 (黏著片之製作) 使用黏著劑組合物(C)代替黏著劑組合物(B),除此以外,以與例4相同之方式獲得本例之附剝離襯墊之雙面黏著片。 於將上述所獲得之各例之附剝離襯墊之雙面黏著片於23℃、50%RH之環境下熟化1日後,對各雙面黏著片進行上述評價試驗。將結果示於表1。 [表1] 如表1所示,於具備第1剝離襯墊與第2剝離襯墊之附剝離襯墊之雙面黏著片中,第2剝離襯墊背面之水接觸角為70°以上之例1~3之黏著片可實現液體回收。另一方面,於第2剝離襯墊背面之水接觸角未達70°之例4、5中,液體回收性不合格。根據該結果得知,具備第1剝離襯墊與第2剝離襯墊並且第1剝離襯墊背面及第2剝離襯墊背面中之一個背面之水接觸角為70°以上的附剝離襯墊之雙面黏著片於用於樣本分析用試驗片之製造時,可防止試驗片製造時之試劑損失。 又,黏著劑層之凝膠分率為25%~55%之例1~3之黏著片可兼具液體保持性及糊劑溢出防止性。又,確認到與凝膠分率為上述範圍外之例4、5相比,耐彎曲性亦優異之傾向。根據該結果得知,黏著劑層之凝膠分率為25%~55%之黏著片於用於樣本分析用試驗片之情形時,可於試驗片內良好地保持試劑。又,認為使用上述黏著片之試驗片於沖裁加工時等不存在糊劑之溢出,即便於試驗片彎曲之情形時亦可良好地維持構成構件之接合狀態。滿足上述特性之黏著片尤其適於樣本分析用試驗片用途。 以上,對本發明之具體例詳細地進行了說明,但該等僅為例示,並不限定申請專利範圍。申請專利範圍所記載之技術包含對以上所例示之具體例進行各種變化、變更而成者。 [交叉引用] 本案主張基於2016年4月8日申請之日本專利申請2016-78325號之優先權,該申請之全部內容係作為參照而組入至本說明書中。Hereinafter, preferred embodiments of the present invention will be described. In addition, the practitioner can understand the content necessary for the implementation of the present invention other than the matters specifically mentioned in the present specification based on the teachings about the implementation of the invention and the technical common sense at the time of application. The present invention can be implemented based on the contents disclosed in this specification and technical common sense in the field. In the drawings below, members and parts that perform the same function will be described with the same reference numerals, and overlapping descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are modeled to clearly illustrate the present invention, and do not accurately indicate the size or reduction ratio of the adhesive sheet or test piece actually provided as a product. In this specification, "adhesive" refers to a material that has a state of being a soft solid (viscoelastic body) at a temperature region near room temperature, and is simply adhered to the adherend by pressure. . The adhesives referred to herein are as defined in "CA Dahlquist," Adhesion: Fundamental and Practice ", McLaren & Sons, (1966) P. 143", and generally have an elastic modulus E that satisfies the complex stretch. * (1 Hz) <10 7 dyne / cm 2 Materials (typically materials having the above properties at 25 ° C). <Configuration Example of Adhesive Sheet with Release Liner> The adhesive sheet with release liner disclosed herein has, for example, a cross-sectional structure as shown in FIG. 1. The adhesive sheet 1 with a release liner includes a double-sided adhesive sheet (double-sided adhesive sheet) 11. The double-sided adhesive sheet 11 includes a plastic film as a substrate 15 and a first adhesive layer 21 and a second adhesive layer 22 which are supported by both sides of the substrate 15, respectively. More specifically, a first adhesive layer 21 and a second adhesive layer 22 are provided on the first surface 15A and the second surface 15B (both of which are non-peelable) of the substrate 15, respectively. In addition, the adhesive sheet 1 with a release liner includes a first adhesive surface covering the double-sided adhesive sheet 11 (the adhesive surface of the first adhesive layer 21, a surface located on the side opposite to the substrate 15 side) 21A first peeling. The liner 31 and the second release liner 32 covering the second adhesive surface of the double-sided adhesive sheet 11 (the adhesive surface of the second adhesive layer 22 on the surface opposite to the substrate 15 side) 22A. In the double-sided adhesive sheet 11 before use (before attaching to an adherend), the first adhesive surface 21A of the first adhesive layer 21 is a surface (front surface) 31A on the side of the first adhesive surface 21A becoming a release surface. The first release liner 31 is protected. The second adhesive surface 22A of the second adhesive layer 22 is protected by a second release liner 32 in which a surface (front surface) 32A on the side of the second adhesive surface 22A is a release surface. The back surface (the surface opposite to the front surface 31A) 31B of the first release liner 31 constitutes the outer surface of the adhesive sheet 1 with the release liner. Moreover, the back surface (surface on the side opposite to the front surface 32A) 32B of the second release liner 32 also forms the outer surface of the adhesive sheet 1 with a release liner in the same manner as the back surface 31B of the first release liner 31. The technology disclosed here can be better applied to the double-sided adhesive sheet with a substrate shown in FIG. 1, and also can be applied to the double-sided adhesive without a substrate (that is, without a substrate) shown in FIG. 2. Sheet 12. As shown in FIG. 2, the double-sided adhesive sheet 12 before use is in the form of an adhesive sheet 2 with a release liner. It has an adhesive layer 20 without a substrate, and has a first adhesive surface (adhesive layer 20) covering it. The first peeling pad 31 of 20A and the second peeling surface covering it (the other sticking surface of the adhesive layer 20, the sticking surface located on the side opposite to the first sticking surface 20A), the second peeling of 20B垫 32。 The pad 32. The first adhesive surface 20A of the double-sided adhesive sheet 12 composed of the baseless adhesive layer 20 is protected by the first release liner 31 where the surface (front surface) 31A on the side of the first adhesive surface 20A becomes the release surface. The second adhesive surface 20B of the double-sided adhesive sheet 12 is protected by a second release liner 32 whose surface (front surface) 32A on the side of the second adhesive surface 20B is a release surface. <The first release liner and the second release liner> The technology disclosed here is characterized by any of the first release liner and the second release liner (hereinafter, collectively referred to as "release liner" in some cases). The water contact angle of the back surface (surface opposite to the side surface (front surface) of the adhesive layer) is 70 ° or more. Therefore, when a test piece is manufactured, even if a reagent is to be injected into a hole opened on the back surface of the first release liner or the second release liner, at least a part of the reagent is not injected into the hole. The injected reagent will not be wetted, diffused or absorbed, and will remain in the form of droplets on the back surface of the release liner. For example, by inclining the release liner or transferring the droplets using an inducing mechanism such as a dropper, and introducing the uninjected reagent (droplet) remaining on the back surface of the release liner into the well, the loss of the reagent can be prevented. Sometimes the operation of recovering the reagents that have not been injected in the injection operation and loading them into the required wells is called recovery injection and re-injection with new reagent droplets into the same wells. Inject to distinguish. In addition, the back surface of the release liner adjusted so that the water contact angle becomes 70 ° or more of water repellency as described above may be referred to as the back surface of the release liner whose water contact angle is less than 70 °. Water-based back). The above-mentioned water contact angle can be adjusted by selection of materials constituting the back surface of the release liner, surface treatment, and the like. The water contact angle of the back surface (water-repellent back surface) of the release liner was measured by the method described in the following examples. The water contact angle of one of the first release liner back surface and the second release liner back surface (water-repellent back surface) is preferably 90 ° or more (typically more than 90 °), more preferably 100 ° or more, and more preferably It is preferably 120 ° or more (for example, 130 ° or more). If the water contact angle is too large, liquid droplets may move too easily on the back surface of the first release liner and fall off from the back surface. Therefore, the water contact angle is preferably about 160 ° or less (for example, 150 ° or less). Furthermore, the water contact angle between the back surface of the first release liner and the other back surface of the second release liner may be less than 70 °, and may be 70 ° or more. The surface free energy of one of the first release liner back surface and the second release liner back surface (water-repellent back surface) disclosed herein is preferably less than 40 mJ / m 2 . This makes it easy to prevent loss of reagents. The above surface free energy is preferably 30 mJ / m 2 Below, more preferably 20 mJ / m 2 Below (e.g. 15 mJ / m 2 the following). From the viewpoint of reagent recoverability, the above surface free energy is more preferably 7 mJ / m 2 Above (e.g. 10 mJ / m 2 the above). In addition, the surface free energy of the back surface of the first release liner and the other back surface of the second release liner may not exceed 40 mJ / m. 2 , Also 40 mJ / m 2 the above. The surface free energy of the back surface (water-repellent back surface) of a release liner was calculated | required by the method as described in the following Example. As the release liner having a water-repellent back surface among the first release liner and the second release liner, a release liner having a front surface as a release surface and a back surface as a water-repellent surface is typically used. As a preferable example of such a release liner, the thing which performed the peeling process and the water repellent process on the release liner base material is mentioned. The release liner may be one that has been subjected to a release treatment on one surface of the release liner substrate and a water repellent treatment to the other surface. In a typical aspect, the release liner having a water-repellent back surface includes a release liner substrate (a release treatment object and a water repellency treatment object) as a support, and a release treatment layer provided on one surface of the substrate. And a water repellent treatment layer provided on the other surface of the substrate. The material of the release liner substrate disclosed herein is not particularly limited. For example, a single layer body (such as a plastic film) or a laminated body formed of plastic, paper, various fibers, or the like can be used. In addition, in this specification, a "plastic film" is typically a non-porous film, and is a concept different from a so-called non-woven fabric or woven fabric. Examples of the plastic film include polyolefins such as polyethylene (PE) and polypropylene (PP); polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and poly (p-phenylene) Films of polyesters such as succinate (PBT); polyamides (so-called nylons); celluloses (so-called selefen). Plastic films can be non-stretchable or stretched (uniaxially stretched or biaxially stretched). As the paper substrate, for example, Japanese paper, foreign paper, dory paper, cellophane, kraft paper, stretch paper, crepe paper, clay coated paper, top coat paper, synthetic paper, and the like can be used. The basis weight of the paper substrate is not particularly limited, and it is generally suitable to use 50 to 100 g / m 2 Left and right. Examples of the various fiber substrates include various fibrous substances (which may be any of natural fibers, semi-synthetic fibers, and synthetic fibers, such as cotton fibers, rayon staple fibers, manila hemp, pulp, cotton, acetate fibers, polyacrylic Ester fibers, polyvinyl alcohol fibers, polyamide fibers, polyolefin fibers, etc.) woven or non-woven fabrics obtained by singly or blending. Examples of the base material including other materials include: rubber sheet materials including natural rubber, butyl rubber, and the like; foaming of foams including foamed polyurethane, foamed polychloroprene rubber, and the like Body sheet materials; aluminum foil, copper foil and other metal foils; such composites. As a laminated body, the paper (for example, Dowling paper) laminated | stacked with the plastic film (for example, PE resin) on both sides is mentioned, for example. As a preferable release liner substrate mentioned above, a polyester film is mentioned, and a PET film is more preferable among them. Corresponding to the above release liner substrate, various surface modification treatments such as corona discharge treatment, plasma treatment, and primer coating may be performed on the surface on which the release treatment layer or water repellent treatment layer is provided. Various surface processing. In addition, if necessary, fillers (inorganic fillers, organic fillers, etc.), anti-aging agents, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, colorants (pigments, dyes, etc.), etc. Various additives. The water-repellent back surface of the release liner disclosed herein can be formed using a water-repellent treatment agent such as a polysiloxane-based water-repellent treatment agent, a fluorine-based water-repellent treatment agent, or a long-chain alkyl-type water-repellent treatment agent. As such a water repellent treatment agent, those who can be used as a peeling treatment agent can select and use a water contact angle satisfying 70 ° or more based on technical common sense. Among them, a polysiloxane-based water repellent treatment agent is preferred. Alternatively, a water-repellent back surface can also be obtained by using the material of the self-releasing liner base material based on technical common sense and selecting a material whose water contact angle becomes 70 ° or more. For example, it is also possible to peel off olefin-based resins (for example, PE, PP, ethylene-propylene copolymer, PE / PP mixture), fluorine-based polymers (for example, polytetrafluoroethylene, polyvinylidene fluoride), and silicone rubber. The liner substrate is used as a release liner without subjecting the surface of the substrate to a water repellent treatment. In this case, the back surface of the release liner can be a water-repellent back surface without being subjected to a water-repellent treatment. As the polysiloxane-based water repellent treatment agent used in a preferred aspect, there is no particular limitation, and various polysiloxane-based materials that can achieve a water contact angle of 70 ° or more can be used. For example, heat-hardening properties (typically, heat-hardening properties) are given after application, and heat is applied by applying heat or free radiation (ultraviolet rays, alpha rays, beta rays, gamma rays, neutron rays, electron beams, etc.). Molding) polysiloxane based water repellent treatment agent, free radiation hardening (typically UV (ultraviolet, ultraviolet) hardening) polysiloxane based water repellent treatment agent, etc. These can be used individually by 1 type or in combination of 2 or more types. From the viewpoints of economical efficiency and simplicity of a device required for coating, a thermosetting (typically, thermosetting addition molding) polysiloxane-based water repellent treatment agent can be preferably used. The water repellent treatment agent may be any of a solvent-free type without a solvent, and a solvent type dissolved or dispersed in an organic solvent. In addition, it can also be used by mixing an appropriate amount of a solvent with a relatively low surface tension in a solvent-free water repellent treatment agent and adjusting the viscosity in a manner that is easy to impart (typically coating). Furthermore, a catalyst such as a platinum-based catalyst for improving reactivity can be added to the polysiloxane-based water repellent treatment agent such as the thermosetting property as described above. From the viewpoint of environmental sanitation or reduction of VOC (volatile organic compounds) when the water-repellent treatment layer is formed, it is preferable to use a solvent-free type that substantially contains no organic solvent and can be directly applied in this state. . The polysiloxane-based water repellent treatment agent as described above can be obtained from, for example, Yuesu Chemical Industry Co., Ltd. Examples of the method for forming the water-repellent treatment layer of the release liner disclosed herein include, for example, applying a water-repellent treatment agent such as a polysiloxane-based water-repellent treatment agent to the substrate of the release liner using various applicators, and drying it. Method for forming water repellent treatment layer. The coating machine can be appropriately selected from, for example, a direct gravure coater, an offset gravure coater, a roll coater, a bar coater, a die coater, and the like. There are no particular restrictions on the drying conditions, and drying conditions suitable for the water repellent treatment agent to be used can be appropriately selected. Usually, the drying temperature is about 80-150 ° C. In the case where the release liner disclosed herein has a water-repellent treatment layer, the thickness of the water-repellent treatment layer is not particularly limited. From the viewpoint of sufficiently obtaining water repellency, the thickness of the water repellent treatment layer is, for example, more preferably about 0.03 μm or more, and more preferably about 0.05 μm or more. From the viewpoints of film formability and cost, the thickness is, for example, about 5 μm or less (typically 3 μm or less). The application amount of the water-repellent treatment agent can be appropriately selected according to the type of the release liner substrate used, the type of the water-repellent treatment agent, and the like. For example, it is more suitable to be 0.01 g / m in terms of solid content. 2 Above, preferably 0.05 g / m 2 Above, more preferably 0.1 g / m 2 Above, more preferably 0.5 g / m 2 Above, more suitable is about 10 g / m 2 Below, preferably 7 g / m 2 Below, more preferably 5 g / m 2 Below, more preferably 4 g / m 2 the following. The release surface of the release liner disclosed herein can be formed by a conventional method using a known or conventional release treatment agent (for example, a release treatment agent such as a silicone-based, fluorine-based, or long-chain alkyl-based release treatment agent). For example, a PE resin surface of a forest paper laminated with a PE resin or a release surface obtained by subjecting a surface of a polyester release liner substrate to a release treatment using a polysiloxane-based release treatment agent can be preferably used. In addition, for example, an olefin-based resin (for example, PE, PP, an ethylene-propylene copolymer, and a PE / PP mixture), a fluoro-based polymer (for example, polytetrafluoroethylene, polyvinylidene fluoride), or silicone rubber can be formed. The release liner substrate is used as a release liner without performing a release treatment on the surface of the substrate. In this case, the surface (typically, the front surface) of the release liner can be a release surface without performing a release treatment. As a method for forming the release treatment layer of the release liner disclosed herein, a conventionally known method can be adopted. For example, the release liner substrate may be coated with a release treatment agent (for example, a silicone release treatment agent) as described above on the release liner substrate using various coaters, and dried to form a release treatment layer. As the above-mentioned coating machine, an example can be appropriately selected and exemplified as a coating machine which can be used in the formation of the water-repellent treatment layer. The drying conditions are not particularly limited, and the drying conditions suitable for the peeling treatment agent to be used can be appropriately selected. When the release liner disclosed herein has a release-treated layer, the thickness of the release-treated layer is not particularly limited. From the viewpoint of obtaining sufficient peelability, the thickness of the peeling treatment layer is, for example, preferably about 0.03 μm or more, and more preferably about 0.05 μm or more. From the viewpoints of film formability and cost, the thickness is, for example, about 5 μm or less (typically 3 μm or less). From the viewpoints of workability and the like, the thickness of the release liner disclosed herein is more preferably about 20 μm or more, preferably 30 μm or more (for example, 50 μm or more, and further 60 μm or more), and the thickness is more than The thickness is suitably about 200 μm or less, and preferably 160 μm or less (for example, 100 μm or less). The thickness of the first release liner and the second release liner may be the same or different. In a state where the release liner is peeled off in the order of the first release liner and the second release liner and an adhesive sheet is used, it is preferable that the thickness of the first release liner is thinner than that of the second release liner. Thereby, the peeling workability of the 1st release liner and the sticking workability of an adhesive sheet are improved. In addition, by providing the second release liner with a thickness to increase rigidity, it is easy to support the adhesive sheet with the second release liner after the first release liner is peeled off. <Adhesive layer> The adhesive layer disclosed here (in the case of a double-sided adhesive sheet with a base material, the first adhesive layer and the second adhesive layer are included, the same applies hereinafter) is known in the field of including an adhesive Acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, polysiloxane polymers, polyamide polymers, fluorine polymers, etc. One or two or more kinds of various rubber-like polymers are used as the base polymer. The details will be described below. The adhesive layer disclosed herein is preferably an acrylic adhesive layer containing an acrylic polymer as a base polymer or a rubber adhesive layer containing a rubber polymer as a base polymer. . Alternatively, it may be an adhesive layer in which an acrylic polymer and a rubber polymer are used as a base polymer. (Acrylic Adhesive Layer) In a preferred aspect, the above-mentioned adhesive layer is in terms of characteristics (typically, adhesion or bending resistance, reagent retention, etc.), molecular design, and stability over time. Is an acrylic adhesive layer containing an acrylic polymer as a base polymer. In addition, in this specification, the "base polymer" of an adhesive means the main component of the polymer component contained in this adhesive (typically, it contains a component exceeding 50 weight%). (Acrylic polymer) As the acrylic polymer, for example, a monomer raw material containing an alkyl (meth) acrylate as a main monomer and further containing a sub-monomer having copolymerizability with the main monomer is preferable. Of polymers. Here, the main monomer refers to a component that accounts for more than 50% by weight of the total monomer components in the monomer raw material. As the alkyl (meth) acrylate, for example, a compound represented by the following formula (1) can be preferably used. CH 2 = C (R 1 COOR 2 (1) Here, R in the above formula (1) 1 Is a hydrogen atom or a methyl group. Again, R 2 Is a chain alkyl group having 1 to 20 carbon atoms (hereinafter, the range of such carbon atoms may be expressed as "C 1-20 "). From the viewpoint of the storage modulus of the adhesive, R is preferred 2 For C 1-14 (E.g. C 2-10 , Typically C 4-8 (Meth) acrylic acid alkyl ester of chain alkyl group, more preferably R 1 Is a hydrogen atom and R 2 For C 4-8 An alkyl acrylate of a chain alkyl group. Above R 2 For C 1-20 The (meth) acrylic acid alkyl ester of a chain alkyl group may be used individually by 1 type, and may be used in combination of 2 or more type. Preferred alkyl (meth) acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA). From the viewpoints of adhesion properties and processability, BA is more preferable. The blending ratio of the main monomer in the total monomer component is preferably 70% by weight or more (for example, 85% by weight or more, and typically 90% by weight or more). The upper limit of the blending ratio of the main monomer is not particularly limited, but is preferably set to 99.5% by weight or less (for example, 95% by weight or less). A secondary monomer having a copolymerizability with the alkyl (meth) acrylate which is a main monomer can play a role of introducing a crosslinking point to an acrylic polymer or improving the cohesive force of the acrylic polymer. As the secondary monomer, for example, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acid anhydride group-containing monomer, a fluorene-containing amino group-containing monomer, an amine-containing monomer, a ketone-group-containing monomer, or a monomer having a nitrogen atom ring One or two or more kinds of functional group-containing monomers, such as a polymer, an alkoxy-containing silane-based monomer, a fluorene-imide-containing monomer, and an epoxy-containing monomer. For example, from the viewpoint of improving cohesion, an acrylic polymer obtained by copolymerizing a carboxyl group-containing monomer and / or a hydroxyl group-containing monomer as the above-mentioned secondary monomer is preferred. Preferred examples of the carboxyl group-containing monomer include acrylic acid (AA) and methacrylic acid (MAA). Examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate Hydroxyalkyl (meth) acrylates such as butyl ester and 4-hydroxybutyl (meth) acrylate, unsaturated alcohols, and the like. Among them, hydroxyalkyl (meth) acrylate is preferred, and 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA) are more preferred. The amount of the above-mentioned secondary monomer is not particularly limited as long as it is appropriately selected so as to achieve the required cohesion. Generally, from the viewpoint of balance between adhesion and cohesion with good balance, the amount of the sub-monomer is more preferably 0.5% by weight or more, and more preferably 1% by weight or more of the total monomer component of the acrylic polymer. . The amount of the sub-monomer is more preferably 30% by weight or less, and preferably 10% by weight or less (for example, 5% by weight or less) of the total monomer components. When a carboxyl group-containing monomer is copolymerized in an acrylic polymer, the content of the carboxyl group-containing monomer is more preferably about 0.1% by weight or more in the total monomer component used in the synthesis of the acrylic polymer. It is preferably 0.5% by weight or more, more preferably 1% by weight or more, and more preferably about 15% by weight or less, more preferably 8% by weight or less, and even more preferably 5% by weight or less. When a hydroxyl-containing monomer is copolymerized in the acrylic polymer, the content of the hydroxyl-containing monomer is more preferably about 0.001% by weight or more in the total monomer component used in the synthesis of the acrylic polymer. It is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and more preferably about 10% by weight or less, more preferably 5% by weight or less, and even more preferably 2% by weight or less. Thereby, an adhesive with a higher level of adhesion and cohesion can be achieved. A monomer other than the above (other monomers) may be copolymerized in the acrylic polymer disclosed herein. The other monomers described above can be used, for example, for the purpose of adjusting the glass transition temperature of an acrylic polymer and adjusting the adhesive properties (for example, peelability). For example, as a monomer which can improve the cohesiveness of an adhesive agent, a sulfonic acid group containing monomer, a phosphate group containing monomer, a cyano group containing monomer, a vinyl ester, an aromatic vinyl compound, etc. are mentioned. These other monomers may be used alone or in combination of two or more. Among them, vinyl esters are mentioned as preferable examples. Specific examples of the vinyl esters include vinyl acetate (VAc), vinyl propionate, vinyl laurate, and the like. Among these, Vac is preferred. The content of the other monomers is more preferably about 30% by weight or less, more preferably 10% by weight or less, and more preferably about 10% by weight of the total monomer components used in the synthesis of the acrylic polymer. 0.01% by weight or more (for example, 0.1% by weight or more). The copolymerization composition of the acryl-based polymer is suitably designed such that the glass transition temperature (Tg) of the polymer becomes -15 ° C or lower (typically -70 ° C or higher and -15 ° C or lower), and preferably- 25 ° C or lower (for example, -60 ° C or higher and -25 ° C or lower), more preferably -40 ° C or lower (for example, -60 ° C or higher and -40 ° C or lower). From the viewpoints of adhesion and the like, it is preferable to set the Tg of the acrylic polymer to the above-mentioned upper limit value or less. The Tg of the acrylic polymer can be adjusted by appropriately changing the monomer composition (that is, the type or amount ratio of the monomers used in the synthesis of the polymer). Here, the Tg of the acrylic polymer refers to the weight fraction (copolymerization ratio based on weight) based on the Tg of the homopolymer of each monomer constituting the polymer and the weight of the monomer, and according to Fox ( Fox). The formula of Fox is as follows, which is the relationship between the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer. 1 / Tg = Σ (Wi / Tgi) In the above formula of Fox, Tg represents the glass transition temperature (unit: K) of the copolymer, and Wi represents the weight fraction (weight) of the monomer i in the copolymer. The basic copolymerization ratio), Tgi represents the glass transition temperature (unit: K) of the homopolymer of monomer i. As the Tg of the homopolymer, a value described in known data is also used. In the technique disclosed here, as the Tg of the homopolymer, specifically, the following values are used. 2-ethylhexyl acrylate-70 ℃ butyl acrylate-55 ℃ vinyl acetate 32 ℃ acrylic acid 106 ℃ methacrylic acid 228 ℃ 2-hydroxyethyl acrylate -15 ℃ 4-hydroxybutyl acrylate -40 ℃ For the Tg of the homopolymer other than those exemplified, the values described in "Polymer Handbook" (3rd Edition, John Wiley & Sons, Inc., 1989) were used. When it is not described in the above-mentioned Polymer Handbook, the value obtained by the measurement method described in Japanese Patent Laid-Open No. 2007-51271 is used. The method for obtaining an acrylic polymer is not particularly limited, and various polymerization methods known as a method for synthesizing an acrylic polymer, such as a solution polymerization method, an emulsion polymerization method, a block polymerization method, and a suspension polymerization method, can be appropriately used. For example, a solution polymerization method can be preferably used. As a method for supplying a monomer when performing solution polymerization, a one-time addition method for supplying all monomer raw materials at a time, a continuous supply (dropwise addition) method, a batchwise supply (dropwise addition) method, and the like can be suitably adopted. The polymerization temperature can be appropriately selected according to the type of the monomers and solvents used, the type of the polymerization initiator, and the like, and can be set to, for example, about 20 ° C to 170 ° C (typically 40 ° C to 140 ° C). Alternatively, photopolymerization (typically, in the presence of a photopolymerization initiator) by irradiation of light such as UV or active energy ray irradiation polymerization such as radiation polymerization by irradiation of beta rays or gamma rays may be used. . The solvent (polymerization solvent) used in the solution polymerization can be appropriately selected from previously known organic solvents. For example, aromatic compounds such as toluene (typically aromatic hydrocarbons); or acetates such as ethyl acetate and butyl acetate; hexane, cyclohexane, and methylcyclohexane can be preferably used. And other aliphatic or alicyclic hydrocarbons. The initiator used in the polymerization can be appropriately selected from previously known polymerization initiators according to the type of the polymerization method. For example, one or two or more azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) can be preferably used. As another example of the polymerization initiator, persulfates such as potassium persulfate; peroxide-based initiators such as benzamidine peroxide and hydrogen peroxide; substituted ethane-based initiators such as phenyl substituted ethane Agents; aromatic carbonyl compounds, etc. As still another example of the polymerization initiator, a redox-based initiator based on a combination of a peroxide and a reducing agent is mentioned. Such a polymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more type. The amount of the polymerization initiator used may be a normal amount, and for example, it can be selected from a range of about 0.005 to 1 part by weight (typically 0.01 to 1 part by weight) with respect to 100 parts by weight of the total monomer component. The weight average molecular weight (Mw) of the base polymer (preferably an acrylic polymer) disclosed herein is not particularly limited. From the viewpoint of balancing cohesion and adhesion at a high level, the Mw of the base polymer (preferably an acrylic polymer) is preferably 10 × 10 4 Above, more preferably 20 × 10 4 Above, more preferably 35 × 10 4 the above. The Mw is preferably 500 × 10. 4 Below, more preferably 110 × 10 4 Following (e.g. 75 × 10 4 Below), more preferably 90 × 10 4 Following (e.g. 65 × 10 4 the following). Here, Mw refers to a standard polystyrene conversion value obtained by gel permeation chromatography (GPC). As the GPC device, for example, the model name "HLC-8320GPC" (column: TSKgel GMH-H (S), manufactured by Tosoh Corporation) may be used. The same applies to the following examples. (Rubber-based polymer) In another preferred aspect, the adhesive layer is composed of a rubber-based adhesive. Here, the rubber-based adhesive refers to an adhesive containing a rubber-based polymer as a base polymer. Examples of the rubber-based polymer include natural rubber, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), isoprene rubber, chloroprene rubber, polyisobutylene, butyl rubber, Recycled rubber, etc. These can be used individually by 1 type or in combination of 2 or more types. A preferred aspect of the rubber-based adhesive contains a block copolymer of a monovinyl-substituted aromatic compound and a conjugated diene compound as a base polymer. The aforementioned monovinyl-substituted aromatic compound refers to a compound having a functional group having a vinyl group bonded to an aromatic ring. As a representative example of the aromatic ring, a benzene ring (a benzene ring substituted with a functional group (for example, an alkyl group) having no vinyl group) may be mentioned. Specific examples of the monovinyl-substituted aromatic compound include styrene, α-methylstyrene, vinyl toluene, and vinyl xylene. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, and the like. Such a block copolymer may be used individually by 1 type, and may use 2 or more types together for a base polymer. The A segment (hard segment) in the block copolymer is preferably 70% by weight or more (more preferably 90% by weight or more) of the copolymerization ratio of the monovinyl-substituted aromatic compound (can be used in combination of two or more types). , Can also be substantially 100% by weight). The B segment (soft segment) in the block copolymer is preferably a copolymerization ratio of the conjugated diene compound (two or more types can be used in combination) of 70% by weight or more (more preferably 90% by weight or more). It may be substantially 100% by weight). According to this block copolymer, a higher-performance adhesive sheet can be realized. The block copolymer may be in the form of a diblock body, a triblock body, a radial body, a mixture of these, and the like. In the triblock body and the radial body, an A segment (for example, a styrene block) is preferably arranged at the end of the polymer chain. The reason for this is that the A segments arranged at the ends of the polymer chains easily aggregate to form domains, thereby forming an approximate cross-linked structure and improving the cohesiveness of the adhesive. As the block copolymer in the technology disclosed herein, from the viewpoint of adhesion (peel strength) or bending resistance to an adherend, for example, a diblock ratio of 30% by weight or more can be preferably used. (More preferably 40% by weight or more, still more preferably 50% by weight or more, even more preferably 60% by weight or more, typically 65% by weight or more, such as 70% by weight or more). From the standpoint of resistance to stress that is continuously applied, a diblock ratio of 90% by weight or less (more preferably 85% by weight or less, such as 80% by weight or less) can be preferably used. For example, a block copolymer having a diblock ratio of 60 to 85% by weight is preferably used. (Styrenic block copolymer) In a preferred aspect of the technology disclosed herein, the base polymer-based styrene-based block copolymer described above. For example, the above-mentioned base polymer can be preferably implemented in a state in which at least one of a styrene isoprene block copolymer and a styrene butadiene block copolymer is included. In the styrene-based block copolymer included in the adhesive, the ratio of the styrene isoprene block copolymer is preferably 70% by weight or more, or the ratio of the styrene butadiene block copolymer is 70% by weight. % Or more, or the total ratio of the styrene isoprene block copolymer and the styrene butadiene block copolymer is 70% by weight or more. In a preferred aspect, substantially all (for example, 95 to 100% by weight) of the styrene-based block copolymer is a styrene-isoprene block copolymer. In another preferred aspect, substantially all (for example, 95 to 100% by weight) of the styrene-based block copolymer is a styrene-butadiene block copolymer. According to this composition, the effect of applying the technology disclosed herein can be better exerted. The styrenic block copolymer may be in the form of a diblock body, a triblock body, a radial body, a mixture of these, and the like. In the triblock body and the radial body, a styrene block is preferably arranged at the end of the polymer chain. The reason is that the styrene blocks arranged at the end of the polymer chain easily aggregate to form a styrene domain, thereby forming an approximate cross-linked structure and improving the cohesiveness of the adhesive. As the styrenic block copolymer used in the technology disclosed herein, in terms of adhesion (peel strength) or bending resistance to an adherend, for example, a diblock ratio can be preferably used. 30% by weight or more (more preferably 40% by weight or more, still more preferably 50% by weight or more, particularly preferably 60% by weight or more, and typically 65% by weight or more). It may be a styrene-based block copolymer having a diblock ratio of 70% by weight or more (for example, 75% by weight or more). From the viewpoint of holding power and the like, a styrene-based block copolymer having a diblock ratio of 90% by weight or less (more preferably 85% by weight or less, such as 80% by weight or less) can be preferably used. For example, a styrene-based block copolymer having a diblock ratio of 60 to 85% by weight can be preferably used. The styrene content of the styrene-based block copolymer may be, for example, 5 to 40% by weight. From the viewpoints of bending resistance and retention, a styrene-based block copolymer having a styrene content of 10% by weight or more (more preferably, 10% by weight or more, for example, 12% by weight or more) is generally preferred. From the viewpoint of adhesion to the adherend, the styrene content is preferably 35% by weight or less (typically 30% by weight or less, more preferably 25% by weight or less, such as less than 20% by weight). ). For example, a styrene-based block copolymer having a styrene content of 12% by weight or more and less than 20% by weight can be preferably used. (Adhesion imparting agent) The adhesive layer disclosed herein may be a composition containing an adhesion imparting agent. The adhesion-imparting agent is not particularly limited. For example, rosin-based adhesion-imparting resins, terpene-based adhesion-imparting resins, hydrocarbon-based adhesion-imparting resins, epoxy-based adhesion-imparting resins, polyamide-based adhesion-imparting resins, and elastic system adhesion can be used. Various adhesion-imparting resins such as resin-imparting agents, phenol-based adhesion-imparting resins, and ketone-based adhesion-imparting resins. Such an adhesion-imparting resin may be used singly or in combination of two or more kinds. Specific examples of the rosin-based adhesion-imparting resin include unmodified rosin (raw rosin) such as rosin gum, wood rosin, tall oil rosin, and the like, which are modified by hydrogenation, disproportionation, and polymerization. Modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, other chemically modified rosin, etc., the same below); other various rosin derivatives. Examples of the above-mentioned rosin derivatives include those obtained by esterifying unmodified rosin with alcohols (that is, esters of rosin), and those obtained by esterifying modified rosin with alcohols (that is, modified Rosin esters) and other rosin esters; Unsaturated fatty acids modified with unsaturated fatty acids or modified rosin modified unsaturated rosins; Unsaturated fatty acids modified rosin esters modified Saturated fatty acid modified rosin esters; Rosin alcohols obtained by reducing the carboxyl group of unmodified rosin, modified rosin, unsaturated fatty acid modified rosin or unsaturated fatty acid modified rosin ester; unmodified Metal salts of rosin (especially rosin esters) such as rosin, modified rosin, various rosin derivatives; phenol and rosin (unmodified rosin, modified rosin, various rosin derivatives, etc.) by using an acid catalyst ) Rosin phenol resin and the like obtained by addition and thermal polymerization. When an acrylic polymer is used as a base polymer, it is preferable to use a rosin-based adhesion-imparting resin. From the viewpoint of improving adhesion properties such as adhesion, it is more preferable to use two or three or more different types and characteristics (for example, softening point) in combination with the rosin-based adhesion-imparting resin. Examples of terpene-based adhesion-imparting resins include terpene resins such as α-pinene polymers, β-pinene polymers, and dipentene polymers; and modification of these terpene resins (phenol modification, Aromatic modification, hydrogenation modification, hydrocarbon modification, etc.). Examples of the modified terpene resin include a terpene-modified phenol resin, a styrene-modified terpene resin, an aromatic-modified terpene resin, and a hydrogenated terpene resin. When an acrylic polymer is used as a base polymer, a terpene-based adhesion-imparting resin (for example, a terpene-modified phenol resin) is preferably used. In particular, from the viewpoint of improving adhesion properties such as adhesion, it is preferred to use one of the above-mentioned terpene-based adhesion-imparting resin (for example, a terpene-modified phenol resin) in combination with a different type or characteristic (for example, softening point) or 2 or more. Examples of the hydrocarbon-based adhesion-imparting resin include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic-aromatic petroleum resins (styrene-olefin copolymers, etc.), Various hydrocarbon resins, such as aliphatic-alicyclic petroleum resin, hydrogenated hydrocarbon resin, lavender resin, lavender-indene resin. In the technology disclosed herein, as the adhesion-imparting resin, a softening point (softening temperature) of about 70 ° C. or higher (preferably about 100 ° C. or higher, more preferably about 110 ° C. or higher) can be preferably used. According to the pressure-sensitive adhesive having an adhesion-imparting resin having a softening point having a softening point above the above-mentioned lower limit value, a pressure-sensitive adhesive sheet having better adhesion can be realized. Among the above-exemplified adhesion-imparting resins, the terpene-based adhesion-imparting resin (for example, a terpene-modified phenol resin) having a softening point and the rosin-based adhesion-imparting resin (for example, an esterified product of polymerized rosin) can be preferably used. The upper limit of the softening point of the adhesion-imparting resin is not particularly limited, and may be, for example, about 200 ° C or lower (typically about 180 ° C or lower). The softening point of the adhesion-imparting resin referred to herein is defined as a value measured by a softening point test method (ring and ball method) specified by any one of JIS K 5902 and JIS K 2207. The use amount of the adhesion-imparting agent is not particularly limited, and can be appropriately set according to the target performance (adhesion, reagent retention, etc.). For example, it is more suitable to set the adhesion-imparting agent to about 10 parts by weight or more, more preferably 20 parts by weight or more, based on 100 parts by weight of the base polymer (for example, acrylic polymer) based on the solid content. It is 30 parts by weight or more, more preferably about 100 parts by weight or less, preferably 80 parts by weight or less, more preferably 60 parts by weight or less, and even more preferably 50 parts by weight or less. (Acrylic Oligomer) The adhesive composition disclosed herein may also include an acrylic oligomer. By using an acrylic oligomer, adhesion and bending resistance can be improved in a good balance. In addition, in the case where the adhesive composition is hardened by active energy ray irradiation (for example, UV irradiation), the acrylic oligomer is less likely to be generated than an adhesion-imparting resin such as a rosin-based or terpene-based resin. Advantages of hardening hindrances, such as hindering polymerization of unreacted monomers. In addition, an acrylic oligomer is a polymer which contains an acrylic monomer as a constituent monomer component, and is defined as a polymer whose Mw is smaller than the said acrylic polymer. The Mw of the acrylic oligomer is not particularly limited, but is typically 0.1 × 10 4 ~ 3 × 10 4 about. From the viewpoint of improving the adhesion properties (such as adhesion or bending resistance), the Mw of the acrylic oligomer is preferably 1.5 × 10. 4 Below, more preferably 1 × 10 4 Hereinafter, it is more preferably 0.8 × 10 4 Following (e.g. 0.6 × 10 4 the following). From the viewpoint of the cohesiveness of the adhesive, the Mw is preferably 0.2 × 10. 4 Above (e.g. 0.3 × 10 4 the above). The molecular weight of the acrylic oligomer can be adjusted during polymerization using a chain transfer agent or the like as necessary. When the adhesive composition disclosed here contains an acrylic oligomer, the content of the acrylic oligomer is more preferably 100 parts by weight relative to 100 parts by weight of the base polymer (typically, an acrylic polymer). 0.5 parts by weight or more. From the viewpoint of making the effect of the acrylic oligomer better, the content of the acrylic oligomer is preferably 1 part by weight or more (for example, 5 parts by weight or more, typically 10 parts by weight or more). ). From the viewpoints of hardenability of the adhesive composition and compatibility with a base polymer (typically an acrylic polymer), the content of the acrylic oligomer is more preferably set to less than 50 weight. Parts (for example, up to 30 parts by weight), preferably up to 20 parts by weight (for example, up to 15 parts by weight). (Crosslinking agent) The adhesive composition for forming an adhesive layer preferably contains a crosslinking agent. The type of the cross-linking agent is not particularly limited, and it can be appropriately selected and used from previously known cross-linking agents. Examples of such a crosslinking agent include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, a melamine-based crosslinking agent, and a carbodiimide. Based crosslinking agents, amine based crosslinking agents, peroxide based crosslinking agents, metal chelate based crosslinking agents, metal alkoxide based crosslinking agents, metal salt based crosslinking agents, and the like. The crosslinking agent may be used singly or in combination of two or more kinds. From the viewpoint of preventing paste overflow or bending resistance, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or a melamine-based crosslinking agent is preferred, and an isocyanate-based crosslinking agent or an epoxy-based crosslinking agent is more preferred. It is particularly preferable to use an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent together. Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate. More specifically, trimethylolpropane / toluene diisocyanate terpolymer adduct (trade name "Coronate L", manufactured by Tosoh Corporation), trimethylolpropane / hexamethylene diisocyanate terpolymer can be exemplified. Isocyanate adducts such as adducts (trade name "Coronate HL", manufactured by Tosoh Corporation), isocyanurate bodies of hexamethylene diisocyanate (trade name "Coronate HX", manufactured by Tosoh Corporation), and the like. These can be used individually by 1 type or in combination of 2 or more types. Examples of the epoxy-based crosslinking agent include N, N, N ', N'-tetraglycidyl-m-xylylenediamine (trade name "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.), 1, 3 -Bis (N, N-diglycidylaminomethyl) cyclohexane (trade name "TETRAD-C", manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like. Examples of the melamine-based crosslinking agent include hexamethylolmelamine, butylated melamine resin (trade name "SUPER BECKAMINE J-820-60N", manufactured by DIC Corporation), and the like. The amount of the cross-linking agent contained in the above-mentioned adhesive composition is not particularly limited. From the viewpoint of considering both the adhesive force and the cohesive force, it is generally more suitable to be 100 relative to the base polymer (typically an acrylic polymer). The weight part is about 0.01 weight part or more, Preferably it is 0.02 weight part or more (for example, 0.1 weight part or more). In addition, it is usually more preferably about 10 parts by weight or less, and preferably 5 parts by weight or less (for example, 3 parts by weight or less) based on 100 parts by weight of the base polymer (typically an acrylic polymer). When the above-mentioned adhesive composition contains an isocyanate-based crosslinking agent as a crosslinking agent, the content of the isocyanate-based crosslinking agent is more preferably set to 100 parts by weight based on 100 parts by weight of the base polymer (typically, an acrylic polymer). 0.1 parts by weight or more, preferably 0.3 parts by weight or more, and more preferably 0.5 parts by weight or more. The content of the isocyanate-based crosslinking agent is more preferably about 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 3 parts by weight or less. When the above-mentioned adhesive composition contains an epoxy-based crosslinking agent as a crosslinking agent, the content of the epoxy-based crosslinking agent is more preferably 100 parts by weight based on 100 parts by weight of the base polymer (typically, an acrylic polymer). It is 0.0001 weight part or more, Preferably it is 0.001 weight part or more, More preferably, it is 0.01 weight part or more. The content of the epoxy-based crosslinking agent is more preferably about 1 part by weight or less, preferably 0.5 part by weight or less, and more preferably 0.1 part by weight or less. (Other Additives) The above-mentioned adhesive composition may contain a leveling agent, a cross-linking aid, a plasticizer, a softener, a filler, a colorant (dye, pigment), an antistatic agent, an anti-aging agent, and an ultraviolet absorbing agent as necessary Various additives commonly used in the field of adhesive composition such as agents, antioxidants, and light stabilizers. About such various additives, a conventionally known one can be used by a conventional method, and since it is not a person who gives a characteristic to this invention in particular, detailed description is abbreviate | omitted. (Method for Forming Adhesive Layer) The adhesive layer disclosed herein can be formed by a conventionally known method. For example, a method of forming an adhesive layer by applying an adhesive composition to a peelable surface (release surface) and drying it can be employed. Alternatively, a method (direct method) of forming an adhesive layer by directly applying (typically applying) an adhesive composition to a film-like substrate and drying it can be employed. In addition, it is also possible to form an adhesive layer on the surface by applying an adhesive composition to a peelable surface (release surface) and drying it, and transfer the adhesive layer to a film-like substrate. Method (transfer method). As the release surface, a surface of a release liner can be used. In addition, the adhesive layer disclosed herein is typically formed continuously, but is not limited to this form. For example, the adhesive layer may be an adhesive layer formed in a regular or random pattern such as dots or stripes. The form of the adhesive composition disclosed herein is not particularly limited. For example, the form (solvent type) of the form (solvent type) of the organic solvent containing the adhesive (adhesive component) having the composition described above may be dispersed in Adhesive composition in the form of an aqueous solvent (water-dispersible type, typically an aqueous latex type), hot-melt type adhesive composition, active energy ray-curable type adhesive composition, and the like. From the viewpoint of easily achieving better adhesion, reagent retention, and bending resistance, a solvent-based or water-dispersible adhesive composition can be preferably used. From the viewpoint of achieving higher adhesive properties, a solvent-based adhesive composition is particularly preferred. Typically, the solvent-based adhesive composition is prepared in the form of a solution containing the above components in an organic solvent. The organic solvent can be appropriately selected from known or commonly used organic solvents. For example, aromatic compounds such as toluene and xylene (typically aromatic hydrocarbons) can be used; acetates such as ethyl acetate and butyl acetate; hexane, cyclohexane, methylcyclohexane, etc. Aliphatic or alicyclic hydrocarbons; halogenated alkanes such as 1,2-dichloroethane; ketones such as methyl ethyl ketone and acetone; or two or more mixed solvents. Although not particularly limited, it is generally more suitable to prepare the solvent-based adhesive composition as a solid content (NV) of 20 to 65% by weight (for example, 25 to 55% by weight). If the NV is too low, the manufacturing cost tends to increase, and if the NV is too high, the operability such as coatability may decrease. The application of the adhesive composition can be performed using, for example, a conventionally known coater such as a gravure roll coater, a die coater, and a bar coater. Alternatively, the adhesive composition may be applied by an impregnation method or a curtain coating method. From the viewpoint of promoting a crosslinking reaction and improving manufacturing efficiency, the drying of the adhesive composition is preferably performed under heating. The drying temperature can be, for example, about 40 to 150 ° C (preferably about 60 to 130 ° C). After the adhesive composition is dried, curing can also be carried out for the purpose of adjusting the movement of components in the adhesive layer, proceeding the cross-linking reaction, and mitigating the deformation that may exist in the substrate or the adhesive layer. In a preferred aspect, the gel fraction of the adhesive layer is 23% or more, and more preferably 25% or more. The adhesive sheet having the above-mentioned gel fraction having a specific value or more has no paste overflow after processing such as punching, and therefore has excellent processability. It does not damage the appearance of the cut test piece. In addition, there is no overflow of the paste, which can be an advantageous feature in an adhesive sheet for a test piece which is subjected to processing such as formation of holes or capillaries. From the viewpoint of reagent retention, the above-mentioned gel fraction is more preferably about 65% or less, preferably 55% or less, more preferably 45% or less, and still more preferably 35% or less (for example, 30% or less). By making the gel fraction of the adhesive layer below a certain value, it is possible to better prevent the reagent contained in the double-sided adhesive sheet from leaking from the adhesive surface of the adhesive sheet. Furthermore, by using an adhesive layer having a gel fraction in the above range, the bending resistance is also improved. The gel fraction of the adhesive layer was measured by the method described in the following examples. The thickness of the adhesive layer disclosed herein is not particularly limited, and may be appropriately selected according to the purpose. Generally, from the standpoint of adhesive properties, the thickness of the adhesive layer is more preferably about 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more. From the viewpoints of productivity such as drying efficiency and test piece size, the thickness of the adhesive layer is more preferably about 200 μm or less, preferably 100 μm or less, more preferably 50 μm or less, and further preferably 30 μm. Or less (for example, 20 μm or less). In the case of a double-sided adhesive sheet having an adhesive layer on both sides of the substrate, the thickness of each adhesive layer may be the same or different. <Substrate> When the technology disclosed here is applied to a double-sided adhesive sheet with a substrate, as the substrate, for example, a polyolefin film such as a PE film, a PP film, and an ethylene-propylene copolymer film can be appropriately selected and used. Polyester films such as series films, PET films, and plastic films such as polyvinyl chloride films; foams containing foams such as polyurethane foam, PE foam, and polychloroprene foam Sheets; woven and non-woven fabrics obtained from various fibrous materials (natural fibers such as hemp and cotton, synthetic fibers such as polyester, vinylon, and semi-synthetic fibers such as acetate, etc.) The concept of paper such as Japanese paper and dory paper); metal foils such as aluminum foil and copper foil. A hydrophilic polymer film containing carboxymethyl cellulose (CMC) or the like can also be used as a substrate. As the plastic film, any of a non-stretched film and a stretched (uniaxially stretched or biaxially stretched) film can be used. Among these, a plastic film is preferred from the viewpoints of dimensional stability, thickness accuracy, economy (cost), workability such as punching, and tensile strength. Among plastic films, polyester films are particularly preferred. The surface of the substrate may also be subjected to surface treatment such as coating of a primer, corona discharge treatment and the like. In a preferred aspect, the substrate may be colored white. The use of a white substrate makes it easy to confirm the presence or absence of attachments such as stains, is excellent in cleanliness, and is also good in terms of hygiene. The adhesive sheet provided with a white substrate can be preferably used as a test piece for medical purposes. In addition, the white substrate has the advantage of easily recognizing the sample taken on the test piece. When the sample is a blood sample, the visibility of the sample is particularly excellent. The degree of whiteness (whiteness) is calculated as L * (lightness) specified by the L * a * b * color system, preferably 87 or more (for example, 87 to 100), and more preferably 90 or more (for example, 90 to 100) . The a * or b * specified by the L * a * b * color system can be appropriately selected according to the value of L *. For example, a * or b * is preferably in a range of -10 to 10 (more preferably -5 to 5 and even more preferably -2.5 to 2.5). Furthermore, in this specification, L *, a *, and b * specified by the L * a * b * colorimetric system are obtained by using a color difference meter (for example, a color difference meter manufactured by Minolta, trade name " CR-200 "). Furthermore, the L * a * b * color system is a color space recommended by the International Commission on Illumination (CIE) in 1976 and referred to as the CIE1976 (L * a * b *) color system. The L * a * b * color measurement system is regulated by JIS Z 8729 in the Japanese Industrial Standards. Examples of the white colorant used when the substrate is colored white include titanium oxide (titanium dioxide such as rutile titanium dioxide and anatase titanium dioxide), zinc oxide, aluminum oxide, silicon oxide, zirconia, and magnesium oxide. , Calcium oxide, tin oxide, barium oxide, cesium oxide, yttrium oxide, magnesium carbonate, calcium carbonate (light calcium carbonate, heavy calcium carbonate, etc.), barium carbonate, zinc carbonate, aluminum hydroxide, calcium hydroxide, hydroxide Magnesium, zinc hydroxide, aluminum silicate, magnesium silicate, calcium silicate, barium sulfate, calcium sulfate, barium stearate, zinc white, zinc sulfide, talc, clay, kaolin, titanium phosphate, mica, gypsum, white carbon , Inorganic white colorants such as diatomite, bentonite, zinc barium white, zeolite, sericite, kaolin, or acrylic resin particles, polystyrene resin particles, polyurethane resin particles, Organic white colorants such as amine resin particles, polycarbonate resin particles, polysiloxane resin particles, urea-formalin resin particles, and melamine resin particles. The amount of the white colorant used is not particularly limited, and it may be an amount that is appropriately adjusted so as to impart desired optical characteristics (typically whiteness). The thickness of the substrate can be appropriately selected according to the purpose. Generally, it is more preferably approximately 1 μm or more. From the viewpoint of strength or processability, it is preferably 2 μm or more, and more preferably 3 μm or more. The thickness of the substrate is usually preferably 500 μm or less (typically 200 μm or less). When the substrate-attached adhesive sheet disclosed here is used for a portable small-sized test piece, the thickness of the substrate is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 30 μm. Or less (for example, 20 μm or less). In a preferred aspect, the thickness of the substrate in the double-sided adhesive sheet with substrate is 15 μm or less (for example, 10 μm or less, typically 7 μm or less). An adhesive sheet having such a thin substrate can be particularly preferably used for a thinner test piece. <Total thickness of double-sided adhesive sheet> The total thickness of the double-sided adhesive sheet (thickness of the double-sided adhesive sheet excluding the release liner) in the technology disclosed herein is not particularly limited. For example, a double-sided adhesive sheet having a thickness of about 10 μm or more can be used. From the viewpoint of exhibiting good adhesive properties (adhesive strength, etc.), the thickness of the double-sided adhesive sheet is preferably 15 μm or more (typically 25 μm or more). The thickness of the double-sided adhesive sheet is usually about 300 μm or less (for example, 200 μm or less). When the double-sided adhesive sheet disclosed here is used for a portable small-sized test piece, the total thickness of the double-sided adhesive sheet is preferably 100 μm or less, more preferably 70 μm or less, and further preferably 50 μm or less (for example, 40 μm or less). The double-sided adhesive sheet having the above-mentioned total thickness is, for example, particularly suitable as a double-sided adhesive sheet that functions as a spacer that specifies a sampling amount of a sample to a test piece. It can be a good response to the decrease in sample size accompanied by the increase in analysis accuracy. <Characteristics of the double-sided adhesive sheet with release liner> The double-sided adhesive sheet disclosed herein is preferably the first adhesive surface and / or the second adhesive surface (preferably the first adhesive surface and the second adhesive surface) of the double-sided adhesive sheet. Both of the second adhesive surfaces) show 180-degree peel strength (also referred to as "adhesive force") of 4 N / 20 mm or more. The double-sided adhesive sheet having the above-mentioned adhesive force can exhibit good bonding strength as an adhesive sheet for a test piece having a small bonding area. The above adhesive force is more preferably 6 N / 20 mm or more, further preferably 7 N / 20 mm or more, and even more preferably 8 N / 20 mm or more (for example, 8.5 N / 20 mm or more). The 180-degree peel strength refers to the use of a stainless steel plate as the adherend, and a 2 kg roller is reciprocated once to press the adhesive surface of the adhesive sheet to the adherend surface. After being left for 30 minutes, the peeling angle is in accordance with JIS Z 0237. Measured at 180 ° and 300 mm / min. More specifically, it measured by the method as described in the following example. In a preferred aspect, the peeling force (peel strength of the first release liner) of the first adhesive surface of the double-sided adhesive sheet may not exceed 1 N / 50 mm (for example, 0.5 N / 50 mm or less, (Typically 0.4 N / 50 mm or less). Similarly, the liner peeling force (peel strength to the second peeling liner) of the second adhesive surface of the double-sided adhesive sheet is preferably less than 1 N / 50 mm (for example, 0.5 N / 50 mm or less. (Less than 0.4 N / 50 mm). The double-sided pressure-sensitive adhesive sheet whose liner peeling force is limited to a specific value or less is easy to remove the peeling liner, and therefore has excellent workability during attachment. In addition, considering that the workability of the liner may be reduced if the liner release force is too small, the liner release force of the first adhesive surface and / or the liner release force of the second adhesive surface of the double-sided adhesive sheet is preferably about 0.01. N / 50 mm or more. Furthermore, in order to prevent the phenomenon that even one release liner is removed when one release liner is removed, it is preferable to make the peeling force of the first adhesive surface different from the peeling force of the second adhesive surface. In a state where the release liner is peeled in the order of the first release liner and the second release liner and an adhesive sheet is used, it is preferable to set the peel strength to the first release liner to be lower than that to the second release liner. Peel peel strength. The peeling force of the liner was measured in an environment of 23 ° C and 50% RH under conditions of a peeling angle of 180 degrees and a tensile speed of 300 mm / min in accordance with JIS Z 0237. More specifically, it measured by the method as described in the following example. In a preferred aspect of the double-sided adhesive sheet, in the bending resistance evaluation test performed by the following method, the floating distance (height) of the end portion is less than 3 mm (more preferably less than 1 mm). It is particularly preferable that the end portion does not float in the bending resistance evaluation test. In addition, in a preferred aspect of the double-sided adhesive sheet, in the paste overflow preventing property evaluation test performed by the following method, the amount of paste overflow is less than 0.1 mm (more preferably 0.09 mm or less, and still more preferably 0.06). mm or less). The adhesive sheet disclosed herein is in a preferred aspect. When the adhesive sheet is kept at 150 ° C for 30 minutes, the amount of toluene emitted from the sheet (toluene emission amount) can be 1 g per 1 g of the adhesive layer. It is 20 μg or less. The adhesive sheet in which the amount of toluene emission is suppressed to a specific value or less can be used comfortably because there is no unpleasant odor because the outgassing amount is suppressed. Such an adhesive sheet is particularly preferably used as a test piece for analyzing a biological sample (for example, a blood sample) for medical or health promotion purposes. The toluene emission amount is more preferably 10 μg or less per 1 g of the adhesive layer, and more preferably 3 μg or less (for example, 1 μg or less, typically 0.3 μg or less). What is necessary is just to use the value measured by the following method as said toluene emission amount. [Measurement of toluene emission amount] After cutting the adhesive sheet to a size of 1 cm × 1 cm, peeling off the release liner to expose the adhesive surface, the adhesive surface was adhered to an aluminum foil as a sample. After the sample was put into a 20 mL vial and fastened, the vial was heated at 150 ° C for 30 minutes, and 1.0 mL of a heated gas was injected into the gas phase layer by a headspace autosampler. The amount of toluene was measured in a GC measurement device, and the toluene emission amount (μg / g) per 1 g of the adhesive layer included in the sample was calculated. At this time, the gas chromatography conditions were set as follows.・ Carrier gas: Helium gas ・ Column: Non-polar capillary column ・ Column temperature: 10 ° C / min heating rate (low temperature) maintained after heating (low temperature) 40 ~ 300 ° C Column head pressure: 113 kPa (40 ° C) Detector: FID (flame ionization detector, flame ionization detector) (temperature 250 ° C). For quantification, a calibration curve can be prepared using a gas containing toluene with a known gas amount, and calculated based on the calibration curve. Specifically, as long as the total area of each peak that appears after the elapse of 20 minutes from the start of temperature rise until 20 minutes has elapsed is converted into a weight based on the calibration curve converted from toluene, the amount of toluene gas emission can be quantified. <Applications of the double-sided adhesive sheet> The double-sided adhesive sheet disclosed herein can be used for a test piece for analyzing a sample (test piece for sample analysis). In the present specification, a "test piece" is defined as a person (also referred to as a test strip) for analyzing a sample. For example, it may have a function of sampling (typically, collecting and / or holding) a sample. Typically, the test strips disclosed herein can be placed on components (components used in conjunction with measurement equipment) of various sample measurement equipment with analysis functions to perform sample analysis. The test piece may preferably be a sensor having a function of analyzing a sample (for example, a function of making information (such as a component concentration) from the sample into a detectable state using a chemical reaction or the like). Here, the sample to be analyzed is not particularly limited, and examples thereof include biological samples such as whole blood, plasma, serum, saliva, urine, and cerebrospinal fluid. In addition, the samples may be various foods or beverage water, drainage, rainwater, and the like. The shape of the sample is not particularly limited, and a sample that is liquid at normal temperature is preferred. In addition, the analysis purpose is not particularly limited, and for example, it can be the measurement of the concentration of a specific component in a sample such as the blood glucose concentration. When the sample is a blood sample, as the analysis target, in addition to the above-mentioned glucose, components such as albumin, lactic acid, bilirubin, and cholesterol can also be cited. The adhesive sheet in the technology disclosed herein can be preferably used for a test piece (hereinafter, also referred to as a biosensor) for analyzing a biological sample (preferably a blood sample). The sample analysis using the test piece can be performed, for example, by placing the test piece holding the sample in a sample measurement device. Such a sample measurement device may be, for example, a portable small-sized measurement device (for example, a biological sample measurement device) for medical or health promotion purposes. The test piece (for example, a medical test piece) disclosed herein may have a structure (shape, size, etc.) detachably connected to the biological sample measuring device as described above. Typically, such test strips can be disposable test strips (typically also referred to as stripes or chips). As an example of the use pattern of the above test piece, the use pattern described below can be cited: carry a box containing a plurality of test pieces and the above-mentioned measuring equipment, perform sample analysis at an appropriate point in time, and discard the used one Test strip. Hereinafter, referring to the drawings, the above-mentioned test piece (biosensor) for measuring the blood glucose concentration that is a suitable application target of the double-sided adhesive sheet disclosed herein and the above-mentioned adhesive sheet with a release liner disclosed herein A method for manufacturing a test piece will be described, but the technology disclosed herein is not limited to this. As shown in FIG. 3, the test piece 100 includes a substrate 110, a coating layer 120, and a double-sided adhesive sheet 11 disposed between the substrate 110 and the coating layer 120. The shape of the test piece 100 may be a long flat plate. In this embodiment, the substrate 110 is a resin substrate and has a laminated structure of a resin plate and an insulating layer. The surface of the substrate on which the following electrodes are to be formed may be made of an insulating material, or may be entirely made of an insulating material. Examples of the material constituting the substrate include polyester such as PET, polyolefin such as PE or PP, polyamide such as nylon, polycarbonate, polyimide, polystyrene, polymethyl methacrylate, and acrylonitrile-butyl. Organic materials (typically resins) such as diene-styrene resin (ABS resin), fluororesin, and inorganic materials such as glass. These can be used individually by 1 type or in combination of 2 or more types. On the surface of the substrate 110, the strip-shaped electrodes 116 are arranged in a stripe shape with a specific interval, thereby forming an electrode pattern on the surface of the substrate 110. The electrodes 116 are used to detect an electric current generated by a reaction between an analysis object and a reagent. The material of the electrode may be a conductive material, and for example, a carbon electrode can be preferably used. Since the electrode pattern is formed on the surface of the substrate 110 as described above, the surface of the substrate 110 has unevenness. The double-sided adhesive sheet 11 has the form of a double-sided adhesive sheet with a base material, which joins the substrate 110 and the coating layer 120 and also functions as a spacer between the substrate 110 and the coating layer 120. A U-shaped notch is provided on one end of the double-sided adhesive sheet 11 in the longitudinal direction of the test piece 100. The space formed by the notch (in other words, the space surrounded by the double-sided adhesive sheet 11 located around the notch and the substrate 110 and the covering layer 120 covering the upper and lower sides thereof) serves as one end in the longitudinal direction of the test piece 100 The function of the capillary portion 150 of the opening (sample introduction port) 152. A blood sample introduced from the opening 152 is held in the capillary portion 150. Moreover, in this embodiment, the width (also the width of the notch) of the capillary portion 150 is approximately 1 mm, and the depth of the capillary portion 150 is approximately 5 mm. The material of the coating layer 120 is not particularly limited, and an appropriate one can be selected from those exemplified as the material that can be used for the substrate 110 and used. Alternatively, a hydrophilic membrane made of a hydrophilic polymer such as CMC may be used from the viewpoint of improving analysis accuracy. In brief, the test strip 100 is used for analysis of a sample, for example, in the following manner. That is, a blood sample as an analysis target is introduced into the capillary portion 150 from the opening 152 located at one end of the test piece 100 by a capillary phenomenon. A reagent 180 is disposed inside the test piece 100 at a portion communicating with the capillary portion 150. In this embodiment, the reagent 180 is accommodated in the hole 160 formed in the double-sided adhesive sheet 11. When the reagent 180 is contained in the test strip 100, it is in a liquid state at normal temperature (for example, 25 ° C), and is in a state of being in a gel state after being processed in the following manner, or is contained in a dry state or contained in a layer Various forms such as states of members and the like are arranged in the test piece 100. The reagent 180 generates an electric current by performing an electrochemical reaction with an analysis object (typically glucose) in a blood sample introduced into the capillary portion 150. The test piece 100 in this state is placed in a test piece insertion port of a measuring device, and the current value generated by the above reaction is measured in the device, thereby calculating the glucose concentration in the blood sample. The reagent contained in the test piece can be appropriately selected and used by a well-known or conventional person who performs an electrochemical reaction or a color development reaction with the analysis object according to the analysis object. For example, in the case where the blood glucose concentration is measured as described above, a reagent containing an oxidoreductase and an electron transfer medium that react with glucose is used. The oxidoreductase that can be included in the reagent is not particularly limited, and examples of the analysis target include NADH (nicotinamide adenine dinucleotide hydride) oxidase (such as xanthase), ethanol Oxidase, glucose oxidase, glucose dehydrogenase, lactate oxidase, lactate dehydrogenase, cholesterol oxidase, bilirubin oxidase and the like. The electron transfer medium is also not particularly limited, and potassium ferricyanide, p-benzoquinone, brown &#134116; methyl sulfate, ferrocene derivative, etc. can be used depending on the enzyme used. The reagent may contain any additional components such as a water-soluble polymer and a filler. Typically, the reagent when the test piece is injected contains a solvent, and for example, it may be in the form of a solution containing the above components such as the oxidoreductase and the electron transport medium in the solvent. The solvent used for the reagent is not particularly limited, and examples thereof include water-based solvents and phosphoric acid containing water (distilled water, ultrapure water, etc.) as the main component (the most contained component, typically containing more than 50% by weight of the component). Buffers such as buffers, alcohols such as ethanol, organic solvents such as dimethylsulfine, and tetrahydrofuran. When the above reagent is used to manufacture a test piece, it is typically contained in the test piece by the following method. Specifically, as shown in FIG. 4, a double-sided adhesive sheet 11 having two adhesive surfaces covered with a release liner is prepared, and a release liner (here, the first release liner) is peeled to make an adhesive surface (here The first adhesive surface is exposed, and the exposed adhesive surface (first adhesive surface) is bonded to the substrate 110. As the pressure-sensitive adhesive sheet with a release liner used, for example, the pressure-sensitive adhesive sheet 1 with a release liner shown in FIG. 1 described above is used. In the adhesive sheet with a release liner (for example, the adhesive sheet 1 with a release liner in FIG. 1), a hole 160 penetrating at least the second release liner 32 and the double-sided adhesive sheet 11 is provided in advance, and the hole 160 is peeled off at the second time. The back surface 32B of the pad 32 is opened. At this time, the double-sided adhesive sheet 11 attached to the substrate 110 is in a state where the second adhesive surface (upper surface) is covered with the second release liner 32. In this state, the reagent 180 is injected into the test piece 1 from the back surface 32B of the second release liner 32. Specifically, the reagent 180 is injected into the hole 160 opened in the back surface 32B of the second release liner 32. Typically, the reagent 180 is injected in a liquid state. That is, when the reagent 180 cannot be injected into the hole 160 with high accuracy and the reagent 180 is attached to the back surface 32B of the second release liner 32 in this injection operation, the water on the back surface 32B of the second release liner 32 is facilitated. The contact angle is 70 ° or more. Therefore, the reagent remains on the back surface 32B of the second release liner 32 without loss of reagents. The residual uninjected reagent can be loaded into the well 160 by induction with a dropper or the like. After the reagent 180 is loaded into the hole 160, the second release liner 32 is peeled off from the double-sided adhesive sheet 11 and the coating layer is adhered to the second adhesive surface of the double-sided adhesive sheet 11, thereby obtaining a figure 3 The illustrated test piece 1 has a laminated structure including a substrate 110, a double-sided adhesive sheet 11 and a coating layer 120. Furthermore, a decorative layer or an adhesive layer (such as an adhesive layer) for fixing the decorative layer may be further provided on the coating layer (typically a hydrophilic film) on the test piece. The size of the test piece disclosed here is not particularly limited, as long as it is appropriately set according to the measurement equipment or the required sample size. For example, test pieces with a length of about 15 to 50 mm (for example, 20 to 40 mm), a width of about 3 to 15 mm (for example, 4 to 10 mm), and a maximum thickness of about 100 to 2000 μm (for example, 300 to 600 μm) can be compared. The double-sided adhesive sheet disclosed herein is preferably used. In addition, the distance between the substrate and the coating layer (that is, the thickness of the spacer) that affects the volume of the capillary portion is usually about 200 μm or less, preferably 120 μm or less (for example, 70 μm or less, typically 50 μm or less). The thickness of the spacer is, for example, the total thickness of the double-sided adhesive sheet in the configuration of the above embodiment. For example, a test piece having the structure described above is obtained by forming a plurality of electrode patterns on the surface of a sheet-like substrate, laminating the coating layer by double-sided adhesive sheets to obtain a laminated structure, and punching the laminated structure into a plurality of pieces (for example 10 or more). The electrode pattern can be formed by a known method such as screen printing as appropriate. The injection of the reagent into the test piece may be performed before the coating layer is laminated as described above. The punching process is performed using a known or conventional processing machine. The double-sided adhesive sheet used in the test piece preferably has a property of closely adhering to the electrode-forming substrate and the covering layer as an adherend without causing undesirable conditions such as peeling that may cause sample leakage (typically, adhesive force) , Reagent retention, etc.). For example, it is preferable to have the following degree of bending resistance: Even when a test piece collected with a sample is placed in a test piece insertion opening of a measurement device, the test piece is caught near the insertion opening and bent, The bonding state of the constituent members of the test piece is well maintained. Furthermore, it is expected that when the adhesive sheet for a test piece is subjected to the above-mentioned punching processing or when a plurality of test pieces integrated by punching processing are separated one by one (typically cutting), the adhesive does not overflow from the cut end surface. EXAMPLES Hereinafter, several examples related to the present invention will be described, but it is not intended to limit the present invention to those shown in the examples. In the following description, unless otherwise specified, "parts" and "%" are based on weight. <Evaluation method> [Water contact angle] The water contact angle on the back surface of the release liner (second release liner) was measured using a commercially available contact angle measuring device in accordance with JIS R 3257: 1999 under the following conditions. (Water contact angle measurement conditions) Measuring device: Contact angle measuring device FACE CA-X (manufactured by Kyowa Interface Chemical Co., Ltd.) Measuring environment: 23 ° C, 50% RH Measuring liquid: Distilled water Measuring time: 1500 ms after dropping [Surface free Energy] The surface free energy γ is given by: γ = γ d + γ p + γ h The value represented. Here, γ in the above formula d , Γ p And γ h Represents the dispersed component, polar component, and hydrogen bonding component of surface free energy. The free surface energy on the back surface of the release liner (second release liner) γ uses water, diiodomethane, and 1-bromonaphthalene as the detection liquid, and according to the contact angle of each detection liquid and according to the Kitasaki- 畑 style (Japan Adhesive Association) Vol.8, No.3, 1972, pp.131-141). The contact angle was measured using a commercially available contact angle meter. [180-degree peel strength] A release liner was peeled from the double-sided adhesive sheet with a release liner of each example to expose an adhesive surface, and a PET film having a thickness of 25 μm was adhered to the exposed adhesive surface. This was cut into a size of 20 mm in width and 150 mm in length as a sample for evaluation. The other release liner was peeled from the sample for evaluation, the other adhesive surface (adhesive surface of the measurement object) was exposed, and a 2 kg roller was reciprocated once at 23 ° C and 50% RH. The other adhesive surface is crimped to the surface of the adherend. After leaving it in the same environment for 30 minutes, a universal tensile compression tester (device name "TCM-1kNB", manufactured by Minebea) was used in accordance with JIS Z 0237 at a peeling angle of 180 degrees and a tensile speed of 300 mm / min. The conditions measured the peel strength (N / 20 mm width). A stainless steel plate (SUS304 plate) was used as the adherend. [Panel peeling force] The double-sided adhesive sheet with a release liner of each example was cut into a size of 50 mm in width and 150 mm in length as a sample for evaluation. This sample for evaluation was measured using a tensile tester (device name "TCM-1kNB", manufactured by Minebea) under conditions of 23 ° C and 50% RH at a peel angle of 180 degrees and a tensile speed of 300 mm / min. The peeling strength when the release liner was peeled from the adhesive surface of the double-sided adhesive sheet, and the highest value was set as the peeling strength (N / 50 mm width). The measurement was performed on both sides of the first adhesive surface (peeling force to the first release liner) and the second adhesive surface (peeling force to the second release liner). [Gel fraction of the adhesive layer] About 0.1 g (weight W1) of the adhesive was collected from each of the adhesive sheets, and a porous polytetrafluoroethylene (PTFE) film (weight W2) with an average pore diameter of 0.2 μm was used to form a purse. Shape, and use a kite string (weight W3) to fasten the mouth. The bundle was immersed in 50 mL of ethyl acetate and kept at room temperature (typically 23 ° C.) for 7 days, so that only the gel component in the adhesive layer was dissolved out of the film, and then the bundle was packaged. The package was taken out and the ethyl acetate adhering to the outer surface was wiped off, the package was dried at 130 ° C for 1 hour, and the weight of the package (W4) was measured. Each value was substituted into the following formula, and the gel fraction (%) of the adhesive layer was calculated | required. Gel fraction (%) = [(W4-W2-W3) / W1] × 100 As the porous PTFE membrane, a trade name "NITOFLON NTF1122" (average pore diameter 0.2 μm, porosity) available from Nitto Denko Corporation was used. 75%, thickness 85 μm). [Liquid recycling property] The double-sided adhesive sheet with a release liner in each example was cut into a size of 10 mm in width and 100 mm in length, the first release liner was peeled off, and a stainless steel (SUS) plate was attached to the exposed The first adhesive surface. With respect to the evaluation sample obtained as described above, as shown in FIG. 5, the evaluation sample 200 was placed on the 30-degree inclined surface with the SUS board 212 side facing downward. The evaluation sample 200 was arrange | positioned so that the longitudinal direction might become the up-down direction (inclined direction) of an inclined surface. One drop (approximately 3 to 5 μL) of pure water 220 was placed on the upper end of the back surface 216B of the second release liner 216 disposed above the evaluation sample 200, and a dropper was used to attach water droplets to the dropper. The front end slides 50 mm in a straight line facing downward (in the direction of the arrow in Fig. 5). In addition, in FIG. 5, reference numeral 214 denotes a double-sided adhesive sheet. The back side where the water droplets move easily becomes the back side where the reagents on the back surface of the release liner can be easily moved and the reagent can be recovered and injected. Therefore, when the total amount of water drops on the back surface 216B of the second release liner 216 can be moved The evaluation was "○", and when the total amount could not be moved, it was evaluated as "×". [Liquid retention] The double-sided adhesive sheet with a release liner of each example was cut into a size of 10 mm in width and 40 mm in length, and a hole having a diameter of 2 mm was formed on one end side in the length direction. Then, the first release liner was peeled from the double-sided adhesive sheet, and a white PET plate was attached to the exposed first adhesive surface. One drop (about 3 to 5 μL) of water colored in red (colored water) was dropped from the opening on the back of the second release liner into the hole of the evaluation sample obtained in the above manner, and as shown in FIG. 2 With the release liner 316 side up, the evaluation sample 300 was placed on a 30-degree inclined surface. The evaluation sample 300 is arranged so that the longitudinal direction becomes the up-down direction (inclined direction) of the inclined surface. After being left for one day in this state, the state of the colored water 320 in the hole 330 in the double-sided adhesive sheet 314 was observed. When the coloring water 320 does not leak from the hole 330, it is evaluated as "○", and when the coloring water 320 leaks from the hole 330 (that is, when it flows out between the PET plate 312 and the double-sided adhesive sheet 314), it is evaluated as "" × ". [Bending resistance] The double-sided adhesive sheet with a release liner in each example was cut into a width of 10 mm and a length of 50 mm, and a PET board cut to the same size and having a thickness of 100 μm was attached (substrate) to the peeling. The second adhesive surface exposed by the second release liner was a PET substrate double-sided adhesive sheet for evaluation. In addition, a copper film having a thickness of 50 μm was laminated on one surface of a resin plate (PET plate) having a thickness of 1 mm, and cut into a size of 10 mm in width and 70 mm in length to obtain a test adherend (Cu resin laminated plate). . The first release liner was peeled from the PET substrate double-sided adhesive sheet used for the test to expose the first adhesive surface, and the first adhesive surface and the test object were adhered using a laminator in an environment of 23 ° C and RH50% The center of the longitudinal direction of the copper film surface of the body was aligned and the two were crimped together, and this was used as a test piece. Next, as shown in FIG. 7, the test piece 400 was bent into an arc shape using a jig so that the chord length in the longitudinal direction of the test piece 400 became 50 mm. The test piece 400 was bent so that the side of the substrate PET plate 412 protruded. This was kept in the same environment for one day, and the state of the end of the double-sided adhesive sheet 414 of the test piece 400 was observed. When the double-sided adhesive sheet 414 followed the surface of the copper film 424 of the adherend 420 for test, it was evaluated as "○", and the end of the double-sided adhesive sheet 414 was bulged from the adherend 420 for test, and the peeling was confirmed. In the case, it was evaluated as "×". In FIG. 7, reference numeral 422 denotes a resin plate of the adherend 400 for testing. [Prevention of paste overflow] The double-sided adhesive sheet with a release liner in each example was cut into a size of 10 mm × 30 mm, a release liner was peeled off, and an acrylic resin plate was attached to the exposed adhesive surface. Then, the acrylic resin plate is placed so that the side becomes downward. The other release liner remained without being peeled off, and an aluminum plate was placed on the release liner to obtain an acrylic resin plate 512, a double-sided adhesive sheet 514, and a release liner 516 laminated in this order from the bottom as shown in FIG. 8. And an evaluation sample 500 made of an aluminum plate 520. For this evaluation sample 500, a pressure of 10 MPa (in the direction of the arrow in FIG. 8) was applied from above for 1 minute, and the paste immediately after the pressure was released was measured from the top by a microscope observation (adhesive for double-sided adhesive sheet 514). The maximum value (mm) of the overflow distance from the end face of the release liner. If the amount of overflow of the paste (the maximum value of the overflow distance) is 0.1 mm or more, the workability is reduced. Therefore, when the amount of overflow of the paste is less than 0.1 mm, it is evaluated as "○", and the amount of overflow is 0.1 mm. The above situation was evaluated as "×". <Example 1> (Preparation of Adhesive Composition (A)) 100 parts of BA, 5 parts of Vac, 3 parts of AA, and HEA were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, reflux condenser, and dropping funnel. 0.1 part of AIBN as a polymerization initiator and toluene as a polymerization solvent were subjected to solution polymerization at 60 ° C. for 6 hours to obtain a toluene solution of an acrylic polymer (A). Mw of the acrylic polymer (A) was 55 × 10 4 . Polymerized rosin pentaerythritol ester (trade name "HARITACK PCJ") is added to 100 parts of the acrylic polymer (A) contained in the toluene solution, based on the solid content. The softening point is 118 to 128. ℃) 10 parts, hydrogenated rosin glyceride (trade name "HARITACK SE10", manufactured by Harima Chemical Co., softening point 75-85 ° C) 10 parts, hydrogenated rosin methyl ester (trade name "Foralyn 5020F", manufactured by Eastman Chemical Co., Ltd.) ) 5 parts, 15 parts of terpene-modified phenol resin (trade name "SUMILITE RESIN PR-12603N", manufactured by Sumitomo Bakelite Co., Ltd.) 15 parts as an adhesion-imparting resin, and an isocyanate-based crosslinking agent (trade name "Coronate L", Tosoh 2 parts of the company) and 0.025 part of an epoxy-based cross-linking agent (trade name "TETRAD-C", manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a cross-linking agent to obtain an acrylic adhesive composition (A). (Production of Adhesive Sheet) As a first release liner, a polyester release film (trade name "DIAFOIL MRF", manufactured by Mitsubishi Polyester Corporation) with a thickness of 38 μm, which had been subjected to a release treatment on one side to become a release surface, was prepared. In addition, one side (front side) was prepared with a polysiloxane-based peeling treatment agent (trade name "KS-3703T", manufactured by Shin-Etsu Chemical Co., Ltd., thermosetting addition molding) to be a peeling side, and the other side (back side) was prepared. Polysiloxane-based water-repellent treatment agent (trade name "KS-847T", manufactured by Shin-Etsu Chemical Industry Co., Ltd., thermosetting addition molding) was water-repellent treated to form a polyester release film with a thickness of 75 μm on the water-repellent surface. The second release liner. An adhesive composition (A) was applied to each of the release surface of the first release liner and the release surface of the second release liner, and dried at 100 ° C. for 2 minutes to form a 13 μm thick film on each release liner. Adhesive layer. The adhesive layer formed on the two release liners was bonded to the first and second sides of a PET substrate film (trade name "Lumirror", manufactured by Toray) with a thickness of 5 μm, respectively, to produce this example. A double-sided adhesive sheet with a substrate. The double-sided adhesive sheet is a double-sided adhesive sheet including a substrate, a first adhesive layer provided on a first surface of the substrate, and a second adhesive layer provided on a second surface of the substrate. The adhesive surface (first adhesive surface) of the adhesive layer is protected by the first release liner, and the adhesive surface (second adhesive surface) of the second adhesive layer is protected by the second release liner. <Example 2> A release film (brand name "FILMBYNA NT") manufactured by Fujimori Industries was used as the second release liner, and the same peeling treatment as in Example 1 was performed on the front side to obtain a release surface (front side) and Release film on the water repellent surface (back). Except for this, a double-sided adhesive sheet with a release liner of this example was obtained in the same manner as in Example 1. <Example 3> A water-repellent material (trade name "TOYAL LOTUS") manufactured by Toyo Aluminium Co., Ltd. was used as the second release liner, a water-repellent surface was provided, and the same peeling treatment as in Example 1 was performed on the front side. A release film with a release surface (front surface) and a water repellent surface (back surface). Except for this, a double-sided adhesive sheet with a release liner of this example was obtained in the same manner as in Example 1. <Example 4> (Preparation of Adhesive Composition (B)) To a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux condenser, and a dropping funnel were added 70 parts of BA as a monomer component, 30 parts of 2EHA, 3 parts of AA and 0.05 parts of 4HBA, 0.08 parts of AIBN as a polymerization initiator, and ethyl acetate as a polymerization solvent, and solution polymerization was performed at 65 ° C for 3.5 hours in a nitrogen gas stream to obtain an acrylic polymer (B) Its solution. A polymerized rosin ester (trade name "PENSEL D125", Arakawa), which is used as an adhesion-imparting resin, is formulated in the solution of the acrylic polymer (B) based on 100 parts of the acrylic polymer (B) based on the solid content. 30 parts of softening point (made by Chemical Industry Co., Ltd.) and 3 parts of isocyanate-based crosslinking agent (trade name "Coronate L", manufactured by Tosoh Corporation) to prepare an acrylic adhesive composition (B). (Production of Adhesive Sheet) As a first release liner, a polyester release film (trade name "DIAFOIL MRF", manufactured by Mitsubishi Polyester Corporation) with a thickness of 38 μm, which had been subjected to a release treatment on one side to become a release surface, was prepared. In addition, a polyester release film having a thickness of 75 μm that has been subjected to a peeling process on only one side (front side) to be a peeled side was prepared as a second release liner. An adhesive composition (B) was applied to each of the release surface of the first release liner and the release surface of the second release liner, and dried at 100 ° C. for 2 minutes to form a 13 μm thickness on each release liner. Adhesive layer. Except for this, a double-sided adhesive sheet with a substrate of this example was produced in the same manner as in Example 1. <Example 5> (Preparation of Adhesive Composition (C)) 95 parts of BA and 5 parts of AA as monomer components were added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux condenser, and a dropping funnel. 0.2 parts of AIBN as a polymerization initiator and toluene as a polymerization solvent were subjected to solution polymerization in a nitrogen gas stream at 60 ° C. for 6 hours to obtain a solution of an acrylic polymer (C). To the solution of the acrylic polymer (C) described above, 15 parts of an acrylic oligomer and an isocyanate-based crosslinking agent (trade name ""CoronateL" (manufactured by Tosoh Corporation) and 0.075 parts of an epoxy-based crosslinking agent (trade name "TETRAD-C", manufactured by Mitsubishi Gas Chemical Co., Ltd.) to obtain an acrylic adhesive composition (C). As the acrylic oligomer, one prepared by the following method was used. Specifically, 95 parts of cyclohexyl methacrylate, 5 parts of AA, and α-methylstyrene dimer were added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux condenser, and a dropping funnel. (Named "Nofmer MSD", manufactured by Nippon Oil Co., Ltd.) 10 parts, 10 parts of AIBN as a polymerization initiator, and toluene as a polymerization solvent, stirred in a stream of nitrogen for 1 hour to remove oxygen in the polymerization system, and then heated to The reaction was performed at 85 ° C. for 5 hours to obtain an acrylic oligomer having a solid content concentration of 50%. The weight average molecular weight of the obtained acrylic oligomer was 4,300. (Production of Adhesive Sheet) A double-sided adhesive sheet with a release liner of this example was obtained in the same manner as in Example 4 except that the adhesive composition (C) was used instead of the adhesive composition (B). After the double-sided adhesive sheet with a release liner of each of the examples obtained above was cured in an environment of 23 ° C. and 50% RH for 1 day, each of the double-sided adhesive sheets was subjected to the above-mentioned evaluation test. The results are shown in Table 1. [Table 1] As shown in Table 1, in the double-sided adhesive sheet with a release liner provided with the first release liner and the second release liner, Examples 1 to 3 in which the water contact angle on the back surface of the second release liner was 70 ° or more Adhesive sheet for liquid recovery. On the other hand, in Examples 4 and 5 in which the water contact angle on the back surface of the second release liner was less than 70 °, the liquid recyclability was unsatisfactory. Based on the results, it was found that the release liner with a release liner having a first release liner and a second release liner and a water contact angle of one of the back surface of the first release liner and the back surface of the second release liner was 70 ° or more. When the double-sided adhesive sheet is used in the manufacture of a test piece for sample analysis, the loss of reagents during the manufacture of the test piece can be prevented. In addition, the adhesive sheet of Examples 1 to 3 having a gel fraction of 25% to 55% can have both liquid retention and paste overflow prevention properties. In addition, it was confirmed that the bending resistance was also superior to those of Examples 4 and 5 outside the above-mentioned gel fraction. Based on the results, it was found that when the adhesive sheet having a gel fraction of 25% to 55% is used in a test piece for sample analysis, the reagent can be held well in the test piece. In addition, it is considered that the test piece using the above-mentioned adhesive sheet does not overflow the paste during punching or the like, and can maintain the joined state of the constituent members well even when the test piece is bent. The adhesive sheet satisfying the above characteristics is particularly suitable for the use of a test piece for sample analysis. The specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of patent application. The technology described in the scope of patent application includes various changes and modifications to the specific examples exemplified above. [Cross Reference] This case claims priority based on Japanese Patent Application No. 2016-78325 filed on April 8, 2016, the entire contents of which are incorporated herein by reference.

1‧‧‧附剝離襯墊之黏著片
2‧‧‧附剝離襯墊之黏著片
11‧‧‧雙面黏著片
12‧‧‧雙面黏著片
15‧‧‧基材
15A‧‧‧基材之第1面
15B‧‧‧基材之第2面
20‧‧‧黏著劑層
20A‧‧‧第1黏著面
20B‧‧‧第2黏著面
21‧‧‧第1黏著劑層
21A‧‧‧第1黏著面
22‧‧‧第2黏著劑層
22A‧‧‧第2黏著面
31‧‧‧第1剝離襯墊
31A‧‧‧第1剝離襯墊之正面
31B‧‧‧第1剝離襯墊之背面
32‧‧‧第2剝離襯墊
32A‧‧‧第2剝離襯墊之正面
32B‧‧‧第2剝離襯墊之背面
100‧‧‧試驗片
110‧‧‧基板
116‧‧‧電極
120‧‧‧被覆層
150‧‧‧毛細管部
152‧‧‧開口
160‧‧‧孔
180‧‧‧試劑
200‧‧‧評價用樣品
212‧‧‧SUS板
214‧‧‧雙面黏著片
216‧‧‧第2剝離襯墊
216B‧‧‧第2剝離襯墊之背面
220‧‧‧純水
300‧‧‧評價用樣品
312‧‧‧PET板
314‧‧‧雙面黏著片
316‧‧‧第2剝離襯墊
320‧‧‧著色水
330‧‧‧孔
400‧‧‧試驗片
412‧‧‧襯底PET板
414‧‧‧雙面黏著片
420‧‧‧試驗用被黏著體
422‧‧‧樹脂板
424‧‧‧銅膜
500‧‧‧評價用樣品
512‧‧‧丙烯酸系樹脂板
514‧‧‧雙面黏著片
516‧‧‧剝離襯墊
520‧‧‧鋁板
1‧‧‧ Adhesive sheet with release liner
2‧‧‧ Adhesive sheet with release liner
11‧‧‧ double-sided adhesive sheet
12‧‧‧ double-sided adhesive sheet
15‧‧‧ substrate
15A‧‧‧First side of substrate
15B‧‧‧The second side of the substrate
20‧‧‧ Adhesive layer
20A‧‧‧The first adhesive surface
20B‧‧‧ 2nd adhesive surface
21‧‧‧The first adhesive layer
21A‧‧‧The first adhesive surface
22‧‧‧Second adhesive layer
22A‧‧‧Second Adhesive Surface
31‧‧‧The first release liner
31A‧‧‧front of 1st release liner
31B‧‧‧Back side of 1st release liner
32‧‧‧ 2nd release liner
32A‧‧‧ Front side of 2nd release liner
32B‧‧‧Back side of 2nd release liner
100‧‧‧test piece
110‧‧‧ substrate
116‧‧‧electrode
120‧‧‧ Coating
150‧‧‧ Capillary section
152‧‧‧ opening
160‧‧‧hole
180‧‧‧ reagent
200‧‧‧ Evaluation sample
212‧‧‧SUS board
214‧‧‧Double-sided adhesive sheet
216‧‧‧The second release liner
216B‧‧‧Back side of 2nd release liner
220‧‧‧pure water
300‧‧‧ Evaluation sample
312‧‧‧PET board
314‧‧‧Double-sided adhesive sheet
316‧‧‧ 2nd release liner
320‧‧‧colored water
330‧‧‧hole
400‧‧‧test piece
412‧‧‧ substrate PET board
414‧‧‧Double-sided adhesive sheet
420‧‧‧ Test adherend
422‧‧‧resin board
424‧‧‧copper film
500‧‧‧Evaluation sample
512‧‧‧acrylic resin board
514‧‧‧Double-sided adhesive sheet
516‧‧‧ Release liner
520‧‧‧aluminum sheet

圖1係表示一實施形態之附剝離襯墊之黏著片(附基材之雙面黏著片)之構成之模式性剖視圖。 圖2係表示另一實施形態之附剝離襯墊之黏著片(無基材之雙面黏著片)之構成之模式性剖視圖。 圖3係表示一實施形態之試驗片之構成之概略立體圖。 圖4係表示製造中之試驗片之構成之概略立體圖。 圖5係用以對液體回收性評價試驗之方法進行說明之模式性側視圖。 圖6係用以對液體保持性評價試驗之方法進行說明之模式性側視圖。 圖7係用以對耐彎曲性評價試驗之方法進行說明之模式性剖視圖。 圖8係用以對糊劑溢出防止性評價試驗之方法進行說明之模式性側視圖。FIG. 1 is a schematic cross-sectional view showing the structure of an adhesive sheet with a release liner (a double-sided adhesive sheet with a substrate) according to an embodiment. FIG. 2 is a schematic cross-sectional view showing the structure of an adhesive sheet with a release liner (a double-sided adhesive sheet without a substrate) according to another embodiment. Fig. 3 is a schematic perspective view showing the structure of a test piece according to an embodiment. FIG. 4 is a schematic perspective view showing the structure of a test piece in production. FIG. 5 is a schematic side view for explaining a method of a liquid recyclability evaluation test. Fig. 6 is a schematic side view for explaining a method of a liquid retention evaluation test. FIG. 7 is a schematic cross-sectional view for explaining a method for evaluating a bending resistance. FIG. 8 is a schematic side view for explaining a method for evaluating a paste overflow prevention property.

1‧‧‧附剝離襯墊之黏著片 1‧‧‧ Adhesive sheet with release liner

11‧‧‧雙面黏著片 11‧‧‧ double-sided adhesive sheet

15‧‧‧基材 15‧‧‧ substrate

15A‧‧‧基材之第1面 15A‧‧‧First side of substrate

15B‧‧‧基材之第2面 15B‧‧‧The second side of the substrate

21‧‧‧第1黏著劑層 21‧‧‧The first adhesive layer

21A‧‧‧第1黏著面 21A‧‧‧The first adhesive surface

22‧‧‧第2黏著劑層 22‧‧‧Second adhesive layer

22A‧‧‧第2黏著面 22A‧‧‧Second Adhesive Surface

31‧‧‧第1剝離襯墊 31‧‧‧The first release liner

31A‧‧‧第1剝離襯墊之正面 31A‧‧‧front of 1st release liner

31B‧‧‧第1剝離襯墊之背面 31B‧‧‧Back side of 1st release liner

32‧‧‧第2剝離襯墊 32‧‧‧ 2nd release liner

32A‧‧‧第2剝離襯墊之正面 32A‧‧‧ Front side of 2nd release liner

32B‧‧‧第2剝離襯墊之背面 32B‧‧‧Back side of 2nd release liner

Claims (8)

一種附剝離襯墊之黏著片,其係用於製造用以分析樣本之試驗片者, 其包括:雙面接著性之黏著片,其具有黏著劑層;第1剝離襯墊,其覆蓋該黏著片之第1黏著面;及第2剝離襯墊,其覆蓋該黏著片之第2黏著面;且 上述第1剝離襯墊之背面及上述第2剝離襯墊之背面中之一個背面之水接觸角為70°以上。An adhesive sheet with a release liner, which is used for manufacturing a test piece for analyzing a sample, includes: a double-sided adhesive sheet having an adhesive layer; and a first release liner covering the adhesive. A first adhesive surface of the sheet; and a second release liner covering the second adhesive surface of the adhesive sheet; and water contact between one of the back surface of the first release liner and the back surface of the second release liner The angle is 70 ° or more. 如請求項1之附剝離襯墊之黏著片,其中上述黏著劑層之凝膠分率為25%~55%。For example, the adhesive sheet with a release liner of claim 1, wherein the gel fraction of the adhesive layer is 25% to 55%. 如請求項1或2之附剝離襯墊之黏著片,其中上述黏著片之黏著面顯示出7 N/20 mm以上之180度剝離強度。For example, the adhesive sheet with a release liner of claim 1 or 2, wherein the adhesive surface of the above adhesive sheet exhibits a 180-degree peel strength of 7 N / 20 mm or more. 如請求項1至3中任一項之附剝離襯墊之黏著片,其中上述黏著片係附基材之雙面黏著片,其包括基材、設置於該基材之一面之第1黏著劑層、及設置於該基材之另一面之第2黏著劑層。For example, the adhesive sheet with a release liner according to any one of claims 1 to 3, wherein the adhesive sheet is a double-sided adhesive sheet with a base material, which includes a base material and a first adhesive agent provided on one side of the base material. Layer, and a second adhesive layer provided on the other side of the substrate. 如請求項1至4中任一項之附剝離襯墊之黏著片,其中上述黏著劑層係包含丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑層。The adhesive sheet with a release liner according to any one of claims 1 to 4, wherein the adhesive layer is an acrylic adhesive layer including an acrylic polymer as a base polymer. 如請求項5之附剝離襯墊之黏著片,其中上述黏著劑層包含相對於上述丙烯酸系聚合物100重量份為20~60重量份之黏著賦予樹脂。The pressure-sensitive adhesive sheet with a release liner according to claim 5, wherein the pressure-sensitive adhesive layer contains an adhesion-imparting resin in an amount of 20 to 60 parts by weight based on 100 parts by weight of the acrylic polymer. 如請求項1至6中任一項之附剝離襯墊之黏著片,其中上述黏著片之厚度為50 μm以下。The adhesive sheet with a release liner according to any one of claims 1 to 6, wherein the thickness of the adhesive sheet is 50 μm or less. 如請求項1至7中任一項之附剝離襯墊之黏著片,其中上述試驗片係裝卸自如地連接於生物樣本測定設備之生物感測器。The adhesive sheet with a release liner according to any one of claims 1 to 7, wherein the test piece is a biosensor that is detachably connected to a biological sample measuring device.
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