TWI739833B - Adhesive sheet and manufacturing method of adhered volume layer - Google Patents

Adhesive sheet and manufacturing method of adhered volume layer Download PDF

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TWI739833B
TWI739833B TW106116021A TW106116021A TWI739833B TW I739833 B TWI739833 B TW I739833B TW 106116021 A TW106116021 A TW 106116021A TW 106116021 A TW106116021 A TW 106116021A TW I739833 B TWI739833 B TW I739833B
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adhesive layer
adhesive
adherend
layer
adhesive sheet
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TW106116021A
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TW201809181A (en
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坂井美和子
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日商索瑪爾股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207—Heat-activated adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/08—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers using foamed adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

提供一種熱剝離型黏著片，其具有即便加熱條件嚴酷(例如100℃，3小時)，黏著層亦不癟縮而可保持膨脹狀態，然後容易自被黏著體剝離之黏著層。黏著片1具有由含有熱發泡劑與黏著劑之熱發泡性黏著劑組成物構成之第1黏著層33。其特徵為於將第1黏著層33之表面積設為「S0」，將於100℃經加熱3小時之情形時之第1黏著層33a表面之算術平均粗糙度設為「Ra」，將凹凸之最高點即上限高度設為「H1」，將凹凸之最低點即下限高度設為「H5」，將H1至H5之範圍之表面積設為「SH1-H5」時，以滿足式1、2與條件a之方式形成有第1黏著層33。式1：(H1-H5)≧50μm，式2：SH1-H5/S0≧2.5，及條件a：Ra為4~8μm。 Provided is a heat-peelable adhesive sheet, which has an adhesive layer that does not shrink but can maintain an expanded state even if the heating conditions are severe (for example, 100° C., 3 hours), and then easily peels off from the adherend. The adhesive sheet 1 has a first adhesive layer 33 composed of a thermally foamable adhesive composition containing a thermal foaming agent and an adhesive. It is characterized in that the surface area of the first adhesive layer 33 is set to "S 0 ", and the arithmetic average roughness of the surface of the first adhesive layer 33a when heated at 100°C for 3 hours is set to "Ra". Set the highest point, that is, the upper limit height, to "H1", set the lowest point, that is, the lower limit height of the bumps, to "H5", and set the surface area of the range from H1 to H5 to "S H1-H5 " to satisfy equations 1, 2 In accordance with the condition a, the first adhesive layer 33 is formed. Formula 1: (H1-H5)≧50μm, Formula 2: S H1-H5 /S 0 ≧2.5, and condition a: Ra is 4-8μm.

Description

黏著片及被黏著體積層物之製造方法 Adhesive sheet and manufacturing method of adhered volume layer

本發明係關於一種具備黏著層之熱剝離型黏著片及使用該黏著片之被黏著體積層物之製造方法，該黏著層與被黏著體之接觸面之黏著力於特定溫度以上之加熱前後會發生變化。 The present invention relates to a heat-peelable adhesive sheet with an adhesive layer and a method for manufacturing an adhered volume layer using the adhesive sheet. The adhesive force of the contact surface between the adhesive layer and the adherend is at a certain temperature or higher before and after heating. Changes.

作為能夠以適度之黏著力貼附於被黏著體，並且結束使用目的而不再需要後可簡單地剝離之再剝離性黏著片，已知有於基材上設置有含有熱膨脹性微球之黏著層的黏著片(專利文獻1)。 As a re-peelable adhesive sheet that can be attached to the adherend with a moderate adhesive force, and can be easily peeled off after the purpose of use is no longer needed, it is known that an adhesive containing thermally expandable microspheres is provided on the substrate Layer of adhesive sheet (Patent Document 1).

專利文獻1：日本特開平11-302614號公報 Patent Document 1: Japanese Patent Application Laid-Open No. 11-302614

於專利文獻1揭示之黏著片於經加熱之情形時，藉由熱膨脹性微球膨脹而使黏著層表面產生凹凸，藉此減小黏著層對於貼附之被黏著體的接觸面積，使黏著力降低，而使被黏著體之剝離變得容易。 When the adhesive sheet disclosed in Patent Document 1 is heated, thermally expandable microspheres expand to produce unevenness on the surface of the adhesive layer, thereby reducing the contact area of the adhesive layer to the adherend and increasing the adhesive force Lower, and make the peeling of the adherend easier.

此外，被黏著體之剝離變得容易之原因在於：於剝離被黏著體時，保持有產生於表面之凹凸，而維持黏著層之膨脹狀態。因此，即便 黏著層所含之熱膨脹性微球膨脹，但隨後一部分發生收縮之情形時，黏著層之膨脹狀態未受到維持，而引起與被黏著體之部分性附著，結果有時會無法輕易地將被黏著體自黏著片剝離。已知此種現象尤其於加熱時間(自加熱開始至被黏著體之剝離開始為止之時間)長之情形時容易發生。 In addition, the reason why the peeling of the adherend becomes easier is that when the adherend is peeled, the unevenness generated on the surface is maintained, and the expanded state of the adhesive layer is maintained. Therefore, even The heat-expandable microspheres contained in the adhesive layer expand, but when a part of the adhesive layer shrinks later, the expanded state of the adhesive layer is not maintained, causing partial adhesion with the adherend. As a result, sometimes it cannot be easily adhered. The body peels off from the adhesive sheet. It is known that this phenomenon is likely to occur especially when the heating time (the time from the start of heating to the start of peeling of the adherend) is long.

然而，有時要求於使黏著片之黏著層對向貼附於被黏著體後，於相對低溫(例如100℃)加熱長時間(例如3小時)後，將被黏著體自黏著層剝離。即使為相對低溫但供於長時間加熱之情形時，自加熱開始起經過30分鐘左右可保持之黏著層之膨脹狀態有時會於加熱結束時即被黏著體之剝離開始時無法保持。認為其原因在於：熱膨脹性微球因加熱而於黏著層中膨脹後，無法保持該狀態而一部分發生收縮，結果膨脹之黏著層暫時癟縮。其結果為，有引起與被黏著體之部分性附著，無法將被黏著體自黏著片容易地剝離之情況。因此，期望開發出具備即便於如此加熱條件嚴酷(例如100℃，3小時)之情形時黏著層亦不癟縮而可保持膨脹狀態之黏著層的黏著片。 However, it is sometimes required that after the adhesive layer of the adhesive sheet is adhered to the adherend in opposite directions, the adherend is peeled off from the adherend after heating for a long time (for example, 3 hours) at a relatively low temperature (for example, 100° C.). Even if it is relatively low temperature but is used for long-term heating, the expansion state of the adhesive layer that can be maintained after about 30 minutes from the start of heating may not be maintained at the end of the heating, that is, when the peeling of the adherend starts. It is believed that the reason is that after the heat-expandable microspheres expand in the adhesive layer due to heating, they cannot maintain this state and partly shrink, resulting in temporary shrinkage of the expanded adhesive layer. As a result, partial adhesion to the adherend may occur, and the adherend may not be easily peeled from the adhesive sheet. Therefore, it is desired to develop an adhesive sheet having an adhesive layer that does not shrink even when the heating conditions are severe (for example, 100° C., 3 hours) and can maintain an expanded state.

本發明之目的在於提供一種具有下述黏著層之熱剝離型黏著片及使用該黏著片之被黏著體積層物之製造方法，該黏著層即便加熱條件嚴酷(例如100℃，3小時)，亦不癟縮而可保持膨脹狀態，然後容易自被黏著體剝離。 The object of the present invention is to provide a heat-peelable adhesive sheet having the following adhesive layer and a method for manufacturing an adhered volume layer using the adhesive sheet. The adhesive layer can be heated even under severe heating conditions (for example, 100°C, 3 hours). It does not shrink but can maintain the expanded state, and then it is easy to peel off from the adherend.

本發明人對即便加熱條件嚴酷(例如100℃，3小時)，亦不癟縮而保持膨脹狀態之加熱後黏著層之表面狀態進行努力觀察並反覆研究。結果查明，以加熱後滿足特定之條件之方式形成黏著層即可，從而完 成本發明。 The present inventors have made diligent observations and repeated studies on the surface state of the adhesive layer after heating that does not shrink and maintains an expanded state even if the heating conditions are severe (for example, 100°C, 3 hours). As a result, it was found that the adhesive layer can be formed in a way that satisfies specific conditions after heating. Cost invention.

即，根據本發明，提供具有以下表示之構成之黏著層的熱剝離型黏著片。該黏著片例如可適用於製造被黏著體之上表面經由已硬化之接著層貼合有覆蓋材料的被黏著體積層物。即，根據本發明，亦提供利用該黏著片之以下所示之被黏著體積層物之製造方法。 That is, according to the present invention, there is provided a heat-peelable pressure-sensitive adhesive sheet having an pressure-sensitive adhesive layer having the configuration shown below. The adhesive sheet may be suitable for manufacturing an adhered volume layer in which a covering material is attached to the upper surface of an adherend via a hardened adhesive layer, for example. That is, according to the present invention, there is also provided a method for manufacturing an adhered volume layer using the adhesive sheet as shown below.

本發明之黏著層(加熱前黏著層)之特徵在於：為熱發泡性，並滿足下述2點。 The adhesive layer (adhesive layer before heating) of the present invention is characterized in that it is thermally foamable and satisfies the following two points.

第1，由黏著劑組成物形成，黏著劑組成物為熱發泡性，含有熱發泡劑(較佳為熱膨脹微球)與黏著劑。 First, it is formed by an adhesive composition, which is thermally foamable and contains a thermal foaming agent (preferably thermally expandable microspheres) and an adhesive.

第2，於將其(加熱前熱發泡性黏著層之)表面積設為「S0」，另外，將於100℃經加熱3小時之情形時之熱發泡性黏著層(加熱後熱發泡性黏著層)表面之算術平均粗糙度設為「Ra」，將凹凸之最高點即上限高度設為「H1」，將凹凸之最低點即下限高度設為「H5」，將H1至H5之範圍之表面積設為「SH1-H5」時，以滿足下述式1、2及下述條件a之方式形成。 Second, set its surface area (the heat-foamable adhesive layer before heating) to "S 0 ", and the heat-foamable adhesive layer when heated at 100°C for 3 hours (heat-generate after heating) Foam adhesive layer) The arithmetic average roughness of the surface is set to "Ra", the highest point or upper limit height of the unevenness is set to "H1", the lowest point or lower limit height of the unevenness is set to "H5", and H1 to H5 When the surface area of the range is set to "S H1-H5 ", it is formed to satisfy the following formulas 1 and 2 and the following condition a.

式1：(H1-H5)≧50μm，式2：SH1-H5/S0≧2.5，及條件a：Ra為4~8μm。 Formula 1: (H1-H5)≧50μm, Formula 2: S H1-H5 /S 0 ≧2.5, and condition a: Ra is 4-8μm.

本發明之被黏著體積層物之製造方法係製造被黏著體(例如顯示器基材)之上表面經由已硬化之接著層貼合有覆蓋材料的被黏著體積層物(例如具有顯示器基材/硬化後接著層/覆蓋材料之層構造的顯示器材料)之方法，其特徵在於：利用上述構成之黏著片，以下表面貼合有該黏著片之熱發泡性黏著層之被黏著體的上表面與覆蓋材料之硬化前接著層 對向之方式，將覆蓋材料重疊於被黏著體，繼而以特定之加熱條件(90~110℃，1~10小時)對整體進行加熱，使硬化前接著層硬化後，自被黏著體之下表面剝離上述黏著片。 The manufacturing method of the adhered volume layer of the present invention is to manufacture the adhered volume layer (e.g., with display substrate/hardened The method of the display material of the layer structure of the subsequent layer/covering material is characterized in that: the adhesive sheet of the above-mentioned structure is used, and the upper surface of the adhered body of the thermally foamable adhesive layer of the adhesive sheet is attached to the lower surface of the adhesive sheet and Adhesive layer before hardening of covering material In the opposite way, the covering material is overlapped on the adherend, and then the whole is heated under specific heating conditions (90~110℃, 1~10 hours), so that the adhesive layer is hardened before hardening, from below the adherend The above-mentioned adhesive sheet was peeled off the surface.

本發明之熱剝離型黏著片由於具有以加熱後滿足特定之條件之方式形成之熱發泡性之黏著層，故而即便加熱條件嚴酷(例如100℃，3小時)，加熱後黏著層亦不癟縮，可保持該膨脹狀態。因此，可謂尤其適合於該特定加熱條件下之被黏著體積層物之製造。 The heat-peelable adhesive sheet of the present invention has a thermally foamable adhesive layer formed by heating to meet specific conditions, so even if the heating conditions are severe (for example, 100°C, 3 hours), the adhesive layer does not collapse after heating Contraction can maintain the expanded state. Therefore, it can be said that it is especially suitable for the manufacture of the adhered volume layer under the specific heating condition.

作為被黏著體積層物，並無特別限定，例如可列舉將顯示器基材用作被黏著體，於其上表面經由已硬化之接著層而貼合有覆蓋材料的具有顯示器基材/硬化後接著層/覆蓋材料之層構造之顯示器材料等。作為顯示器材料，例如可列舉用於供用戶觀賞圖像或影像等之具備小型液晶面板之能夠頭戴之隨身顯示器(或頭戴式顯示器(Head Mount Display))的表面材料，或能夠於彎曲或彎折狀態下觀賞圖像或影像等之軟性顯示器等。 The volume layer to be adhered is not particularly limited. For example, a display substrate is used as an adherend, and a covering material is attached to the upper surface of the substrate via a hardened adhesive layer/has a display substrate after curing. The display material of the layer structure of the layer/covering material, etc. As the display material, for example, a surface material for a head-mounted portable display (or head-mounted display (Head Mount Display)) with a small liquid crystal panel for the user to view images or images, or the surface material can be bent or A flexible display for viewing images or images in the bent state.

1‧‧‧黏著片 1‧‧‧Adhesive sheet

3‧‧‧黏著層 3‧‧‧Adhesive layer

5‧‧‧第1隔片 5‧‧‧First spacer

7‧‧‧第2隔片 7‧‧‧Second spacer

20‧‧‧顯示器材料(被黏著體積層物之一例) 20‧‧‧Display material (an example of the volume layer being adhered)

21‧‧‧顯示器基材 21‧‧‧Display substrate

23‧‧‧接著層(硬化前) 23‧‧‧Adhesive layer (before hardening)

23a‧‧‧接著層(硬化後) 23a‧‧‧Adhesive layer (after hardening)

25‧‧‧覆蓋材料 25‧‧‧Cover material

31‧‧‧基材 31‧‧‧Substrate

33‧‧‧第1黏著層(加熱前) 33‧‧‧The first adhesive layer (before heating)

33a‧‧‧第1黏著層(加熱後) 33a‧‧‧The first adhesive layer (after heating)

35‧‧‧第2黏著層 35‧‧‧Second Adhesive Layer

40‧‧‧第1被黏著體 40‧‧‧The first adherend

50‧‧‧第1積層體 50‧‧‧Layer 1

52‧‧‧第2積層體 52‧‧‧Layer 2

54‧‧‧第3積層體 54‧‧‧Layer 3

56‧‧‧第4積層體 56‧‧‧Layer 4

圖1係表示作為本發明一例之黏著片的剖面圖。 Fig. 1 is a cross-sectional view showing an adhesive sheet as an example of the present invention.

圖2係表示作為藉由本發明方法製造之被黏著體積層物一例之顯示器材料的剖面圖。 FIG. 2 is a cross-sectional view showing a display material as an example of an adhered volume layer manufactured by the method of the present invention.

圖3係表示製造圖2之顯示器材料之第1步驟之一狀態的剖面圖。 FIG. 3 is a cross-sectional view showing a state of a first step of manufacturing the display material of FIG. 2. FIG.

圖4係於第1步驟準備之第1積層體之剖面圖。 Fig. 4 is a cross-sectional view of the first laminate prepared in the first step.

圖5係表示第2步驟之一狀態之剖面圖。 Fig. 5 is a cross-sectional view showing a state of the second step.

圖6係於第2步驟準備之第2積層體之剖面圖。 Fig. 6 is a cross-sectional view of the second laminate prepared in the second step.

圖7係於第3步驟準備之第3積層體之剖面圖。 Fig. 7 is a cross-sectional view of the third laminate prepared in the third step.

圖8係表示於第4步驟準備之第4積層體與其加熱處理之情況的剖面圖。 Fig. 8 is a cross-sectional view showing the state of the fourth laminate prepared in the fourth step and its heat treatment.

圖9係表示於第5步驟獲得之顯示器材料的剖面圖。 FIG. 9 is a cross-sectional view showing the display material obtained in the fifth step.

圖10係說明表面積之測定範圍的圖。 Fig. 10 is a diagram illustrating the measurement range of the surface area.

以下，對本發明之黏著片進行詳細說明。 Hereinafter, the adhesive sheet of the present invention will be described in detail.

本發明之黏著片係用於以下步驟之熱剝離型黏著片：於製造被黏著體之上表面經由已硬化之接著層貼合有覆蓋材料之被黏著體積層物時，以下表面貼合有熱發泡性黏著層之被黏著體之上表面與覆蓋材料之硬化前接著層對向之方式，將上述覆蓋材料重疊於上述被黏著體，繼而對整體進行加熱，使上述硬化前接著層硬化後，自上述被黏著體之下表面剝離上述熱發泡性黏著層。於將該熱發泡性黏著層之表面積設為「S0」，將於100℃經加熱3小時之情形時之熱發泡性黏著層表面之算術平均粗糙度設為「Ra」，將凹凸之最高點即上限高度設為「H1」，將凹凸之最低點即下限高度設為「H5」，將H1至H5之範圍之表面積設為「SH1-H5」時，上述熱發泡性黏著層以滿足下述式1、2及下述條件之方式形成。 The adhesive sheet of the present invention is a heat-peelable adhesive sheet used in the following steps: when manufacturing an adhered volume layer with a covering material on the upper surface of an adherend through a hardened adhesive layer, the lower surface is adhered with heat The upper surface of the adherend of the foamable adhesive layer is opposed to the adhesive layer before hardening of the covering material. The covering material is overlapped on the adherend, and then the whole is heated to harden the adhesive layer before hardening. , Peel the thermally foamable adhesive layer from the lower surface of the adherend. Set the surface area of the thermally foamable adhesive layer as "S 0 ", and set the arithmetic average roughness of the surface of the thermally foamable adhesive layer when heated at 100°C for 3 hours as "Ra". When the highest point or upper limit height is set to "H1", the lowest point or lower limit height of the bumps is set to "H5", and the surface area of the range from H1 to H5 is set to "S H1-H5 ", the above-mentioned thermal foaming adhesion The layer is formed so as to satisfy the following formulas 1 and 2 and the following conditions.

式1：(H1-H5)≧50μm，式2：SH1-H5/S0≧2.5，條件：Ra為4~8μm Formula 1: (H1-H5)≧50μm, Formula 2: S H1-H5 /S 0 ≧2.5, condition: Ra is 4~8μm

本發明之黏著片重要的是具有上述熱發泡性黏著層。上述熱 發泡性黏著層含有含熱發泡劑與黏著劑之熱發泡性黏著劑組成物。本發明之黏著片進而可具有形成於上述熱發泡性黏著層之下表面的基材層與形成於該基材層之下表面的微黏著層。 It is important for the adhesive sheet of the present invention to have the above-mentioned thermally foamable adhesive layer. Above heat The foamable adhesive layer contains a thermal foamable adhesive composition containing a thermal foaming agent and an adhesive. The adhesive sheet of the present invention may further have a substrate layer formed on the lower surface of the thermally foamable adhesive layer and a micro adhesive layer formed on the lower surface of the substrate layer.

如圖1所示，作為本發明之黏著片一例的黏著片1可應用於製造顯示器材料(軟性顯示器之表面材料一例)，具有黏著層3，於本例中係藉由將該黏著層3配置於第1隔片5與第2隔片7之間而構成。 As shown in FIG. 1, the adhesive sheet 1 as an example of the adhesive sheet of the present invention can be applied to the manufacture of display materials (an example of the surface material of a flexible display), and has an adhesive layer 3, in this example by disposing the adhesive layer 3 It is formed between the first spacer 5 and the second spacer 7.

黏著層3於本例中係以於基材之正反兩面具有2層黏著層之態樣而構成，具體而言，具有於基材31之一面形成熱發泡性之第1黏著層33作為熱發泡性黏著層，於基材31之另一面(與設置有第1黏著層33相反之面)形成微黏著性第2黏著層35作為微黏著層之至少3層構造。 In this example, the adhesive layer 3 is formed with two adhesive layers on the front and back sides of the substrate. Specifically, the first adhesive layer 33 having thermal foamability formed on one side of the substrate 31 is used as The thermally foamable adhesive layer has a micro-adhesive second adhesive layer 35 formed on the other side of the substrate 31 (the side opposite to the first adhesive layer 33) as at least a three-layer structure of the micro-adhesive layer.

作為基材31，並無特別限定，例如可使用聚對酞酸乙二酯、聚對苯二甲酸丙二酯(polytrimethylene terephthalate)、聚萘二甲酸乙二酯(polyethylene naphthalate)、聚對酞酸丁二酯(polybutylene terephthalate)、聚碳酸酯、三乙醯纖維素、聚醯亞胺、聚醯胺、聚醚碸、聚醚醯亞胺、芳香族聚醯胺、聚碸、丙烯酸、聚氯乙烯、氟樹脂等各種合成樹脂之膜。 The substrate 31 is not particularly limited. For example, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polyethylene terephthalate can be used. Butylene terephthalate (polybutylene terephthalate), polycarbonate, triacetate cellulose, polyimide, polyimide, polyether imide, polyether imide, aromatic polyimide, polyimide, acrylic acid, polychloride Films made of various synthetic resins such as ethylene and fluororesin.

基材31之厚度並無特別限定，一般為10μm~250μm，較佳為25μm~125μm左右。 The thickness of the substrate 31 is not particularly limited, and is generally 10 μm to 250 μm, preferably about 25 μm to 125 μm.

第1黏著層33相當於本發明言及之加熱前發泡性黏著層，於本例中，恰當地調整其物性。此外，以下言及「第1黏著層33」之情形時，意指「加熱前」之狀態，另外，言及「第1黏著層33a」之情形時，意指「加熱後」之狀態。 The first adhesive layer 33 corresponds to the foamable adhesive layer before heating referred to in the present invention, and its physical properties are appropriately adjusted in this example. In addition, when referring to the "first adhesive layer 33" below, it means the state "before heating", and when referring to the "first adhesive layer 33a", it means the state "after heating".

首先，將第1黏著層33之表面積設為「S0」。該值係藉由如下方式獲得： 使用在例如厚度50μm之透明之聚對酞酸乙二酯膜的單面形成有第1黏著層33之黏著片樣品，利用形狀分析雷射顯微鏡(VK-9510：其恩斯公司)等對該第1黏著層33之露出側表面進行測定。 First, the surface area of the first adhesive layer 33 is set to "S 0 ". This value is obtained by the following method: For example, a transparent polyethylene terephthalate film with a thickness of 50 μm is used on one side of a transparent polyethylene terephthalate film with the first adhesive layer 33 formed on one side of the adhesive sheet, and the shape analysis laser microscope (VK-9510 (Cines Corporation) and others measured the exposed side surface of the first adhesive layer 33.

其次，將於100℃將含有第1黏著層33之上述黏著片樣品之整體加熱3小時之情形時之第1黏著層33a表面之算術平均粗糙度設為「Ra」。於本例中，進而將第1黏著層33a表面之最大高度設為「Ry」，將十點平均粗糙度設為「Rz」。此處之Ra、Ry及Rz例如可與上述同樣地利用形狀分析雷射顯微鏡進行測定。 Next, the arithmetic average roughness of the surface of the first adhesive layer 33a when the whole of the adhesive sheet sample containing the first adhesive layer 33 is heated for 3 hours at 100°C is set to "Ra". In this example, the maximum height of the surface of the first adhesive layer 33a is further set to "Ry", and the ten-point average roughness is set to "Rz". Here, Ra, Ry, and Rz can be measured with a shape analysis laser microscope in the same manner as described above, for example.

其次，將存在於第1黏著層33a之表面的凹凸之最高點即上限高度設為「H1」，將最低點即下限高度設為「H5」。另外，將H1至H5之範圍之表面積設為「SH1-H5」。於本例中，進而以上述H1為基準，分別將較該基準低10μm之位置之高度設為「H2」，低20μm之位置之高度設為「H3」，低30μm之位置之高度設為「H4」。進而，將H1至H2之範圍之表面積設為「SH1-H2」，將H1至H3之範圍之表面積設為「SH1-H3」，將H1至H4之範圍之表面積設為「SH1-H4」。 Next, the upper limit height, which is the highest point of the unevenness existing on the surface of the first adhesive layer 33a, is set to "H1", and the lowest point, which is the lower limit height, is set to "H5". In addition, the surface area in the range of H1 to H5 is set to "S H1-H5 ". In this example, using the above H1 as the reference, the height of the position 10μm lower than the reference is set to "H2", the height of the position lower than 20μm is set to "H3", and the height of the position lower than 30μm is set to "H4". Furthermore, the surface area in the range of H1 to H2 is set to "S H1-H2 ", the surface area in the range of H1 to H3 is set to "S H1-H3 ", and the surface area in the range of H1 to H4 is set to "S H1- H4 ".

於如上所述進行定義之情形時，於本例中，以至少滿足上述式1、式2及條件a之方式形成有第1黏著層33。 In the case of the definition as described above, in this example, the first adhesive layer 33 is formed so as to satisfy at least the above formula 1, formula 2, and condition a.

式1係H1與H5之差(H1-H5)成為特定值以上之條件。於本例中，該值可為50μm以上，較佳為55μm以上。該參數(H1-H5)係用以確定存在於第1黏著層33a表面的凹凸之高低差之程度者。 Formula 1 is the condition that the difference between H1 and H5 (H1-H5) becomes a specific value or more. In this example, the value may be 50 μm or more, preferably 55 μm or more. This parameter (H1-H5) is used to determine the degree of the height difference of the unevenness existing on the surface of the first adhesive layer 33a.

式2係將H1至H5之範圍之表面積(SH1-H5)除以第1黏著層33之表面積(S0)獲得之值(SH1-H5/S0)成為特定值以上之條件。於本 例中，該值可為2.5以上，較佳為3.0以上。上限並無特別限定，例如可為3.8左右以下。該參數(SH1-H5/S0)係用以確定與被黏著體之剝離性者。 Formula 2 is the condition that the value (S H1-H5 /S 0 ) obtained by dividing the surface area (S H1-H5 ) of the range of H1 to H5 by the surface area (S 0 ) of the first adhesive layer 33 becomes a specific value or more. In this example, the value can be 2.5 or more, preferably 3.0 or more. The upper limit is not particularly limited, and may be, for example, about 3.8 or less. This parameter (S H1-H5 /S 0 ) is used to determine the peelability from the adherend.

條件a係第1黏著層33a表面之算術平均粗糙度(Ra)成為特定值範圍之條件。於本例中，該值可為4μm以上，較佳為6μm以上，8μm以下。該參數(Ra)係用以確定存在於第1黏著層33a表面的凹凸之粗糙度者。 The condition a is a condition that the arithmetic average roughness (Ra) of the surface of the first adhesive layer 33a becomes a specific value range. In this example, the value may be 4 μm or more, preferably 6 μm or more and 8 μm or less. This parameter (Ra) is used to determine the roughness of the concavities and convexities existing on the surface of the first adhesive layer 33a.

於本例中，發現藉由以加熱後之第1黏著層33a之表面成為特定者之方式形成加熱前之第1黏著層33，即便加熱條件嚴酷(例如100℃，3小時)，亦可保持加熱後之第1黏著層33a之膨脹狀態，結果可容易地進行自被黏著體(下述)之剝離。 In this example, it is found that by forming the first adhesive layer 33 before heating in such a way that the surface of the heated first adhesive layer 33a becomes a specific one, it can be maintained even if the heating conditions are severe (for example, 100°C, 3 hours) The expanded state of the first adhesive layer 33a after heating results in easy peeling from the adherend (described below).

本例之第1黏著層33可以除了滿足上述式1、式2及條件a之全部以外，亦滿足下述式3、式4、式5、條件b及條件c之至少一個(最佳為該等全部)之方式加以調整。 The first adhesive layer 33 of this example may not only satisfy all of the above formula 1, formula 2 and condition a, but also satisfy at least one of the following formula 3, formula 4, formula 5, condition b and condition c (the most preferred is the Etc.) to be adjusted.

式3係將H1至H2之範圍之表面積(SH1-H2)除以第1黏著層33之表面積(S0)獲得之值(SH1-H2/S0)成為特定值範圍之條件。於本例中，該值可為0.13以上，較佳為0.17以上，且可為0.25以下，較佳為0.23以下。 Formula 3 is the condition that the value (S H1-H2 /S 0 ) obtained by dividing the surface area (S H1-H2 ) of the range of H1 to H2 by the surface area (S 0 ) of the first adhesive layer 33 becomes a specific value range. In this example, the value can be 0.13 or more, preferably 0.17 or more, and can be 0.25 or less, preferably 0.23 or less.

式4係將H1至H3之範圍之表面積(SH1-H3)除以第1黏著層33之表面積(S0)獲得之值(SH1-H3/S0)成為特定值範圍之條件。於本例中，該值可為0.90以上，較佳為1.00以上，且可為1.72以下，較佳為1.50以下。 Formula 4 is the condition that the value (S H1-H3 /S 0 ) obtained by dividing the surface area (S H1-H3 ) of the range of H1 to H3 by the surface area (S 0 ) of the first adhesive layer 33 becomes a specific value range. In this example, the value can be 0.90 or more, preferably 1.00 or more, and can be 1.72 or less, preferably 1.50 or less.

式5係將H1至H4之範圍之表面積(SH1-H4)除以第1黏著 層33之表面積(S0)獲得之值(SH1-H4/S0)成為特定值範圍之條件。於本例中，該值可為2.28以上，較佳為2.40以上，且可為3.00以下，較佳為2.90以下。 Formula 5 is the condition that the value (S H1-H4 /S 0 ) obtained by dividing the surface area (S H1-H4 ) of the range of H1 to H4 by the surface area (S 0 ) of the first adhesive layer 33 becomes a specific value range. In this example, the value can be 2.28 or more, preferably 2.40 or more, and can be 3.00 or less, preferably 2.90 or less.

條件b係第1黏著層33a表面之最大高度(Ry)成為特定值範圍之條件。於本例中，該值可為50μm以上，較佳為53μm以上，且可為65μm以下，較佳為63μm以下。 The condition b is a condition that the maximum height (Ry) of the surface of the first adhesive layer 33a becomes a specific value range. In this example, the value may be 50 μm or more, preferably 53 μm or more, and may be 65 μm or less, preferably 63 μm or less.

條件c係第1黏著層33a表面之十點平均粗糙度(Rz)成為特定值範圍之條件。於本例中，該值可為45μm以上，較佳為50μm以上，且可為65μm以下，較佳為61μm以下。 The condition c is a condition that the ten-point average roughness (Rz) of the surface of the first adhesive layer 33a becomes a specific value range. In this example, the value may be 45 μm or more, preferably 50 μm or more, and may be 65 μm or less, preferably 61 μm or less.

上述式3~5以及條件b及c之各參數(SH1-H2/S0)、(SH1-H3/S0)、(SH1-H4/S0)、Ry及Rz之任一者均係用以確定與加熱發泡後之被黏著體之剝離性者。 Any of the above formulas 3 to 5 and the parameters of conditions b and c (S H1-H2 /S 0 ), (S H1-H3 /S 0 ), (S H1-H4 /S 0 ), Ry and Rz Both are used to determine the peelability of the adherend after heating and foaming.

具備上述物性之第1黏著層33係利用含有熱發泡劑與黏著劑作為必須成分之黏著劑組成物形成。 The first adhesive layer 33 having the above-mentioned physical properties is formed using an adhesive composition containing a thermal foaming agent and an adhesive as essential components.

作為熱發泡劑，並無特別限制，可適當選擇例如習知之熱發泡劑(熱分解型者、膨脹石墨、經微膠囊化者等)而使用，其中，可適宜地使用經微膠囊化者(以下稱為「熱膨脹性微球」)。 The thermal foaming agent is not particularly limited. For example, conventional thermal foaming agents (thermally decomposable, expanded graphite, microencapsulated, etc.) can be appropriately selected and used. Among them, microencapsulated can be suitably used. Those (hereinafter referred to as "heat-expandable microspheres").

作為熱膨脹性微球，可列舉下述微球作為適例：具有於有彈性之外殼之內部封入發泡劑之構造，整體顯示出熱膨脹性(因加熱而整體膨脹之性質)。作為有彈性之外殼之適例，可列舉利用熱熔融性物質或因熱膨脹而破壞之物質等例如偏二氯乙烯-丙烯腈共聚物、聚乙烯醇、聚乙烯醇縮丁醛、聚甲基丙烯酸甲酯、聚丙烯腈、聚偏二氯乙烯、聚碸等形成者。 作為發泡劑，主要可列舉容易因加熱發生氣化而膨脹之物質，例如異丁烷、丙烷、戊烷等烴。作為熱膨脹性微球之市售品，例如可列舉商品名「Matsumoto Microsphere」系列(松本油脂製藥公司製造)、Advancell EM系列(積水化學工業公司製造)、Expancel(日本Ferrite公司製造)等。 As the thermally expandable microspheres, the following microspheres can be cited as a suitable example: a structure in which a foaming agent is enclosed in an elastic shell, and the whole exhibits thermal expansion (the property of overall expansion due to heating). Suitable examples of elastic shells include hot-melt materials or materials that are destroyed by thermal expansion, such as vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, and polymethacrylic acid. Formers such as methyl ester, polyacrylonitrile, polyvinylidene chloride, polysulfide, etc. As the foaming agent, substances that are easy to swell due to gasification due to heating, such as hydrocarbons such as isobutane, propane, and pentane, are mainly cited. As commercially available products of thermally expandable microspheres, for example, the brand name "Matsumoto Microsphere" series (manufactured by Matsumoto Oil and Fat Pharmaceutical Co., Ltd.), Advancell EM series (manufactured by Sekisui Chemical Industry Co., Ltd.), Expancel (manufactured by Ferrite Co., Ltd., Japan) and the like can be cited.

熱膨脹性微球之大小可根據黏著片1之用途而適當選擇，具體而言，以質量平均粒徑計較佳為10~20μm。藉由將使用之熱膨脹性微球之大小設為此範圍，可容易地調整初始之黏著力，另外，可容易地控制加熱剝離後之黏著層之表面形狀。 The size of the heat-expandable microspheres can be appropriately selected according to the application of the adhesive sheet 1. Specifically, the mass average particle diameter is preferably 10-20 μm. By setting the size of the heat-expandable microspheres to be used in this range, the initial adhesion can be easily adjusted, and in addition, the surface shape of the adhesive layer after heating and peeling can be easily controlled.

熱膨脹性微球亦可調整其粒度分佈後使用。粒度分佈之調整可將使用之熱膨脹性微球所含有之粒徑相對較大者利用離心力型風力分級機、乾式分級機、篩分機等進行分級而去除。藉由去除粒徑大於平均粒徑之粒子，使粒度分佈陡峭，可提高形成之第1黏著層33之表面之平滑性，使加熱時之表面形狀均勻。具體而言，熱膨脹性微球之粒度分佈之標準偏差理想為設為5.0μm以下，較佳設為4.5μm以下，進而較佳設為4.0μm以下。藉由將標準偏差設為5.0μm以下，可容易地控制加熱剝離後之黏著層之表面形狀。 Thermally expandable microspheres can also be used after adjusting their particle size distribution. The particle size distribution can be adjusted by using a centrifugal force type wind classifier, dry classifier, sieving machine, etc., to remove the relatively large particle size contained in the thermally expandable microspheres used. By removing particles with a particle size larger than the average particle size, the particle size distribution can be made steep, the surface smoothness of the formed first adhesive layer 33 can be improved, and the surface shape during heating can be made uniform. Specifically, the standard deviation of the particle size distribution of the thermally expandable microspheres is desirably 5.0 μm or less, preferably 4.5 μm or less, and more preferably 4.0 μm or less. By setting the standard deviation to 5.0μm or less, the surface shape of the adhesive layer after heating and peeling can be easily controlled.

另外，使用熱膨脹性微球時，藉由預先進行分級，而變得容易調整形成之第1黏著層33之厚度。例如，於將加熱前之第1黏著層33之厚度設為25~35μm左右之情形時，除使用質量平均粒徑為10~20μm左右之熱膨脹性微球以外，亦可使用將質量平均粒徑未達10μm者及大粒徑(例如，粒徑超過20μm者)者分級而去除之熱膨脹性微球。根據如此將熱膨脹性微球加以分級之方法，可直接利用至今為止使用之熱膨脹性微 球。因此，無需重新把握膨脹特性、舉動等，而可縮短開發時間，提高開發效率。 In addition, when thermally expandable microspheres are used, it is easy to adjust the thickness of the first adhesive layer 33 formed by grading in advance. For example, when the thickness of the first adhesive layer 33 before heating is set to about 25~35μm, in addition to using thermally expandable microspheres with a mass average particle size of about 10-20μm, the mass average particle size can also be used. Thermally expandable microspheres that are less than 10 μm and those with large particle diameters (for example, those with a particle diameter of more than 20 μm) are classified and removed. According to the method of classifying the thermally expandable microspheres in this way, the thermally expandable microspheres used so far can be directly used. ball. Therefore, it is not necessary to re-understand the expansion characteristics, behavior, etc., but can shorten the development time and improve the development efficiency.

此外，上述中所謂「粒度分佈」及「質量平均粒徑」係利用雷射繞射式粒度分佈測定裝置測得之值。 In addition, the above-mentioned "particle size distribution" and "mass average particle size" are values measured by a laser diffraction type particle size distribution measuring device.

熱膨脹性微球之發泡倍率為1.5倍以上即可，較佳為5倍以上，進而較佳為7倍以上。另一方面，較佳為15倍以下，進而較佳為12倍以下。若本例使用之熱膨脹性微球之發泡倍率位於較佳為5倍以上且15倍以下之範圍，則藉由加熱處理，可高效率地降低第1黏著層33a之黏著力。此外，熱膨脹性微球之外殼較佳為具有即便該熱膨脹性微球膨脹至上述特定之發泡倍率之情形時亦不破裂的適度強度者。 The expansion ratio of the thermally expandable microspheres may be 1.5 times or more, preferably 5 times or more, and more preferably 7 times or more. On the other hand, it is preferably 15 times or less, and more preferably 12 times or less. If the expansion ratio of the thermally expandable microspheres used in this example is preferably in the range of 5 times or more and 15 times or less, the heat treatment can efficiently reduce the adhesive force of the first adhesive layer 33a. In addition, the outer shell of the heat-expandable microspheres preferably has a moderate strength that does not break even when the heat-expandable microspheres expand to the above-mentioned specific expansion ratio.

另外，作為其他熱發泡劑，可列舉熱分解型發泡劑或膨脹石墨等。熱分解型發泡劑分為無機系與有機系。 In addition, other thermal foaming agents include thermally decomposable foaming agents, expanded graphite, and the like. Thermal decomposition foaming agents are classified into inorganic and organic types.

作為無機系發泡劑，例如可列舉碳酸銨、碳酸氫銨、碳酸氫鈉、亞硝酸銨、硼氫化鈉、疊氮化合物類等。作為有機系發泡劑，例如可列舉水、氟氯化烷烴(例如三氯單氟甲烷、二氯單氟甲烷等)、偶氮系化合物(例如偶氮雙異丁腈、偶氮二甲醯胺(ADCA)、偶氮二羧酸鋇等)、肼系化合物(例如對甲苯磺醯肼或二苯碸-3,3'-二磺醯肼、4,4'-氧基雙(苯磺醯肼)、烯丙基雙(磺醯肼)等)、胺脲系化合物(例如對甲苯磺醯基(p-toluylenesulfonyl)胺脲、4,4'-氧基雙(苯磺醯基胺脲)等)、***系化合物(例如5-嗎啉基(morpholyl)-1,2,3,4-噻***等)、N-亞硝基系化合物(例如N,N'-二亞硝基五亞甲基四胺、N,N'-二甲基-N,N'-二亞硝基對苯二甲醯胺等)等。 As an inorganic foaming agent, ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, azide compounds etc. are mentioned, for example. Examples of organic blowing agents include water, chlorofluoroalkanes (e.g., trichloromonofluoromethane, dichloromonofluoromethane, etc.), and azo compounds (e.g., azobisisobutyronitrile, azobismethyl cyanide). Amine (ADCA), barium azodicarboxylate, etc.), hydrazine compounds (such as p-toluenesulfonamide or diphenylsulfonium-3,3'-disulfonylhydrazine, 4,4'-oxybis(benzenesulfonate) Hydrazine), allyl bis(sulfonyl hydrazine), etc.), semicarbazide compounds (e.g. p-toluylenesulfonyl semicarbazide, 4,4'-oxy bis(benzenesulfonyl sulphazamide) ) Etc.), triazole compounds (e.g. 5-morpholyl (morpholyl)-1,2,3,4-thiatriazole, etc.), N-nitroso compounds (e.g. N,N'-dinitroso Pentamethylenetetramine, N,N'-dimethyl-N,N'-dinitroso-p-xylylenedimethamide, etc.).

該等熱發泡劑可單獨使用，或將多種混合而使用。 These thermal foaming agents can be used alone or in combination of multiple types.

於使用熱膨脹性微球作為熱發泡劑之情形時，其摻合量相對於下述黏著劑100質量份，較佳設為10質量份以上，更佳設為13質量份以上，較佳設為50質量份以下，更佳設為40質量份以下。若熱膨脹性微球之摻合量過小，則有加熱後之剝離性變得不充分之情況。另一方面，若摻合量過多，則有初始之黏著力過度降低之情況。 In the case of using heat-expandable microspheres as the thermal foaming agent, the blending amount is preferably 10 parts by mass or more, more preferably 13 parts by mass or more, relative to 100 parts by mass of the following adhesive It is 50 parts by mass or less, more preferably 40 parts by mass or less. If the blending amount of the heat-expandable microspheres is too small, the peelability after heating may become insufficient. On the other hand, if the blending amount is too large, the initial adhesion may be excessively reduced.

熱發泡劑之摻合比率以能夠充分地形成加熱後之第1黏著層33a表面之凹凸之方式適當選擇即可，通常相對於下述黏著劑：100質量份，而為10~50質量份之範圍。於實驗中，若熱發泡劑之摻合比率未達10質量份，則加熱後之第1黏著層33a表層之凸部變少，而有變得難以剝離之傾向，另外，若超過50質量份，則會於加熱前之第1黏著層33表面形成凹凸，而有與被黏著體(本例中為下述顯示器基材21；以下僅稱為「被黏著體」之情形時亦相同)之加熱前之密接性降低之傾向，故而欠佳。就與被黏著體之加熱前之密接性及自被黏著體之加熱後之剝離性方面而言，較佳之摻合比率為13~40質量份，更佳為15~30質量份。 The blending ratio of the thermal foaming agent may be appropriately selected so as to sufficiently form the unevenness on the surface of the first adhesive layer 33a after heating, and it is usually 10-50 parts by mass relative to the following adhesive: 100 parts by mass The scope. In the experiment, if the blending ratio of the thermal foaming agent is less than 10 parts by mass, the protrusions on the surface of the first adhesive layer 33a after heating will decrease, and it will tend to be difficult to peel off. In addition, if it exceeds 50 parts by mass It will form irregularities on the surface of the first adhesive layer 33 before heating, and have the same as the adherend (in this example, the display substrate 21 is described below; the same is true when it is only referred to as the "adherent" below) The adhesion before heating tends to decrease, so it is not good. In terms of adhesion to the adherend before heating and peelability from the adherend after heating, the preferred blending ratio is 13 to 40 parts by mass, and more preferably 15 to 30 parts by mass.

於本例中，作為使用之熱發泡劑，使用其熱發泡溫度為80℃以上(尤其是90℃以上)，且為110℃以下(尤其是100℃以下)者。藉由使用熱發泡溫度屬於特定範圍之熱發泡劑，可容易地維持熱發泡劑最佳地發泡之狀態。熱發泡溫度於使用熱膨脹性微球作為熱發泡劑之情形時相當於熱膨脹溫度，使用熱分解型發泡劑作為熱發泡劑之情形時相當於熱分解溫度。此處，所謂「熱膨脹溫度」係與發泡開始溫度含義相同，本例中意指TMA測定中之熱膨脹開始溫度，並非意指體積膨脹至最大限度之最大膨脹溫度。若熱發泡溫度為屬於特定範圍者，則亦可將2種以上組合而使 用。 In this example, as the thermal foaming agent used, one whose thermal foaming temperature is 80°C or higher (especially 90°C or higher) and 110°C or lower (especially 100°C or lower) is used. By using a thermal foaming agent whose thermal foaming temperature falls within a specific range, the optimal foaming state of the thermal foaming agent can be easily maintained. The thermal foaming temperature corresponds to the thermal expansion temperature when the thermally expandable microspheres are used as the thermal foaming agent, and corresponds to the thermal decomposition temperature when the thermally decomposable foaming agent is used as the thermal foaming agent. Here, the so-called "thermal expansion temperature" has the same meaning as the foaming start temperature. In this example, it means the thermal expansion start temperature in the TMA measurement, and does not mean the maximum expansion temperature at which the volume expands to the maximum. If the thermal foaming temperature falls within a specific range, you can also combine two or more of them to make use.

於使用熱膨脹性微球作為熱發泡劑之情形時，可使用其最大膨脹溫度為120℃以上(尤其是125℃以上)，且為140℃以下(尤其是135℃以下)者。 When using thermally expandable microspheres as the thermal foaming agent, the maximum expansion temperature of 120°C or higher (especially 125°C or higher) and 140°C or lower (especially 135°C or lower) can be used.

作為黏著劑，可自先前形成含有熱發泡劑之黏著層時使用之黏著劑中適當選擇。其中，就使熱發泡劑發泡時之第1黏著層33a表面形成之凹凸形狀或初始黏著力、再剝離性之方面而言，較佳使用丙烯酸系黏著劑。丙烯酸系黏著劑之組成並無特別限制。其中，較佳使用酸值為30以上之丙烯酸系黏著劑。其原因在於：藉由將丙烯酸系黏著劑之酸值設為30以上，於使用交聯劑進行交聯之情形時可達成充分之交聯密度，因此黏著劑藉由加熱處理而容易自被黏著體無糊劑殘留地剝離，就此方面而言較便利。此外，所謂「酸值」，係指將1g試樣(丙烯酸系黏著劑)中所含之游離脂肪酸或樹脂酸加以中和所需之氫氧化鉀之量(mg)，可依據JIS K0070進行測定，並根據下述式(1)，藉由中和滴定法而算出。 As the adhesive, it can be appropriately selected from the adhesives previously used when forming the adhesive layer containing the thermal foaming agent. Among them, it is preferable to use an acrylic adhesive in terms of the uneven shape formed on the surface of the first adhesive layer 33a when the thermal foaming agent is foamed, the initial adhesive force, and the releasability. The composition of the acrylic adhesive is not particularly limited. Among them, it is preferable to use an acrylic adhesive having an acid value of 30 or more. The reason is that by setting the acid value of the acrylic adhesive to 30 or more, sufficient crosslinking density can be achieved when the crosslinking agent is used for crosslinking, so the adhesive is easily self-adhesive by heat treatment The body peels off without any paste residue, which is more convenient in this respect. In addition, the "acid value" refers to the amount of potassium hydroxide (mg) required to neutralize the free fatty acid or resin acid contained in 1 g of the sample (acrylic adhesive), which can be measured in accordance with JIS K0070 , And calculated by the neutralization titration method according to the following formula (1).

酸值A=B×F×5.611/S…(1) Acid value A=B×F×5.611/S…(1)

[B：用於測定之0.1ml/1氫氧化鉀之乙醇溶液之量，F：0.1莫耳/1氫氧化鉀之乙醇溶液之因數，S：試樣之質量(g)，5.611：氫氧化鉀之式量(56.11×1/10)] [B: The amount of 0.1ml/1 potassium hydroxide ethanol solution used for determination, F: the factor of 0.1 mol/1 potassium hydroxide ethanol solution, S: the mass of the sample (g), 5.611: hydroxide Formula weight of potassium (56.11×1/10)]

丙烯酸系黏著劑之重量平均分子量並無特別限定，較佳為1萬~200萬，進而較佳為10萬~150萬，尤佳為20萬~100萬。藉由將丙烯酸系黏著劑之重量平均分子量設為上述範圍內，容易成為具有對於進行更 高精度之加工而言充分之黏著力，且對於被黏著體無糊劑殘留而剝離性更良好者。 The weight average molecular weight of the acrylic adhesive is not particularly limited, and is preferably 10,000 to 2 million, more preferably 100,000 to 1.5 million, and particularly preferably 200,000 to 1 million. By setting the weight average molecular weight of the acrylic adhesive within the above range, it is easy to For high-precision processing, sufficient adhesive force, no paste residue on the adherend, and better peelability.

丙烯酸系黏著劑較佳為能夠與交聯劑進行反應者。該丙烯酸系黏著劑包含丙烯酸烷基酯及/或甲基丙烯酸烷基酯與具有能夠與交聯劑進行反應之官能基之單體的共聚物。作為丙烯酸烷基酯及甲基丙烯酸烷基酯之「烷基酯」，例如可列舉甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、第二丁酯、第三丁酯、戊酯、己酯、庚酯、辛酯、異辛酯、2-乙基己酯、異癸酯、十二基酯、十三基酯、十五基酯、十八基酯、十九基酯、二十基酯等。作為能夠與交聯劑進行反應之官能基，可列舉羧基、羥基。 The acrylic adhesive is preferably one capable of reacting with the crosslinking agent. The acrylic adhesive includes a copolymer of alkyl acrylate and/or alkyl methacrylate and a monomer having a functional group capable of reacting with a crosslinking agent. Examples of "alkyl esters" of alkyl acrylates and alkyl methacrylates include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, and tertiary butyl. Ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, isooctyl ester, 2-ethylhexyl ester, isodecyl ester, dodecyl ester, tridecyl ester, pentadecyl ester, octadecyl ester, ten Nonayl ester, eicosyl ester, etc. Examples of the functional group capable of reacting with the crosslinking agent include a carboxyl group and a hydroxyl group.

作為能夠與交聯劑進行反應之官能基為羧基之單體，可列舉丙烯酸、甲基丙烯酸、丙烯酸基羧乙酯、丙烯酸羧基戊酯、衣康酸、順丁烯二酸、反丁烯二酸、丁烯酸等。另外，作為官能基為羥基之單體，可列舉丙烯酸羥基乙酯、甲基丙烯酸羥基乙酯、丙烯酸羥基丙酯、甲基丙烯酸羥基丙酯、丙烯酸羥基丁酯、甲基丙烯酸羥基丁酯、丙烯酸羥基己酯、甲基丙烯酸羥基己酯、丙烯酸羥基辛酯、甲基丙烯酸羥基辛酯、丙烯酸羥基癸酯、甲基丙烯酸羥基癸酯、丙烯酸羥基月桂酯、甲基丙烯酸羥基月桂酯等。 As a monomer whose functional group that can react with the crosslinking agent is a carboxyl group, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and fumaric acid can be cited. Acid, crotonic acid, etc. In addition, examples of monomers whose functional groups are hydroxyl groups include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and acrylic acid. Hydroxyhexyl ester, hydroxyhexyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate, hydroxydecyl acrylate, hydroxydecyl methacrylate, hydroxylauryl acrylate, hydroxylauryl methacrylate, etc.

具有能夠與交聯劑進行反應之官能基之單體可單獨使用，或將兩種以上組合而使用。(甲基)丙烯酸烷基酯與具有能夠與交聯劑進行反應之官能基之單體之比以質量比計較佳為85：15~98：2之範圍。若具有能夠與交聯劑進行反應之官能基之單體的摻合比少於該範圍，則於熱膨脹性微球膨脹之情形時，有自被黏著體之剝離性受損之傾向。另一方面，若具有 能夠與交聯劑進行反應之官能基之單體的摻合比多於該範圍，則有缺乏對被黏著體之黏著力之傾向。就提高對被黏著體之黏著性與自被黏著體之剝離性之觀點而言，(甲基)丙烯酸烷基酯與具有能夠與交聯劑進行反應之官能基之單體的比以質量比計進而較佳為88：12~93：7。 The monomer having a functional group capable of reacting with the crosslinking agent can be used alone or in combination of two or more. The ratio of the alkyl (meth)acrylate to the monomer having a functional group capable of reacting with the crosslinking agent is preferably in the range of 85:15 to 98:2 in terms of mass ratio. If the blending ratio of the monomer having a functional group capable of reacting with the crosslinking agent is less than this range, when the thermally expandable microspheres expand, the peelability from the adherend tends to be impaired. On the other hand, if you have If the blending ratio of the monomer of the functional group capable of reacting with the crosslinking agent is more than this range, there is a tendency that the adhesive force to the adherend is lacking. From the viewpoint of improving the adhesion to the adherend and the peelability from the adherend, the ratio of the alkyl (meth)acrylate to the monomer having a functional group capable of reacting with the crosslinking agent is in terms of mass ratio The calculation is further preferably 88:12~93:7.

此外，視需要亦可併用(甲基)丙烯酸烷基酯、及具有能夠與交聯劑進行反應之官能基之單體以外之其他單體。作為其他單體，例如可列舉苯乙烯、乙酸乙烯酯、丙烯腈、丙烯醯胺、聚乙二醇丙烯酸酯、N-乙烯基吡咯啶酮、丙烯酸四氫糠酯等。 In addition, if necessary, other monomers other than the alkyl (meth)acrylate and the monomer having a functional group capable of reacting with the crosslinking agent may be used in combination. Examples of other monomers include styrene, vinyl acetate, acrylonitrile, acrylamide, polyethylene glycol acrylate, N-vinylpyrrolidone, and tetrahydrofurfuryl acrylate.

丙烯酸系黏著劑可藉由使單體成分進行自由基共聚合而獲得。該情形時之共聚合法為先前公知者，可列舉乳化聚合法、溶液聚合法、塊狀聚合法、懸浮聚合法、光聚合法等。另外，丙烯酸系黏著劑之玻璃轉移溫度較佳為-50~-15℃。若玻璃轉移溫度超過-15℃，則有對被黏著體之黏著力降低之傾向。另一方面，若玻璃轉移溫度未達-50℃，則自被黏著體剝離時容易發生糊劑殘留，而有剝離性難以變得良好之傾向。就提高對被黏著體之黏著性及自被黏著體之剝離性之觀點而言，丙烯酸系黏著劑之玻璃轉移溫度進而較佳為-40℃~-20℃。 The acrylic adhesive can be obtained by radically copolymerizing monomer components. The copolymerization method in this case is previously known, and examples thereof include an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method. In addition, the glass transition temperature of the acrylic adhesive is preferably -50 to -15°C. If the glass transition temperature exceeds -15°C, the adhesion to the adherend tends to decrease. On the other hand, if the glass transition temperature is less than -50°C, paste residue is likely to occur when peeling from the adherend, and the peelability tends to be difficult to become good. From the viewpoint of improving the adhesion to the adherend and the peelability from the adherend, the glass transition temperature of the acrylic adhesive is further preferably -40°C to -20°C.

其次，對交聯劑進行說明。交聯劑可根據使用之丙烯酸系黏著劑而適當選擇，並無特別制約。作為交聯劑之具體例，可列舉異氰酸酯系交聯劑、金屬螯合交聯劑、環氧系交聯劑等。該等中，就提高加熱至熱膨脹性微球發生膨脹之溫度後自被黏著體之剝離性，而防止對被黏著體之糊劑殘留之觀點而言，較佳使用環氧系交聯劑。作為環氧系交聯劑，例如可列舉雙酚系環氧樹脂(例如，雙酚A型、雙酚F型、雙酚AD型)、苯酚 酚醛清漆型環氧樹脂、乙二醇二縮水甘油醚、1,6-己二醇縮水甘油醚、三羥甲基丙烷三縮水甘油醚、二縮水甘油基苯胺、二縮水甘油胺、N,N,N',N'-四縮水甘油基間苯二甲胺、1,3-雙(N,N'-二縮水甘油基胺基甲基)環己烷等。 Next, the crosslinking agent will be described. The crosslinking agent can be appropriately selected according to the acrylic adhesive used, and there is no particular restriction. As a specific example of a crosslinking agent, an isocyanate type crosslinking agent, a metal chelate crosslinking agent, an epoxy type crosslinking agent, etc. are mentioned. Among them, from the viewpoint of improving the peelability from the adherend after heating to the temperature at which the thermally expandable microspheres expand, and preventing the paste remaining on the adherend, it is preferable to use an epoxy-based crosslinking agent. As the epoxy crosslinking agent, for example, bisphenol epoxy resin (for example, bisphenol A type, bisphenol F type, bisphenol AD type), phenol Novolac type epoxy resin, ethylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diglycidylamine, N,N ,N',N'-tetraglycidyl metaxylylenediamine, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, etc.

另外，就常溫下之與被黏著體之黏著性，及熱膨脹性微球膨脹後之自被黏著體之剝離性之方面而言，較佳為多官能之環氧系交聯劑，進而較佳為4官能之環氧系交聯劑。具體而言，可列舉N,N,N',N'-四縮水甘油基間苯二甲胺、1,3-雙(N,N'-二縮水甘油基胺基甲基)環己烷。其中，該等環氧系交聯劑由於有交聯反應速度變慢之傾向，故而於交聯反應不充分之情形時，為了促進交聯反應，較理想為(1)添加胺等觸媒，(2)使用具有胺系官能基之單體作為黏著劑之構成成分，(3)對交聯劑併用氮丙啶系交聯劑。尤佳對N,N,N',N'-四縮水甘油基間苯二甲胺等交聯劑添加具有觸媒效果之三級胺。 In addition, in terms of the adhesion to the adherend at room temperature and the peelability of the thermally expandable microspheres from the adherend after expansion, a multifunctional epoxy-based crosslinking agent is preferred, and more preferred It is a 4-functional epoxy crosslinking agent. Specifically, N,N,N',N'-tetraglycidyl metaxylylenediamine and 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane can be cited. Among them, these epoxy-based crosslinking agents tend to slow down the crosslinking reaction rate, so when the crosslinking reaction is insufficient, in order to promote the crosslinking reaction, it is more desirable to (1) add a catalyst such as an amine, (2) Use a monomer having an amine-based functional group as a constituent of the adhesive, and (3) use an aziridine-based cross-linking agent in combination with the cross-linking agent. It is especially good to add a tertiary amine with catalytic effect to cross-linking agents such as N,N,N',N'-tetraglycidyl metaxylylenediamine.

交聯劑可單獨使用，亦可將兩種以上組合而使用。交聯劑之摻合比率與上述熱膨脹性微球、丙烯酸系黏著劑、及視需要使用之下述黏著賦予樹脂一併以第1黏著層33成為較佳之彈性模數之方式適當選擇即可，並無特別限制。其中，黏著劑組成物所含之交聯劑之比率以相對於丙烯酸系黏著劑之比率計設為0.5當量以下時與基材31之密接性提高，故而較佳。若交聯劑之比率以相對於丙烯酸系黏著劑之比率計超過0.5當量，則有對被黏著體之黏著力變得容易降低，使熱膨脹性微球加熱膨脹前，被黏著體變得容易剝離之傾向，故而欠佳。就與基材31及被黏著體之密接性之方面而言，黏著劑組成物所含之交聯劑之比率以相對於丙烯酸系黏著劑之 比率計進而較佳為設為1×10-3~0.3當量。 The crosslinking agent may be used alone or in combination of two or more kinds. The blending ratio of the crosslinking agent, the above-mentioned thermally expandable microspheres, acrylic adhesives, and the following adhesion-imparting resins as needed may be appropriately selected in such a way that the first adhesive layer 33 becomes a better modulus of elasticity. There are no special restrictions. Among them, when the ratio of the crosslinking agent contained in the adhesive composition is 0.5 equivalent or less with respect to the acrylic adhesive, the adhesion to the substrate 31 is improved, which is preferable. If the ratio of the cross-linking agent exceeds 0.5 equivalent in terms of the ratio of the acrylic adhesive, the adhesive force to the adherend becomes easy to decrease, and the adherend becomes easy to peel off before the heat-expandable microspheres are heated and expanded. The tendency is therefore not good. In terms of the adhesion to the substrate 31 and the adherend, the ratio of the crosslinking agent contained in the adhesive composition to the ratio of the acrylic adhesive is more preferably set to 1×10 -3 ~0.3 equivalent.

若將第1黏著層33於20℃之彈性模數設為1.0×104Pa以上且未達1.0×106Pa之範圍，則有初始剝離力降低之傾向，故而有對被黏著體之密接性降低之情況。因而，亦假定被黏著體之加工精度或加工良率降低之情況。因此，使形成第1黏著層33之黏著劑組成物含有黏著賦予樹脂作為黏著賦予劑時，常溫附近之對被黏著體之密接性之調整變得容易，故而較佳。 If the elastic modulus of the first adhesive layer 33 at 20°C is set to 1.0×10 4 Pa or more and less than 1.0×10 6 Pa, the initial peeling force tends to decrease, so there is a close contact with the adherend Conditions of reduced sex. Therefore, it is also assumed that the processing accuracy or processing yield of the adherend is reduced. Therefore, when the adhesive composition forming the first adhesive layer 33 contains an adhesion-imparting resin as an adhesion-imparting agent, it is easier to adjust the adhesion to the adherend in the vicinity of room temperature, which is preferable.

作為黏著賦予樹脂，較佳為其軟化點為120℃以上者。作為黏著賦予樹脂之具體例，可列舉α-蒎烯系、β-蒎烯系、雙戊烯系、萜烯-酚系等萜烯系樹脂；膠質系、木系、妥爾油系等天然系松香；對該等天然系松香進行氫化、歧化、聚合、順丁烯二醯化、酯化等處理之松香系衍生物等松香系樹脂；石油樹脂；薰草哢-茚樹脂等。 As the adhesion-imparting resin, one having a softening point of 120°C or higher is preferred. Specific examples of adhesion-imparting resins include terpene-based resins such as α-pinene-based, β-pinene-based, dipentene-based, and terpene-phenol-based resins; natural resins such as gum-based, wood-based, and tall oil-based resins. Rosin; rosin-based resins such as rosin-based derivatives that undergo hydrogenation, disproportionation, polymerization, maleization, and esterification of these natural rosins; petroleum resins; lavender-indene resins, etc.

該等中，進而較佳為軟化點為120~160℃之範圍內者，尤佳為140~160℃之範圍者。若使用軟化點為上述範圍內之黏著賦予樹脂，則對被黏著體之污染、糊劑殘留較少，不僅如此，進而可提高作業環境下之對被黏著體之密接性。另外，容易將第1黏著層33之彈性模數調整至所需之特定範圍內，而且即便第1黏著層33之彈性模數未達10×106Pa亦可提高初始剝離力，故而較佳。進而，若使用萜酚系之黏著賦予樹脂作為黏著賦予樹脂，則對被黏著體之污染、糊劑殘留較少，不僅如此，於50~90℃之環境下之對被黏著體之黏著性提高，並且熱膨脹性微球膨脹後，自被黏著體之剝離變得更容易。 Among these, those having a softening point in the range of 120 to 160°C are more preferred, and those in the range of 140 to 160°C are particularly preferred. If the softening point is within the above range of the adhesion imparting resin, there will be less contamination to the adherend and less paste residue. Not only that, but also the adhesion to the adherend under the working environment can be improved. In addition, it is easy to adjust the elastic modulus of the first adhesive layer 33 to a specific range required, and even if the elastic modulus of the first adhesive layer 33 does not reach 10×10 6 Pa, the initial peeling force can be improved, so it is better . Furthermore, if a terpene phenol-based adhesion-imparting resin is used as the adhesion-imparting resin, there will be less contamination and paste residue on the adherend. Not only that, the adhesion to the adherend under an environment of 50~90℃ is improved. And after the heat-expandable microspheres expand, the peeling from the adherend becomes easier.

黏著賦予樹脂之摻合比率以能夠將第1黏著層33之彈性模 數調整至所需之特定數值範圍內之方式適當選擇即可，並無特別限制。其中，就第1黏著層33之彈性模數及初始剝離力之方面而言，相對於丙烯酸系黏著劑100質量份，較佳設為10~100質量份。若黏著賦予樹脂之摻合比率相對於丙烯酸系黏著劑100質量份未達10質量份，則有作業時對被黏著體之密接性降低之傾向。另一方面，若超過100質量份，則常溫下之對被黏著體之貼附性降低。就對被黏著體之密接性及常溫下之貼附性之方面而言，進而較佳將黏著賦予樹脂之摻合比率相對於丙烯酸系黏著劑100質量份設為15~50質量份。另外，黏著賦予樹脂之羥值較佳為30mg/KOHg以上。藉由將黏著賦予樹脂之羥值設為30mg/KOHg以上，則加熱處理後之剝離時，變得更難於被黏著體上發生糊劑殘留。 The blending ratio of the adhesive imparting resin can be used to make the elastic mold of the first adhesive layer 33 The method of adjusting the number to the required specific value range can be selected appropriately, and there is no particular limitation. Among them, in terms of the elastic modulus and initial peeling force of the first adhesive layer 33, it is preferably 10-100 parts by mass relative to 100 parts by mass of the acrylic adhesive. If the blending ratio of the adhesion-imparting resin is less than 10 parts by mass relative to 100 parts by mass of the acrylic adhesive, the adhesion to the adherend during operation tends to decrease. On the other hand, if it exceeds 100 parts by mass, the adhesion to the adherend at room temperature decreases. In terms of the adhesion to the adherend and the adherence at room temperature, it is more preferable to set the blending ratio of the adhesion-imparting resin to 15-50 parts by mass relative to 100 parts by mass of the acrylic adhesive. In addition, the hydroxyl value of the adhesion-imparting resin is preferably 30 mg/KOHg or more. By setting the hydroxyl value of the adhesion-imparting resin to 30 mg/KOHg or more, it becomes more difficult for the paste to remain on the adherend during peeling after the heat treatment.

此外，只要為無損作為黏著劑組成物之功能之範圍，則第1黏著層33可含有反應促進劑、界面活性劑、顏料、潤滑劑、著色劑、抗靜電劑、難燃劑、抗菌劑、防黴劑、紫外線吸收劑、光穩定劑、抗氧化劑、勻染劑、流動調整劑、消泡劑等各種添加劑。 In addition, the first adhesive layer 33 may contain reaction accelerators, surfactants, pigments, lubricants, colorants, antistatic agents, flame retardants, antibacterial agents, as long as it does not impair the function of the adhesive composition. Various additives such as anti-mold agent, ultraviolet absorber, light stabilizer, antioxidant, leveling agent, flow regulator, defoamer, etc.

黏著劑組成物可藉由以任意順序添加上述黏著劑、熱發泡劑、進而視需要之交聯劑、黏著賦予劑、溶劑、以及添加劑，並使之溶解或分散而獲得。上述原材料之混合可利用分散攪拌機、行星式混合機、蝶形混合機等混合機或混練機而進行。混合溫度根據組成而異，需要在熱發泡劑之熱發泡溫度(T1)以下進行。 The adhesive composition can be obtained by adding the above-mentioned adhesive, thermal foaming agent, and optionally crosslinking agent, adhesive imparting agent, solvent, and additives in any order, and dissolving or dispersing them. The mixing of the above-mentioned raw materials can be performed using a mixer or kneader such as a dispersion mixer, a planetary mixer, or a butterfly mixer. The mixing temperature varies according to the composition and needs to be performed below the thermal foaming temperature (T1) of the thermal foaming agent.

第1黏著層33可藉由將上述黏著劑組成物塗佈於基材31之一面，視需要使之乾燥而獲得。 The first adhesive layer 33 can be obtained by coating the above-mentioned adhesive composition on one surface of the substrate 31 and drying it as necessary.

於本例中，第1黏著層33之厚度以所選擇之熱發泡劑之大 小(質量平均粒徑)為基準，可較佳設為其15%以上，更佳設為20%以上，且較佳設為75%以下，更佳設為60%以下。例如，於使用質量平均粒徑為9μm~15μm者作為熱發泡劑之情形時，對於第1黏著層33之厚度，較佳將下限設為20μm以上，進而35μm以上，且較佳將上限設為60μm以下，進而50μm以下。藉由將第1黏著層33之厚度設為20μm以上，容易使初始之黏著力變得充分。藉由將第1黏著層33之厚度設為60μm以下，加熱處理後之剝離時變得難以發生凝集破壞，而容易獲得更良好之剝離性。另外，由於加熱處理時用以使熱發泡劑充分發泡之能量容易傳遍整個黏著層，故而加熱處理後之剝離時更難發生糊劑殘留。 In this example, the thickness of the first adhesive layer 33 is as large as the selected thermal foaming agent Small (mass average particle diameter) is a reference, and it can be preferably set to 15% or more, more preferably 20% or more, and more preferably 75% or less, and more preferably 60% or less. For example, when a mass average particle diameter of 9 μm to 15 μm is used as the thermal foaming agent, the thickness of the first adhesive layer 33 is preferably set to the lower limit of 20 μm or more, and further 35 μm or more, and the upper limit is preferably set It is 60 μm or less, and furthermore, 50 μm or less. By setting the thickness of the first adhesive layer 33 to 20 μm or more, it is easy to make the initial adhesive force sufficient. By setting the thickness of the first adhesive layer 33 to 60 μm or less, it becomes difficult to cause cohesive failure during peeling after the heat treatment, and it is easy to obtain better peelability. In addition, since the energy used to fully foam the thermal foaming agent during the heating process is easily transmitted throughout the entire adhesive layer, it is more difficult to cause paste residue during peeling after the heating process.

此外，根據第1黏著層33中殘存之揮發成分之量(殘存揮發成分量)，有時會對加熱處理後之自被黏著體之剝離性、糊劑殘留性產生影響。因此，較佳將第1黏著層33中之殘存揮發成分量設為4質量%以下，進而較佳設為2質量%以下。 In addition, depending on the amount of volatile components remaining in the first adhesive layer 33 (the amount of remaining volatile components), the releasability from the adherend after the heat treatment and the paste residue may be affected. Therefore, the amount of the remaining volatile components in the first adhesive layer 33 is preferably 4% by mass or less, and more preferably 2% by mass or less.

第1黏著層33由於以加熱後滿足特定條件(至少式1、式2及條件a)之方式形成，故而即便供於如90~110℃、1~10小時之嚴酷條件之加熱，加熱後發生膨脹之第1黏著層33a(下述)亦不癟縮而保持其膨脹狀態。 The first adhesive layer 33 is formed in a manner that satisfies specific conditions (at least formula 1, formula 2 and condition a) after heating, so even if it is heated under severe conditions such as 90 to 110°C for 1 to 10 hours, it will be heated. The expanded first adhesive layer 33a (described below) also does not shrink and maintains its expanded state.

第2黏著層35可將其加熱處理前之剝離力(對於聚對酞酸乙二酯膜)調整至0.4N/25mm以下左右，較佳調整至0.1~0.4(N/25mm)左右，其組成(黏著劑組成物)並無特別限定。其中，於本例中，第2黏著層35不包括第1黏著層33所含之熱發泡劑。 The second adhesive layer 35 can adjust its peeling force before heat treatment (for polyethylene terephthalate film) to about 0.4N/25mm or less, preferably to about 0.1~0.4 (N/25mm), and its composition (Adhesive composition) is not particularly limited. Among them, in this example, the second adhesive layer 35 does not include the thermal foaming agent contained in the first adhesive layer 33.

第2黏著層35可藉由將特定組成之黏著劑組成物塗佈於基材31之另一 面(與設置有第1黏著層33之面相反之面)，並視需要使之乾燥而獲得。 The second adhesive layer 35 can be formed by applying an adhesive composition of a specific composition to the other of the substrate 31 The surface (the surface opposite to the surface on which the first adhesive layer 33 is provided) is obtained by drying it as needed.

第2黏著層35之厚度並無特別限定，例如較佳將下限設為3μm以上，進而設為5μm以上，且較佳將上限設為15μm以下，進而10μm以下。若第2黏著層35之厚度過厚，則容易產生重貼或加工後之去除變困難等不良情況，另外，若過薄，難以獲得因設置其而產生之效果。 The thickness of the second adhesive layer 35 is not particularly limited. For example, the lower limit is preferably 3 μm or more, and further 5 μm or more, and the upper limit is preferably 15 μm or less, and further 10 μm or less. If the thickness of the second adhesive layer 35 is too thick, problems such as re-attachment or difficulty in removal after processing are likely to occur, and if it is too thin, it is difficult to obtain the effect due to its placement.

作為第1隔片5及第2隔片7，並無特別限定，例如可使用聚乙烯層壓紙、或聚丙烯、聚乙烯、聚對酞酸乙二酯、聚對酞酸丁二酯、聚萘二甲酸乙二酯、聚碳酸酯、三乙醯纖維素、聚氯乙烯、丙烯酸系樹脂、聚苯乙烯、聚醯胺、聚醯亞胺、偏二氯乙烯-氯乙烯共聚物等之塑膠膜，或對上述塑膠膜之一面實施過脫模處理者等。 The first separator 5 and the second separator 7 are not particularly limited. For example, polyethylene laminated paper, or polypropylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, Polyethylene naphthalate, polycarbonate, triacetyl cellulose, polyvinyl chloride, acrylic resin, polystyrene, polyamide, polyimide, vinylidene chloride-vinyl chloride copolymer, etc. Plastic film, or those who have performed demolding treatment on one side of the above-mentioned plastic film, etc.

第1隔片5及第2隔片7之厚度並無特別限定，一般為10μm~250μm，較佳為25μm~125μm。 The thickness of the first spacer 5 and the second spacer 7 is not particularly limited, and is generally 10 μm to 250 μm, preferably 25 μm to 125 μm.

本例之黏著片1由於具有含有以加熱後滿足特定條件(至少式1、式2及條件a)之方式形成之熱發泡性第1黏著層33之黏著層3，即便供於如90~110℃、1~10小時之嚴酷條件之加熱，加熱後膨脹之第1黏著層33a亦不癟縮而保持其膨脹狀態。因此，可作為加熱前能夠以適度之黏著力貼附於被黏著體(下述中為顯示器基材21)，加熱後可自被黏著體簡單剝離之再剝離性黏著片而應用於各種作業(被黏著體積層物之製造等；尤其是圖2之顯示器材料20之製造)。 Since the adhesive sheet 1 of this example has the adhesive layer 3 containing the thermally foamable first adhesive layer 33 formed by heating and satisfying specific conditions (at least formula 1, formula 2 and condition a), even if it is applied to 90~ When heated under severe conditions at 110°C for 1 to 10 hours, the expanded first adhesive layer 33a does not shrink and maintains its expanded state after heating. Therefore, it can be used as a re-peelable adhesive sheet that can be attached to an adherend (display substrate 21 in the following) with a moderate adhesive force before heating, and can be easily peeled off from the adherend after heating, and can be applied to various tasks ( The manufacturing of the adhered volume layer, etc.; especially the manufacturing of the display material 20 in FIG. 2).

其次，對製造本發明之被黏著體積層物之方法進行詳細說明。 Next, the method for manufacturing the adhered volume layer of the present invention will be described in detail.

本發明之製造被黏著體積層物之方法係一種製造被黏著體之上表面經 由已硬化之接著層貼合有覆蓋材料之被黏著體積層物的方法，該方法由以下構成：使用如下黏著片，以下表面貼合有該黏著片之熱發泡性黏著層之被黏著體之上表面與覆蓋材料之硬化前接著層對向之方式，將覆蓋材料重疊於被黏著體，繼而於90~110℃對整體加熱1~10小時，使硬化前接著層硬化後，自被黏著體之下表面剝離上述黏著片，該黏著片具有由含有熱發泡劑與黏著劑之熱發泡性黏著劑組成物構成之熱發泡性黏著層，且於將該熱發泡性黏著層之表面積設為「S0」，將於100℃經加熱3小時之情形時之熱發泡性黏著層表面之算術平均粗糙度設為「Ra」，將凹凸之最高點即上限高度設為「H1」，將加熱前之熱發泡性黏著層之凹凸之最低點即下限高度設為「H5」，將H1至H5之範圍之表面積設為「SH1-H5」時，以滿足下述式1、2及下述條件方式形成有黏著層。 The method of manufacturing an adhered volume layer of the present invention is a method of manufacturing an adhered volume layer in which a covering material is attached to the upper surface of an adherend through a hardened adhesive layer. The method consists of the following: use the following adhesive sheet , The upper surface of the adherend with the thermally foamable adhesive layer of the adhesive sheet attached to the lower surface is opposed to the adhesive layer before hardening of the covering material, and the covering material is overlapped on the adherend, and then 90~110 Heat the whole at ℃ for 1~10 hours, after hardening the adhesive layer before curing, peel off the adhesive sheet from the lower surface of the adherend. The adhesive sheet is composed of a thermal foaming adhesive containing a thermal foaming agent and an adhesive. Arithmetic of the surface of the thermally foamable adhesive layer when the thermally foamable adhesive layer is heated at 100°C for 3 hours when the surface area of the thermally foamable adhesive layer is set to "S 0 " The average roughness is set to "Ra", the highest point of the unevenness is set to "H1", and the lowest point of the thermally foamable adhesive layer before heating is set to "H5". Set H1 to When the surface area of the range of H5 is set to "S H1-H5 ", an adhesive layer is formed so as to satisfy the following formulas 1, 2 and the following conditions.

式1：(H1-H5)≧50μm Formula 1: (H1-H5)≧50μm

式2：SH1-H5/S0≧2.5，條件：Ra為4~8μm。 Formula 2: S H1-H5 /S 0 ≧2.5, condition: Ra is 4~8μm.

作為本發明之製造方法製造之被黏著體積層物，並無特別限定，例如可列舉使用顯示器基材作為被黏著體，於其上表面經由已硬化之接著層而貼合有覆蓋材料的具有顯示器基材/硬化後接著層/覆蓋材料之層構造之顯示器材料等。作為顯示器材料，例如可列舉用以供用戶觀賞圖像或影像等之具備小型液晶面板之能夠頭戴之隨身顯示器(或頭戴式顯示器(Head Mount Display))之表面材料，或能夠於彎曲或彎折狀態下觀賞圖像或影像等之軟性顯示器等。 The volume layer to be adhered produced by the manufacturing method of the present invention is not particularly limited. For example, a display substrate can be used as an adherend, and a cover material is attached to the upper surface of the substrate via a hardened adhesive layer. Display materials of base material/adhesive layer after hardening/covering material layer structure, etc. As the display material, for example, the surface material of a head-mounted portable display (or head-mounted display (Head Mount Display)) with a small liquid crystal panel for users to view images or images, or can be bent or A flexible display for viewing images or images in the bent state.

圖2係表示作為被黏著體積層物一例之顯示器材料的剖面 圖。於本例中，例示使用圖1所表示之黏著片1而製造作為被黏著體積層物一例之圖2所表示之顯示器材料20之情況。 Figure 2 shows a cross-section of a display material as an example of an adhered volume layer picture. In this example, an example of using the adhesive sheet 1 shown in FIG. 1 to manufacture the display material 20 shown in FIG. 2 as an example of an adhered volume layer is illustrated.

首先，對作為製造對象之顯示器材料20之構成進行說明。如圖2所示，顯示器材料20係藉由在顯示器基材21之上表面經由已硬化之接著層23a貼合覆蓋材料25而構成。此外，以下，於言及「接著層23a」之情形時，意指「硬化後」之狀態，於言及「接著層23」之情形時，意指「硬化前」之狀態。 First, the structure of the display material 20 to be manufactured will be described. As shown in FIG. 2, the display material 20 is formed by laminating a covering material 25 on the upper surface of the display substrate 21 via a hardened adhesive layer 23a. In addition, in the following, when referring to the "adhesive layer 23a", it means the state "after hardening", and when referring to the "adhesive layer 23", it means the state "before hardening".

作為顯示器基材21，可列舉玻璃、塑膠基板等。 As the display substrate 21, glass, plastic substrates, and the like can be cited.

接著層23a係藉由加熱使由接著劑組成物形成之特定厚度之接著層23(硬化前)硬化而成者。 The adhesive layer 23a is formed by curing the adhesive layer 23 (before curing) of a specific thickness formed of the adhesive composition by heating.

覆蓋材料25可列舉玻璃、塑膠材料等。 Examples of the covering material 25 include glass and plastic materials.

其次，對顯示器材料20之製造方法之詳細內容進行說明。首先，如圖3及圖4所示，自圖1之黏著片1拉離第1隔片5，於第2隔片7上使黏著層3之一側(第2黏著層35)露出，重疊於第1被黏著體40，而準備第1積層體50(第1步驟)。作為第1被黏著體40，可舉玻璃基板等。 Next, the details of the manufacturing method of the display material 20 will be described. First, as shown in FIGS. 3 and 4, pull away the first spacer 5 from the adhesive sheet 1 of FIG. 1, and expose one side of the adhesive layer 3 (the second adhesive layer 35) on the second spacer 7, and overlap For the first adherend 40, the first laminated body 50 is prepared (first step). As the 1st to-be-adhered body 40, a glass substrate etc. are mentioned.

其次，如圖5及圖6所示，自第1積層體50拉離第2隔片7，於第1被黏著體40上使黏著層3之另一側(第1黏著層33)露出，重疊於作為第2被黏著體之顯示器基材21，而準備第2積層體52(第2步驟)。 Next, as shown in FIGS. 5 and 6, the second spacer 7 is pulled away from the first laminate 50, and the other side of the adhesive layer 3 (the first adhesive layer 33) is exposed on the first adherend 40. It is superposed on the display substrate 21 as the second adherend to prepare the second laminate 52 (second step).

繼而，如圖7所示，將第2積層體52衝壓成特定形狀，去除不需要之部分，而準備第3積層體54(第3步驟)。 Next, as shown in FIG. 7, the second laminated body 52 is punched into a specific shape, unnecessary parts are removed, and the third laminated body 54 is prepared (third step).

繼而，如圖8所示，於第3積層體54之顯示器基材21，使覆蓋材料25之接著層23對向重疊，而準備第4積層體56後，實施加熱處理(第4步驟)。 加熱條件於本例中設為100℃、3小時。 Next, as shown in FIG. 8, the adhesive layer 23 of the cover material 25 is overlapped on the display substrate 21 of the third layered body 54 to face each other to prepare the fourth layered body 56, and then heat treatment is performed (the fourth step). The heating conditions are set to 100°C for 3 hours in this example.

藉由此種加熱處理，如圖9所示，第1黏著層33膨脹變成第1黏著層33a，顯示器基材21側之黏著降低。並且，覆蓋材料25之接著層23發生硬化，成為接著層23a而獲得圖2所表示之顯示器材料20(第5步驟)。 By this heat treatment, as shown in FIG. 9, the first adhesive layer 33 swells to become the first adhesive layer 33a, and the adhesion on the side of the display substrate 21 decreases. Then, the adhesive layer 23 of the cover material 25 is cured to become the adhesive layer 23a, and the display material 20 shown in FIG. 2 is obtained (the fifth step).

若根據使用黏著片1之本例之方法，則即便將圖8所表示之第4積層體56於100℃、3小時之嚴酷條件下進行加熱，與顯示器基材21接觸之第1黏著層33a亦不癟縮而保持膨脹狀態。其結果為，如圖9所示，可容易地進行顯示器材料20之剝離，變得能夠抑制顯示器材料20製造良率之降低。 According to the method of this example using the adhesive sheet 1, even if the fourth laminate 56 shown in FIG. 8 is heated under severe conditions of 100°C for 3 hours, the first adhesive layer 33a in contact with the display substrate 21 It does not deflate and maintains an expanded state. As a result, as shown in FIG. 9, peeling of the display material 20 can be easily performed, and it becomes possible to suppress a decrease in the manufacturing yield of the display material 20.

實施例 Example

以下，基於實驗例(包括實施例及比較例)對本發明進行具體說明，但本發明並不限定於該等實施例。 Hereinafter, the present invention will be specifically described based on experimental examples (including examples and comparative examples), but the present invention is not limited to these examples.

1.黏著片之製作 1. Making of Adhesive Sheet

[實驗例1~7] [Experimental examples 1~7]

於厚度50μm之透明PET膜之單面，利用Baker式敷料器分別塗佈以表1記載之固形物成分比均勻地混合並溶解下述構成成分而製備之熱發泡性黏著層形成塗佈液a1及b。將各塗佈液之黏著劑等之固形物成分比(質量換算)示於表1。各塗佈液中之全固形物成分均製備為40%。然後，藉由在80℃充分地乾燥而形成熱發泡性黏著層後，於該熱發泡性黏著層之表面配設其一表面經矽酮脫模處理之厚度38μm之PET膜(隔片)，藉此製作各例之黏著片。 On one side of a transparent PET film with a thickness of 50μm, a Baker-type applicator was used to coat the heat-foamable adhesive layer forming coating solution prepared by uniformly mixing and dissolving the following components with the solid content ratio described in Table 1. a1 and b. Table 1 shows the solid content ratio (mass conversion) of the adhesive and the like of each coating liquid. The total solid content in each coating liquid is prepared to be 40%. Then, after fully drying at 80°C to form a thermally foamable adhesive layer, a 38μm-thick PET film (separator) with one surface treated with silicone release treatment was placed on the surface of the thermally foamable adhesive layer. ), to make the adhesive sheet of each case.

《黏著層形成塗佈液a1及b之構成成分》 "Components of Adhesive Layer Formation Coating Liquids a1 and b"

‧黏著劑(固形物成分34%)：294質量份(固形物成分100) ‧Adhesive (solid content 34%): 294 parts by mass (solid content 100)

(Nissetsu PE-121，丙烯酸-丙烯酸丁酯共聚物(AA/BA=10/90)，分子量：50萬，玻璃轉移溫度：-20℃，酸值：78，NIPPON CARBIDE公司製造) (Nissetsu PE-121, acrylic acid-butyl acrylate copolymer (AA/BA=10/90), molecular weight: 500,000, glass transition temperature: -20°C, acid value: 78, manufactured by NIPPON CARBIDE)

‧熱膨脹性微球：表1記載之種類與固形物成分比 ‧Heat-expandable microspheres: the type and solid content ratio listed in Table 1

‧環氧系交聯劑：表1記載之固形物成分比 ‧Epoxy crosslinking agent: the ratio of solid content in Table 1

(Tetrad X，N,N,N',N'-四縮水甘油基間苯二甲胺，環氧當量100，三菱瓦斯化學公司製造) (Tetrad X, N,N,N',N'-tetraglycidyl metaxylylenediamine, epoxy equivalent 100, manufactured by Mitsubishi Gas Chemical Corporation)

‧黏著賦予劑(固形物成分100%)：表1記載之種類與固形物成分比 ‧Adhesive agent (solid content 100%): the type and solid content ratio listed in Table 1

‧甲苯：226質量份 ‧Toluene: 226 parts by mass

Figure 106116021-A0202-12-0024-1
Figure 106116021-A0202-12-0024-1

此外，表1中，黏著賦予劑之「Y1」為萜酚系黏著賦予樹脂(YS Polystar K125，萜酚系，軟化點125℃，分子量1000，安原化學公司製造)，「Y2」為萜酚系黏著賦予樹脂(YS Polystar G150，萜酚系，軟化點150℃，分子量700，安原化學公司製造)。 In addition, in Table 1, "Y1" of the adhesion-imparting agent is a terpene phenol-based adhesion-imparting resin (YS Polystar K125, terpene phenol-based, softening point 125°C, molecular weight 1000, manufactured by Yasuhara Chemical Co., Ltd.), and "Y2" is a terpene phenol-based adhesion-imparting resin Adhesion-imparting resin (YS Polystar G150, terpene phenolic, softening point 150°C, molecular weight 700, manufactured by Yasuhara Chemical Co., Ltd.).

熱膨脹性微球之「Z1」係質量平均粒徑為13μm，熱膨脹溫度(與熱發泡溫度含義相同；以下相同)為80℃，發泡倍率為1.5~5倍之熱發泡粒子(Matsumoto Microsphere，F-36D，松本油脂製藥公司製造)，「Z2」係質 量平均粒徑為12μm，熱膨脹溫度為100℃，發泡倍率為1.5~5倍之熱發泡粒子(Matsumoto Microsphere，F-48D，松本油脂製藥公司製造)。 The "Z1" of thermally expandable microspheres has a mass average particle diameter of 13μm, a thermal expansion temperature (the same meaning as thermal foaming temperature; the same below) of 80℃, and a foaming ratio of 1.5 to 5 times the thermally expanded particles (Matsumoto Microsphere , F-36D, manufactured by Matsumoto Oil Pharmaceutical Co., Ltd.), "Z2" series quality Thermally expanded particles (Matsumoto Microsphere, F-48D, manufactured by Matsumoto Oil Pharmaceutical Co., Ltd.) with an average particle diameter of 12μm, a thermal expansion temperature of 100°C, and an expansion ratio of 1.5 to 5 times.

2.測定、算出及物性之評價 2. Measurement, calculation and evaluation of physical properties

(2-1)S0、Ra、Ry及Rz之測定 (2-1) Determination of S 0 , Ra, Ry and Rz

對各例獲得之黏著片，於剝離其隔片後，使用形狀分析雷射顯微鏡(VK-9510：其恩斯公司)，以倍率：50測定露出之黏著層之表面積(S0)。然後，於使黏著層露出之狀態下於100℃之烘箱中加熱3小時(加熱條件如表3所示)，使黏著層熱膨脹後(加熱後樣品)，使用S0之測定使用之形狀分析雷射顯微鏡，於下述條件下測定加熱膨脹後之黏著層表面之算術平均粗糙度(Ra)、最大高度(Ry)及十點平均粗糙度(Rz)。將結果示於表2。 For the adhesive sheets obtained in each example, after peeling off the spacers, the surface area (S 0 ) of the exposed adhesive layer was measured at a magnification of 50 using a shape analysis laser microscope (VK-9510: Qiens Company). Then, the adhesive layer was exposed and heated in an oven at 100°C for 3 hours (heating conditions are shown in Table 3), after the adhesive layer was thermally expanded (the sample after heating), the shape analysis mine used for the measurement of S 0 was used. Under the following conditions, the arithmetic average roughness (Ra), maximum height (Ry) and ten-point average roughness (Rz) of the surface of the adhesive layer after heating and expansion were measured under the following conditions. The results are shown in Table 2.

(2-2)(H1-H5)及(SH1-H2/S0)~(SH1-H5/S0)之算出 (2-2) Calculation of (H1-H5) and (S H1-H2 /S 0 )~(S H1-H5 /S 0)

對於上述2.使用之加熱後樣品，同樣地使用上述2.中S0等之測定使用之形狀分析雷射顯微鏡，測定黏著層表面所存在之凹凸的上限高度(最高點H1)及下限高度(最低點H5)後，算出H1與H5之差(H1-H5)。另外，測定H1至H5之範圍之表面積(SH1-H5)後(例如參照圖10)，將該測定值除以上述2.獲得之黏著層(加熱前)之表面積(S0)之測定值，藉此算出(SH1-H5/S0)之值。進而，於以上述H1為基準，分別設定較該基準低10μm之位置之高度(H2)、低20μm之位置之高度(H3)、低30μm之位置之高度(H4)時，測定H1至H2之範圍之表面積(SH1-H2)、H1至H3之範圍之表面積(SH1-H3)及H1至H4之範圍之表面積(SH1-H4)後，分別將該等測定值除以上述2.獲得之黏著層(加熱前)之表面積(S0)之測定值，藉此算出(SH1-H2/S0)~(SH1-H4/S0)之各值。將結果示於表2。 For the heated sample used in 2. above, use the shape analysis laser microscope used in the measurement of S 0 in 2. above to measure the upper limit height (highest point H1) and lower limit height ( After the lowest point H5), calculate the difference between H1 and H5 (H1-H5). In addition, after measuring the surface area (S H1-H5 ) in the range of H1 to H5 (for example, refer to Figure 10), divide the measured value by the above 2. Obtain the measured value of the surface area (S 0 ) of the adhesive layer (before heating) , To calculate the value of (S H1-H5 /S 0 ). Furthermore, when setting the height (H2) of a position 10μm lower than the reference, the height of a position 20μm lower (H3), and the height (H4) of a position 30μm lower than the reference, using the above-mentioned H1 as a reference, measure H1 to H2 After the surface area of the range (S H1-H2 ), the surface area of the range of H1 to H3 (S H1-H3 ) and the surface area of the range of H1 to H4 (S H1-H4 ), the measured values are divided by the above 2. Obtain the measured value of the surface area (S 0 ) of the adhesive layer (before heating), and calculate the values of (S H1-H2 /S 0 )~(S H1-H4 /S 0 ). The results are shown in Table 2.

此外，各表面積之單位均為μm2。 In addition, the unit of each surface area is μm 2 .

Figure 106116021-A0202-12-0026-2
Figure 106116021-A0202-12-0026-2

3.評價 3. Evaluation

對各例獲得之黏著片，藉由以下之方法對黏著層之厚度、及加熱剝離性(加熱處理後之剝離性)進行測定或評價。 With respect to the adhesive sheets obtained in each example, the thickness of the adhesive layer and the heat peelability (peelability after heat treatment) were measured or evaluated by the following methods.

(3-1)[黏著層之厚度] (3-1) [The thickness of the adhesive layer]

使用測微計測定包括2片PET片在內之厚度，並自測定值減去2片PET片之厚度，藉此算出黏著層之厚度。將結果示於表2。 Use a micrometer to measure the thickness including 2 PET sheets, and subtract the thickness of the 2 PET sheets from the measured value to calculate the thickness of the adhesive layer. The results are shown in Table 2.

(3-2)[加熱處理後之剝離性] (3-2) [Peelability after heat treatment]

準備2cm×10cm之實驗例獲得之黏著片，將剝離其隔片而露出之黏著層貼合於玻璃板(厚度1.0mm，15cm×10cm)，於烘箱內進行加熱。加熱條件設為如表3所示。放置冷卻後，於室溫(23℃)，根據以下之基準，目視評價黏著片之黏著層是否自玻璃板剝離。將結果示於表3。 Prepare the adhesive sheet obtained in the experimental example of 2cm×10cm, and attach the exposed adhesive layer after peeling off the separator to a glass plate (thickness 1.0mm, 15cm×10cm), and heat it in an oven. The heating conditions are as shown in Table 3. After being left to cool, at room temperature (23°C), visually evaluate whether the adhesive layer of the adhesive sheet is peeled from the glass plate according to the following criteria. The results are shown in Table 3.

「◎」：全部剝離(非常良好)。 "◎": All peeled off (very good).

「○」：全部剝離，但表面產生少量黏著(良好)。 "○": All peeled off, but a small amount of adhesion occurred on the surface (good).

「△」：大部分剝離，但有少部分未剝離(不太良好)。 "△": Most of it peeled off, but a small part was not peeled off (not so good).

「×」：未剝離(不良)。 "×": No peeling (bad).

此外，對基於上述2.(2-2)之算出值之以下之物性評價， 彙總示於表3。 In addition, the evaluation of physical properties below the calculated value based on the above 2.(2-2), The summary is shown in Table 3.

針對式1((H1-H5)≧50μm)、式2(SH1-H5/S0≧2.5)、及條件a(Ra為4~8μm)之各者，評價是否滿足條件。另外，根據以下之基準，對式3((SH1-H2/S0)=0.13~0.25)、式4((SH1-13/S0)=0.90~1.72)、式5((SH1-H4/S0)=2.28~3.00)、條件b(Ry=50~65μm)、及條件c(Rz=45~65μm)之各者評價是否滿足。 For each of Formula 1 ((H1-H5)≧50μm), Formula 2 (S H1-H5 /S 0 ≧2.5), and condition a (Ra is 4-8μm), evaluate whether the conditions are met. In addition, according to the following criteria, the formula 3 ((S H1-H2 /S 0 )=0.13~0.25), formula 4 ((S H1-13 /S 0 )=0.90~1.72), formula 5 ((S H1 -H4 /S 0 )=2.28~3.00), condition b (Ry=50~65μm), and condition c (Rz=45~65μm) to evaluate whether they are satisfied.

「○」：滿足。「×」：不滿足。 "○": Satisfied. "×": Not satisfied.

Figure 106116021-A0202-12-0027-3
Figure 106116021-A0202-12-0027-3

4.考察 4. Investigation

於100℃經加熱3小時之情形時之熱發泡性黏著層之表面滿足特定條件((H1-H5)≧50μm，SH1-H5/S0≧2.5，Ra為4~8μm；以下相同)之黏著片的實驗例1~4中(表2)，即便對於其他加熱條件(於100℃ 1小時、3小時、5小時、7小時)，加熱處理後之剝離性亦良好(表3)。 When heated at 100°C for 3 hours, the surface of the thermally foamable adhesive layer meets specific conditions ((H1-H5)≧50μm, S H1-H5 /S 0 ≧2.5, Ra is 4~8μm; the same as below) In Experimental Examples 1 to 4 of the adhesive sheet (Table 2), even for other heating conditions (1 hour, 3 hours, 5 hours, 7 hours at 100°C), the peelability after heat treatment was good (Table 3).

相對於此，不滿足全部特定條件之黏著片的實驗例5及6(表2)與滿足全部特定條件之實驗例1~4相比，加熱處理後之剝離性差(表3)。 In contrast, in Experimental Examples 5 and 6 (Table 2) of the adhesive sheet that did not satisfy all the specific conditions, the peelability after the heat treatment was inferior (Table 3) compared with Experimental Examples 1 to 4 that met all the specific conditions.

Claims (1)

一種被黏著體積層物之製造方法，其係製造被黏著體之上表面經由已硬化之接著層貼合有覆蓋材料之被黏著體積層物的方法，其特徵在於：使用黏著片，以下表面貼合有該黏著片之熱發泡性黏著層的被黏著體之上表面與覆蓋材料之硬化前接著層對向之方式，將覆蓋材料重疊於被黏著體，繼而於90~110℃對整體加熱1~10小時，使硬化前接著層硬化後，自被黏著體之下表面剝離該黏著片，該黏著片具有由含有熱發泡劑與黏著劑之熱發泡性黏著劑組成物構成之熱發泡性黏著層，於將該熱發泡性黏著層之表面積設為「S0」，將於100℃經加熱3小時之情形時之熱發泡性黏著層表面之算術平均粗糙度設為「Ra」，將凹凸之最高點即上限高度設為「H1」，將凹凸之最低點即下限高度設為「H5」，將H1至H5之範圍之表面積設為「SH1-H5」時，以滿足下述式1、2及下述條件之方式形成有黏著層，式1：(H1-H5)≧50μm，式2：SH1-H5/S0≧2.5，條件：Ra為4~8μm。 A method for manufacturing an adhered volume layer, which is a method of manufacturing an adhered volume layer in which a covering material is attached to the upper surface of the adherend through a hardened adhesive layer, characterized in that: an adhesive sheet is used, and the following surface is attached The upper surface of the adherend with the thermally foamable adhesive layer of the adhesive sheet is opposed to the adhesive layer before hardening of the covering material. The covering material is overlapped on the adherend, and then the whole is heated at 90~110℃ After hardening the adhesive layer before hardening for 1-10 hours, peel off the adhesive sheet from the lower surface of the adherend. The adhesive sheet has a thermal foaming adhesive composition containing a thermal foaming agent and an adhesive. For the foamable adhesive layer, the surface area of the thermally foamable adhesive layer is set to "S 0 ", and the arithmetic average roughness of the surface of the thermally foamable adhesive layer when heated at 100°C for 3 hours is set as For "Ra", set the highest point or upper limit height of the unevenness to "H1", set the lowest point or lower limit height of the unevenness to "H5", and set the surface area of the range from H1 to H5 to "S H1-H5 ", The adhesive layer is formed to satisfy the following formulas 1, 2 and the following conditions, formula 1: (H1-H5)≧50μm, formula 2: S H1-H5 /S 0 ≧2.5, condition: Ra is 4~8μm .
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