TWI815278B - adhesive sheet - Google Patents

adhesive sheet Download PDF

Info

Publication number
TWI815278B
TWI815278B TW111101660A TW111101660A TWI815278B TW I815278 B TWI815278 B TW I815278B TW 111101660 A TW111101660 A TW 111101660A TW 111101660 A TW111101660 A TW 111101660A TW I815278 B TWI815278 B TW I815278B
Authority
TW
Taiwan
Prior art keywords
adhesive
liner
adhesive sheet
adhesive layer
weight
Prior art date
Application number
TW111101660A
Other languages
Chinese (zh)
Other versions
TW202239907A (en
Inventor
平山高正
西尾昭德
Original Assignee
日商日東電工股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商日東電工股份有限公司 filed Critical 日商日東電工股份有限公司
Publication of TW202239907A publication Critical patent/TW202239907A/en
Application granted granted Critical
Publication of TWI815278B publication Critical patent/TWI815278B/en

Links

Images

Classifications

    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本發明提供一種黏著片材，其具備可使對半導體晶片進行密封之密封樹脂於其表面變動較小地流動之黏著劑層。 本發明之黏著片材具備基材、及配置於該基材之至少單側之黏著劑層，且將該黏著劑層貼合於聚對苯二甲酸乙二酯時之23℃下之黏著力為0.1 N/20 mm～8 N/20 mm，該黏著劑層含有包含基礎聚合物之黏著劑，該基礎聚合物之sp值為7(cal/cm 3) 1/2～10(cal/cm 3) 1/2，該黏著片材之含水率為0.05重量%～6重量%。 The present invention provides an adhesive sheet having an adhesive layer that allows a sealing resin for sealing a semiconductor chip to flow on its surface with little change. The adhesive sheet of the present invention includes a base material and an adhesive layer arranged on at least one side of the base material, and the adhesive force at 23°C when the adhesive layer is bonded to polyethylene terephthalate is 0.1 N/20 mm ~ 8 N/20 mm. The adhesive layer contains an adhesive containing a base polymer. The sp value of the base polymer is 7 (cal/cm 3 ) 1/2 ~ 10 (cal/cm 3 ) 1/2 , the moisture content of the adhesive sheet is 0.05% to 6% by weight.

Description

黏著片材adhesive sheet

本發明係關於一種黏著片材。The present invention relates to an adhesive sheet.

近年來，於包含半導體晶片之半導體零件之製造中，為了防止半導體晶片受損、使金屬配線擴張等，有時對該半導體晶片進行樹脂密封。於樹脂密封步驟中，就作業性等觀點而言，有時於黏著片材上對半導體晶片進行樹脂密封。例如，為了防止半導體晶片移動，將複數個半導體晶片配置於特定之作為暫時固定材之黏著片材上，並於該黏著片材上一次性對半導體晶片進行密封。In recent years, in the manufacture of semiconductor parts including semiconductor wafers, in order to prevent the semiconductor wafer from being damaged, metal wirings from being expanded, etc., the semiconductor wafer may be sealed with resin. In the resin sealing step, from the viewpoint of workability and the like, the semiconductor wafer may be resin-sealed on an adhesive sheet. For example, in order to prevent the semiconductor wafer from moving, a plurality of semiconductor wafers are arranged on a specific adhesive sheet as a temporary fixing material, and the semiconductor wafers are sealed on the adhesive sheet at once.

於樹脂密封之步驟中，塗佈具有流動性之密封樹脂前驅物來覆蓋半導體晶片，其後，降低該前驅物之流動性，藉此將半導體晶片密封。此時之該前驅物之流動性係影響密封品質(尤其是作業時間、密封之均勻性)之一個因素。一般而言，上述前驅物之流動性依存於供密封樹脂塗佈之面(即黏著片材之黏著劑層表面)與密封樹脂之親和性。然而，有時儘管黏著劑層及密封樹脂之組成沒有變化，上述前驅物之流動性亦未必不變。 先前技術文獻 專利文獻 In the resin sealing step, a fluid sealing resin precursor is coated to cover the semiconductor wafer, and then the fluidity of the precursor is reduced to seal the semiconductor wafer. At this time, the fluidity of the precursor is a factor that affects the sealing quality (especially the operating time and the uniformity of the seal). Generally speaking, the fluidity of the above-mentioned precursor depends on the affinity between the surface to be coated with the sealing resin (ie, the surface of the adhesive layer of the adhesive sheet) and the sealing resin. However, sometimes even though the composition of the adhesive layer and sealing resin does not change, the fluidity of the above-mentioned precursor may not remain unchanged. Prior technical literature patent documents

專利文獻1：日本專利特開2001-308116號公報 專利文獻2：日本專利特開2001-313350號公報 Patent Document 1: Japanese Patent Application Publication No. 2001-308116 Patent Document 2: Japanese Patent Application Publication No. 2001-313350

[發明所欲解決之問題][Problem to be solved by the invention]

本發明係為了解決上述先前之課題而成者，其目的在於提供一種黏著片材，其具備可使對半導體晶片等進行密封之密封樹脂於其表面變動較小地流動之黏著劑層。 [解決問題之技術手段] The present invention was made in order to solve the above-mentioned previous problems, and an object thereof is to provide an adhesive sheet having an adhesive layer that allows sealing resin for sealing semiconductor wafers and the like to flow with small fluctuations on its surface. [Technical means to solve problems]

本發明之黏著片材具備基材、及配置於該基材之至少單側之黏著劑層，將該黏著劑層貼合於聚對苯二甲酸乙二酯時之23℃下之黏著力為0.1 N/20 mm～8 N/20 mm，該黏著劑層含有包含基礎聚合物之黏著劑，該基礎聚合物之sp值為7(cal/cm 3) 1/2～10(cal/cm 3) 1/2，該黏著片材之含水率為0.05重量%～6重量%。 於一個實施方式中，上述基材係包含玻璃轉移溫度(Tg)為60℃～450℃之樹脂之樹脂片材。 於一個實施方式中，上述基材包含芳香族性聚醯亞胺系樹脂。 於一個實施方式中，上述黏著劑層之厚度為2 μm～15 μm。 於一個實施方式中，上述黏著劑層之凝膠分率為60%～100%。 於一個實施方式中，上述基礎聚合物係丙烯酸系聚合物，該丙烯酸系聚合物包含源自含羥基單體之結構單元，該源自含羥基單體之結構單元之含量相對於構成該丙烯酸系聚合物之總結構單元100重量份為0.1重量份～20重量份。 於一個實施方式中，上述黏著片材於上述基材之與上述黏著劑層相反側進而具備第2黏著劑層。 於一個實施方式中，上述黏著片材於製造CSP(Chip Size/Scale Package，晶片級封裝)或WLP(Wafer Level Package，晶圓級封裝)時用作暫時固定半導體晶片之片材。 於一個實施方式中，上述半導體晶片係經密封樹脂密封，該樹脂密封時之加工溫度為100℃以上。 根據本發明之另一態樣，提供一種上述黏著片材之製造方法。該製造方法包括：於基材上形成包含黏著劑之組合物之塗佈層之步驟；於該塗佈層面上配置襯墊而形成積層體之步驟；及將該積層體於溫度及濕度受到管理之環境下放置特定加濕熱時間(例如2小時～7天)之加濕熱步驟；且加濕熱步驟中之加濕熱時間、溫度及濕度之乘積為100～300000℃・RH%・h。 [發明之效果] The adhesive sheet of the present invention includes a base material and an adhesive layer arranged on at least one side of the base material. When the adhesive layer is bonded to polyethylene terephthalate, the adhesive force at 23°C is 0.1 N/20 mm ~ 8 N/20 mm. The adhesive layer contains an adhesive containing a base polymer. The sp value of the base polymer is 7 (cal/cm 3 ) 1/2 ~ 10 (cal/cm 3 ) 1/2 , the moisture content of the adhesive sheet is 0.05% to 6% by weight. In one embodiment, the above-mentioned base material is a resin sheet including a resin with a glass transition temperature (Tg) of 60°C to 450°C. In one embodiment, the base material includes an aromatic polyimide resin. In one embodiment, the thickness of the adhesive layer ranges from 2 μm to 15 μm. In one embodiment, the gel fraction of the adhesive layer is 60% to 100%. In one embodiment, the above-mentioned base polymer is an acrylic polymer. The acrylic polymer includes structural units derived from hydroxyl-containing monomers, and the content of the structural units derived from hydroxyl-containing monomers is relative to the content of the acrylic polymer. The total structural unit of the polymer ranges from 0.1 to 20 parts by weight per 100 parts by weight. In one embodiment, the adhesive sheet further includes a second adhesive layer on the side of the base material opposite to the adhesive layer. In one embodiment, the above-mentioned adhesive sheet is used as a sheet for temporarily fixing semiconductor chips when manufacturing CSP (Chip Size/Scale Package) or WLP (Wafer Level Package). In one embodiment, the semiconductor wafer is sealed with a sealing resin, and the processing temperature when the resin is sealed is 100° C. or above. According to another aspect of the present invention, a method for manufacturing the above-mentioned adhesive sheet is provided. The manufacturing method includes: forming a coating layer of a composition containing an adhesive on a substrate; arranging a liner on the coating layer to form a laminate; and controlling the temperature and humidity of the laminate. The humidification heat step is to place the humidification heat for a specific humidification heat time (for example, 2 hours to 7 days) in the environment; and the product of the humidification heat time, temperature and humidity in the humidification heat step is 100 to 300000℃·RH%·h. [Effects of the invention]

根據本發明，可提供一種黏著片材，其具備可使對半導體晶片等進行密封之密封樹脂於其表面變動較小地流動之黏著劑層。According to the present invention, it is possible to provide an adhesive sheet having an adhesive layer that allows a sealing resin for sealing a semiconductor chip or the like to flow on the surface with little change.

A. 黏著片材之概要圖1係本發明之一實施方式之黏著片材之概略剖視圖。黏著片材100具備基材10、及配置於基材10之至少單側之黏著劑層(第1黏著劑層)20。 A. Overview of Adhesive Sheet Figure 1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention. The adhesive sheet 100 includes a base material 10 and an adhesive layer (first adhesive layer) 20 arranged on at least one side of the base material 10 .

關於本發明之黏著片材，將黏著劑層貼合於聚對苯二甲酸乙二酯時之23℃下之黏著力為0.1 N/20 mm～8 N/20 mm。又，上述黏著劑層含有包含基礎聚合物之黏著劑，該基礎聚合物之sp值為 7(cal/cm 3) 1/2～10(cal/cm 3) 1/2。又，上述黏著片材之含水率為0.05重量%～6重量%。 Regarding the adhesive sheet of the present invention, the adhesive force at 23°C when the adhesive layer is bonded to polyethylene terephthalate is 0.1 N/20 mm to 8 N/20 mm. In addition, the above-mentioned adhesive layer contains an adhesive containing a base polymer, and the sp value of the base polymer is 7 (cal/cm 3 ) 1/2 to 10 (cal/cm 3 ) 1/2 . In addition, the moisture content of the above-mentioned adhesive sheet is 0.05% by weight to 6% by weight.

本發明之黏著片材可適宜用作對半導體晶片進行樹脂密封時之暫時固定材。更詳細而言，本發明之黏著片材可用作如下情況時之半導體晶片之暫時固定材：將半導體晶片排列於該黏著片材之黏著劑層上，用密封樹脂(通常為環氧系樹脂)前驅物覆蓋該半導體晶片，使該密封樹脂前驅物硬化，藉此對半導體晶片進行樹脂密封。對半導體晶片進行樹脂密封後，於特定後續步驟(例如密封樹脂之背面研削、圖案形成、凸塊形成、單片化(切斷))時，上述黏著片材可自包含密封樹脂與半導體晶片之構造體剝離。密封樹脂之環氧當量例如為50 g/eq～500 g/eq。The adhesive sheet of the present invention can be suitably used as a temporary fixing material when resin sealing a semiconductor wafer. More specifically, the adhesive sheet of the present invention can be used as a temporary fixing material for semiconductor wafers when the semiconductor wafers are arranged on the adhesive layer of the adhesive sheet and sealed with a sealing resin (usually an epoxy resin). ) precursor covers the semiconductor wafer to harden the sealing resin precursor, thereby resin sealing the semiconductor wafer. After the semiconductor wafer is resin-sealed, during specific subsequent steps (such as back grinding of the sealing resin, pattern formation, bump formation, and singulation (cutting)), the above-mentioned adhesive sheet can self-contain the sealing resin and the semiconductor wafer. Construct stripping. The epoxy equivalent of the sealing resin is, for example, 50 g/eq to 500 g/eq.

於本發明之黏著片材中，如上所述，特定出黏著劑層所含有之基礎聚合物之sp值，且特定出黏著片材含水率，藉此可使密封樹脂前驅物於上述黏著劑層上適宜流動。又，密封樹脂前驅物之流動性之變動得到抑制，故於半導體晶片之量產步驟中，可縮短密封步驟之時間，可穩定地進行均勻性優異之樹脂密封。如上所述，本發明之黏著片材之特徵在於黏著性與剝離性之平衡性優異(即暫時固定性優異)且可有助於提高密封品質。又，本發明之黏著片材即便於高溫下亦可有助於提高密封品質，就該方面而言尤其有用。In the adhesive sheet of the present invention, as mentioned above, the sp value of the base polymer contained in the adhesive layer is specified, and the moisture content of the adhesive sheet is specified, thereby allowing the sealing resin precursor to be added to the adhesive layer Suitable for flow. In addition, fluctuations in the fluidity of the sealing resin precursor are suppressed, so in the mass production process of semiconductor wafers, the time of the sealing step can be shortened, and resin sealing with excellent uniformity can be stably performed. As described above, the adhesive sheet of the present invention is characterized by an excellent balance between adhesiveness and peelability (that is, excellent temporary fixability) and can contribute to improving sealing quality. In addition, the adhesive sheet of the present invention can help improve sealing quality even at high temperatures, and is particularly useful in this regard.

圖2係本發明之另一實施方式之黏著片材之概略剖視圖。黏著片材200係雙面黏著片材，於基材10之與黏著劑層20相反側進而具備第2黏著劑層30。即，黏著片材200依序具備黏著劑層20、基材10、及第2黏著劑層30。藉由具備第2黏著劑層30，於台座上進行樹脂密封時，可將第2黏著劑層30側貼合於該台座，固定性良好地使用黏著片材200。FIG. 2 is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention. The adhesive sheet 200 is a double-sided adhesive sheet and further has a second adhesive layer 30 on the side of the base material 10 opposite to the adhesive layer 20 . That is, the adhesive sheet 200 includes the adhesive layer 20, the base material 10, and the second adhesive layer 30 in this order. By providing the second adhesive layer 30, when performing resin sealing on the base, the second adhesive layer 30 side can be bonded to the base, and the adhesive sheet 200 can be used with good fixation.

於一個實施方式中，第2黏著劑層包含熱膨脹性微球。該熱膨脹性微球可於特定溫度下膨脹。包含此種熱膨脹性微球之黏著劑層藉由加熱至特定溫度以上使熱膨脹性微球膨脹，於黏著面(即第2黏著劑層表面)產生凹凸，從而使黏著力降低或消失。若形成包含熱膨脹性微球之第2黏著劑層，則對黏著片材進行固定時(例如固定於台座時)會表現出所需黏著性，於將黏著片材剝離時(例如自台座剝離時)，藉由加熱使黏著力降低或消失，從而表現出良好之剝離性。In one embodiment, the second adhesive layer includes thermally expandable microspheres. The heat-expandable microspheres can expand at a specific temperature. The adhesive layer containing such heat-expandable microspheres is heated to a specific temperature or above to expand the heat-expandable microspheres, causing unevenness on the adhesive surface (i.e., the surface of the second adhesive layer), thereby reducing or disappearing the adhesive force. If the second adhesive layer containing heat-expandable microspheres is formed, the adhesive sheet will exhibit the required adhesiveness when the adhesive sheet is fixed (for example, when fixed on a pedestal), and when the adhesive sheet is peeled off (for example, when peeled off from the pedestal) ), the adhesive force is reduced or eliminated by heating, thereby showing good peelability.

本發明之黏著片材將黏著劑層貼合於聚對苯二甲酸乙二酯時之23℃下之黏著力如上所述，為0.1 N/20 mm～8 N/20 mm，較佳為0.2 N/20 mm～7.5 N/20 mm，更佳為0.5 N/20 mm～6 N/20 mm，進而較佳為0.8 N/20 mm～5 N/20 mm，最佳為0.8 N/20 mm～3 N/20 mm。若為此種範圍，則可獲得可較佳地固定被黏著體(例如半導體晶片)且剝離時之糊劑殘留較少之黏著片材。再者，於本說明書中，「將黏著劑層貼合於聚對苯二甲酸乙二酯時之23℃下之黏著力」係指將黏著片材(寬20 mm×長140 mm)之黏著劑層貼合(貼合條件：2 kg輥往返1次)於聚對苯二甲酸乙二酯膜(厚度25 μm)，並於23℃之環境溫度下放置30分鐘後，將該試樣供給至拉伸試驗(剝離速度：300 mm/min、剝離角度180°)所測得之黏著力。The adhesive force of the adhesive sheet of the present invention when the adhesive layer is bonded to polyethylene terephthalate at 23°C is as described above, and is 0.1 N/20 mm to 8 N/20 mm, preferably 0.2 N/20 mm～7.5 N/20 mm, more preferably 0.5 N/20 mm～6 N/20 mm, further preferably 0.8 N/20 mm～5 N/20 mm, most preferably 0.8 N/20 mm ~3N/20mm. If it is within this range, an adhesive sheet can be obtained that can better fix an adherend (such as a semiconductor wafer) and has less paste residue when peeled off. Furthermore, in this specification, "the adhesive force at 23°C when the adhesive layer is bonded to polyethylene terephthalate" refers to the adhesion of the adhesive sheet (width 20 mm × length 140 mm) The agent layer is bonded (laminated condition: 2 kg roller back and forth once) on the polyethylene terephthalate film (thickness 25 μm), and placed at an ambient temperature of 23°C for 30 minutes, and then the sample is supplied The adhesive force measured by the tensile test (peeling speed: 300 mm/min, peeling angle 180°).

如上所述，黏著片材之含水率為0.05重量%～6重量%。黏著片材之含水率較佳為0.1重量%～5重量%，進而較佳為0.5重量%～4重量%，進而較佳為1重量%～3重量%。若為此種範圍，則可形成與密封樹脂前驅物之親和性被適度調整而可有助於提高樹脂密封品質之黏著劑層。又，可防止密封樹脂之變質。上述含水率可利用卡氏滴定法進行測定。黏著片材之含水率可藉由任意適當之方法進行調整。例如，可藉由黏著劑層形成時(黏著劑塗佈時)之黏著劑之含水率之調整、黏著劑中所包含之基礎聚合物之構成、加濕熱步驟之實施(下述)等進行調整。As mentioned above, the moisture content of the adhesive sheet is 0.05% by weight to 6% by weight. The moisture content of the adhesive sheet is preferably 0.1% to 5% by weight, more preferably 0.5% to 4% by weight, and further preferably 1% to 3% by weight. If it is within this range, the affinity with the sealing resin precursor can be appropriately adjusted to form an adhesive layer that can contribute to improving the quality of resin sealing. In addition, it can prevent the sealing resin from deteriorating. The above-mentioned moisture content can be measured by Karl Fischer titration method. The moisture content of the adhesive sheet can be adjusted by any appropriate method. For example, adjustment can be made by adjusting the moisture content of the adhesive when the adhesive layer is formed (when applying the adhesive), the composition of the base polymer contained in the adhesive, the implementation of the humidification heat step (described below), etc. .

本發明之黏著片材之厚度較佳為3 μm～300 μm，更佳為5 μm～150 μm，進而較佳為10 μm～100 μm。The thickness of the adhesive sheet of the present invention is preferably 3 μm to 300 μm, more preferably 5 μm to 150 μm, and further preferably 10 μm to 100 μm.

B. 黏著劑層上述黏著劑層含有包含基礎聚合物之黏著劑。再者，「基礎聚合物」係指黏著劑中所包含之聚合物之主成分。又，於該說明書中，「主成分」於未特別記載之情形時係指包含超過50重量%之成分。 B. Adhesive layer The above-mentioned adhesive layer contains an adhesive containing a base polymer. Furthermore, "base polymer" refers to the main component of the polymer contained in the adhesive. In addition, in this specification, "main component" means a component containing more than 50% by weight unless otherwise specified.

上述黏著劑層之厚度較佳為1 μm～50 μm，更佳為3 μm～30 μm，進而較佳為5 μm～20 μm。若為此種範圍，則可獲得即便藉由密封步驟時之加壓亦不易將半導體晶片埋入樹脂中之黏著片材。於一個實施方式中，上述黏著劑層之厚度為2 μm～15 μm。若為此種範圍，則水分自黏著劑層之散逸被適度調整，可使密封樹脂前驅物之流動性較佳。The thickness of the above-mentioned adhesive layer is preferably 1 μm to 50 μm, more preferably 3 μm to 30 μm, and further preferably 5 μm to 20 μm. If it is within this range, it is possible to obtain an adhesive sheet in which the semiconductor chip is not easily embedded in the resin even by applying pressure during the sealing step. In one embodiment, the thickness of the adhesive layer ranges from 2 μm to 15 μm. If it is within this range, the dissipation of moisture from the adhesive layer is moderately adjusted, allowing the sealing resin precursor to have better fluidity.

如上所述，上述基礎聚合物之sp值為7(cal/cm 3) 1/2～10(cal/cm 3) 1/2，上述基礎聚合物之sp值較佳為7.5(cal/cm 3) 1/2～9.5(cal/cm 3) 1/2，更佳為8(cal/cm 3) 1/2～9(cal/cm 3) 1/2。若為此種範圍，則可適度地調整對密封樹脂之親和性，從而可形成可有助於提高樹脂密封品質之黏著劑層。sp值係藉由Fedors之方法(山本秀樹著、「sp值基礎・應用及計算方法」、資訊機構股份有限公司出版、2006年4月3日發行、66～67頁)而求出。具體而言，該sp值係根據形成聚合物之各原子或原子團之25℃下之蒸發能量Δe(cal)、及形成聚合物之各原子或原子團之25℃下之莫耳容積ΔV(cm3)並藉由以下式算出。於聚合物為共聚物之情形時，該sp值係算出構成該共聚物之各結構單元各者之單獨共聚物之sp值，並將該等sp值分別乘以各結構單元之莫耳分率，將所得者進行累加而算出。 sp值＝(ΣΔe/ΣΔv) 1/2 As mentioned above, the sp value of the above-mentioned base polymer is 7 (cal/cm 3 ) 1/2 to 10 (cal/cm 3 ) 1/2 , and the sp value of the above-mentioned base polymer is preferably 7.5 (cal/cm 3 ) 1/2 ~ 9.5 (cal/cm 3 ) 1/2 , more preferably 8 (cal/cm 3 ) 1/2 ~ 9 (cal/cm 3 ) 1/2 . If it is within this range, the affinity for the sealing resin can be appropriately adjusted, and an adhesive layer can be formed that can contribute to improving the quality of resin sealing. The sp value is obtained by Fedors' method ("Sp Value Basics, Applications and Calculation Methods" by Hideki Yamamoto, published by Information Agency Co., Ltd., issued on April 3, 2006, pages 66-67). Specifically, the sp value is based on the evaporation energy Δe (cal) of each atom or atomic group forming the polymer at 25°C, and the molar volume ΔV (cm3) of each atom or atomic group forming the polymer at 25°C. And calculated by the following formula. When the polymer is a copolymer, the sp value is calculated by calculating the sp value of the individual copolymers of each structural unit constituting the copolymer, and multiplying the sp values by the molar fraction of each structural unit. , calculated by adding up the results. sp value=(ΣΔe/ΣΔv) 1/2

上述黏著劑層之水之接觸角較佳為70°～120°，更佳為80°～110°，進而較佳為90°～105°。若為此種範圍，則可形成可適度地調整與密封樹脂前驅物之親和性、從而可有助於提高樹脂密封品質之黏著劑層。水之接觸角可將使用接觸角計(例如協和界面公司製造，商品名「CX-A型」)於23℃/50%RH環境下向黏著劑層表面滴加純水2 μl，滴加5秒後測定液滴之接觸角之操作重複進行5次，並根據其平均值而求出。The water contact angle of the adhesive layer is preferably 70° to 120°, more preferably 80° to 110°, and further preferably 90° to 105°. If it is within this range, an adhesive layer can be formed that can appropriately adjust the affinity with the sealing resin precursor, thereby contributing to improvement in resin sealing quality. The contact angle of water can be determined by using a contact angle meter (for example, manufactured by Xiehe Interface Company, trade name "CX-A") in a 23℃/50%RH environment, adding 2 μl of pure water to the surface of the adhesive layer, and adding 5 The operation of measuring the contact angle of the droplet after seconds is repeated five times, and the average value is calculated.

上述黏著劑層之凝膠分率較佳為60%～100%，更佳為70%～99%，進而較佳為75%～98%，尤佳為80%～95%。若為此種範圍，則水分自黏著劑層之散逸被適度調整，可使密封樹脂前驅物之流動性較佳。又，可形成具有適度之黏著性、不存在剝離時之糊劑殘留等而不易污染被黏著體之黏著劑層。凝膠分率之測定方法於下文中進行說明。The gel fraction of the adhesive layer is preferably 60% to 100%, more preferably 70% to 99%, further preferably 75% to 98%, particularly preferably 80% to 95%. If it is within this range, the dissipation of moisture from the adhesive layer is moderately adjusted, allowing the sealing resin precursor to have better fluidity. In addition, it can form an adhesive layer that has moderate adhesion, does not have paste residue when peeling off, and is less likely to contaminate the adherend. The method for measuring the gel fraction is explained below.

上述黏著劑層之25℃下之藉由奈米壓痕法所得之彈性模數較佳為未達100 MPa，更佳為0.1 MPa～50 MPa，進而較佳為0.1 MPa～10 MPa。若為此種範圍，則可獲得具有適當之黏著力之黏著片材。藉由奈米壓痕法所得之彈性模數係指如下彈性模數：於負載時、卸載時連續測定將壓頭壓入試樣時之對壓頭之負載荷重與壓入深度，根據所獲得之負載荷重-壓入深度曲線求出。於本說明書中，藉由奈米壓痕法所得之彈性模數係將測定條件設為荷重：1 mN、負載・卸載速度：0.1 mN/s、保持時間：1 s並以如上方式測定所得之彈性模數。The elastic modulus of the above-mentioned adhesive layer obtained by the nanoindentation method at 25°C is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, and further preferably 0.1 MPa to 10 MPa. If it is within this range, an adhesive sheet with appropriate adhesive force can be obtained. The elastic modulus obtained by the nanoindentation method refers to the following elastic modulus: when the indenter is pressed into the sample, the negative load weight and the indentation depth of the indenter are measured continuously during loading and unloading. According to the obtained load Calculate the load-pressure depth curve. In this specification, the elastic modulus obtained by the nanoindentation method is measured as above by setting the measurement conditions as load: 1 mN, loading/unloading speed: 0.1 mN/s, and holding time: 1 s. modulus.

(丙烯酸系黏著劑) 於一個實施方式中，構成黏著劑層之黏著劑係丙烯酸系黏著劑。作為上述丙烯酸系黏著劑，例如可例舉：將使用1種或2種以上之(甲基)丙烯酸烷基酯作為單體成分之丙烯酸系聚合物(均聚物或共聚物)作為預聚物，並將該預聚物之交聯體作為基礎聚合物之丙烯酸系黏著劑等。再者，於本說明書中，黏著劑層中之丙烯酸系黏著劑中所包含之「基礎聚合物」意指使預聚物(未交聯聚合物)交聯而形成之聚合物。於一個實施方式中，上述基礎聚合物具有藉由丙烯酸系聚合物與環氧交聯劑所得之交聯體結構。 (Acrylic adhesive) In one embodiment, the adhesive constituting the adhesive layer is an acrylic adhesive. Examples of the acrylic adhesive include an acrylic polymer (homopolymer or copolymer) using one or more alkyl (meth)acrylates as a monomer component as a prepolymer. , and use the cross-linked body of the prepolymer as the base polymer for acrylic adhesives, etc. In addition, in this specification, the "base polymer" contained in the acrylic adhesive in the adhesive layer means a polymer formed by crosslinking a prepolymer (uncrosslinked polymer). In one embodiment, the base polymer has a cross-linked structure obtained by an acrylic polymer and an epoxy cross-linking agent.

作為上述(甲基)丙烯酸烷基酯之具體例，可例舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等(甲基)丙烯酸C1-20烷基酯。其中，較佳為具有碳數為4～20(更佳為6～20，尤佳為8～18)之直鏈狀或者支鏈狀烷基之(甲基)丙烯酸烷基酯，更佳為(甲基)丙烯酸2-乙基己酯。再者，於本說明書中，(甲基)丙烯酸意指丙烯酸及/或甲基丙烯酸。Specific examples of the alkyl (meth)acrylate include (methyl)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, and isopropyl(meth)acrylate. , butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, ( Isononyl methacrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate )Tridecyl acrylate, Tetradecyl (meth)acrylate, Pentadecyl (meth)acrylate, Cetyl (meth)acrylate, Heptadecyl (meth)acrylate Ester, C1-20 alkyl (meth)acrylate such as stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosanyl (meth)acrylate, etc. Among them, a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having a carbon number of 4 to 20 (more preferably 6 to 20, particularly preferably 8 to 18) is more preferred. 2-Ethylhexyl (meth)acrylate. In addition, in this specification, (meth)acrylic acid means acrylic acid and/or methacrylic acid.

為了對凝聚力、耐熱性、交聯性等進行改質，上述丙烯酸系聚合物(預聚物)亦可視需要包含與可與上述(甲基)丙烯酸烷基酯共聚合之其他單體成分對應之單元。作為此種單體成分，例如可例舉：丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸等含羧基單體；順丁烯二酸酐、伊康酸酐等酸酐單體；(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基己酯、(甲基)丙烯酸羥基辛酯、(甲基)丙烯酸羥基癸酯、(甲基)丙烯酸羥基月桂酯、(4-羥甲基環己基)甲基丙烯酸甲酯等含羥基單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體；(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體；(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等(甲基)丙烯酸胺基烷基系單體；(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體；N-環己基順丁烯二醯亞胺、N-異丙基順丁烯二醯亞胺、N-月桂基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺等順丁烯二醯亞胺系單體；N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體；N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體；乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯啶酮、甲基乙烯基吡咯啶酮、乙烯基吡啶、乙烯基哌啶、乙烯基嘧啶、乙烯基哌𠯤、乙烯基吡𠯤、乙烯基吡咯、乙烯基唑、乙烯基㗁唑、乙烯基嗎啉、N-乙烯基羧醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等乙烯系單體；丙烯腈、甲基丙烯腈等氰基丙烯酸酯單體；(甲基)丙烯酸縮水甘油酯等含環氧基丙烯酸系單體；聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸甲氧基乙二醇、(甲基)丙烯酸甲氧基聚丙二醇等二醇系丙烯酸酯單體；(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯等具有雜環、鹵素原子、矽原子等之丙烯酸酯系單體；己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧丙烯酸酯、聚酯丙烯酸酯、胺基甲酸酯丙烯酸酯等多官能單體；異戊二烯、丁二烯、異丁烯等烯烴系單體；乙烯醚等乙烯醚系單體等。該等單體成分可單獨或將2種以上組合使用。In order to modify cohesion, heat resistance, cross-linking properties, etc., the acrylic polymer (prepolymer) may optionally contain other monomer components that can be copolymerized with the alkyl (meth)acrylate. unit. Examples of such monomer components include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like containing carboxyl groups. Monomers; anhydride monomers such as maleic anhydride and Iconic anhydride; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyl (meth)acrylate Hydroxyl-containing monomers such as hexyl ester, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate; Styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, (meth)acrylic acid sulfopropyl ester, (meth)acrylamide-2-methylpropanesulfonic acid Sulfonic acid group-containing monomers such as meth)acryloxynaphthalene sulfonic acid; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)propylene (N-substituted) amide monomers such as amide, N-methylol (meth)acrylamide, N-methylolpropane (meth)acrylamide, etc.; (meth)acrylic acid aminoethyl ester , N,N-dimethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate and other (meth)acrylic aminoalkyl monomers; methyl (meth)acrylate (meth)acrylic acid alkoxyalkyl ester monomers such as oxyethyl ester and ethoxyethyl (meth)acrylate; N-cyclohexylmaleimide, N-isopropylbutane Maleenedimine-based monomers such as enediamide, N-laurylmaleimide, N-phenylmaleimide, etc.; N-methyleconidimine , N-Ethyl Ikonimide, N-Butyl Ikonimide, N-Octyl Ikonimide, N-2-ethylhexyl Ikonimide, N-cyclohexyl Ikonimide Ikonidimine-based monomers such as ethyleneimine and N-lauryl icotrimide; N-(meth)acryloxymethylenesuccinimide and N-(meth)acrylyl -Succinimide monomers such as 6-oxyhexamethylenesuccinimide and N-(meth)acryl-8-oxyoctamethylenesuccinimide; vinyl acetate, propylene Vinyl acid ester, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidine, vinylpyrimidine, vinylpiperdine, vinylpyrrolidone, vinylpyrrole, vinylazole , vinyl ethazole, vinyl morpholine, N-vinyl carboxamides, styrene, α-methylstyrene, N-vinyl caprolactam and other vinyl monomers; acrylonitrile, methacrylamide Cyanoacrylate monomers such as nitrile; epoxy-containing acrylic monomers such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, (meth)acrylate, ) Diol acrylate monomers such as methoxyethylene glycol acrylate and methoxypolypropylene glycol acrylate; tetrahydrofurfuryl (meth)acrylate, fluoro(meth)acrylate, polysiloxane ( Meth)acrylate and other acrylate monomers with heterocyclic rings, halogen atoms, silicon atoms, etc.; hexylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly) ) Propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate Multifunctional monomers such as acrylate, dipentaerythritol hexa(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, etc.; olefin monomers such as isoprene, butadiene, isobutylene, etc. Monomers; vinyl ether monomers such as vinyl ether, etc. These monomer components can be used individually or in combination of 2 or more types.

於一個實施方式中，上述丙烯酸系聚合物(預聚物)進而包含源自含羥基單體之結構單元。源自含羥基單體之結構單元之含量相對於構成丙烯酸系聚合物之總結構單元100重量份，較佳為0.1重量份～20重量份，更佳為0.1重量份～10重量份。更佳為0.5重量份～10重量份。若為此種範圍，則可形成水分自黏著劑層之散逸被適度調整、含水率被較佳地調整之黏著劑層。又，可形成具有適度之凝聚性而糊劑殘留較少之黏著劑層。羥基可為醇性羥基，亦可為羧基等酸性羥基。In one embodiment, the acrylic polymer (prepolymer) further includes structural units derived from hydroxyl-containing monomers. The content of the structural unit derived from the hydroxyl-containing monomer is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the total structural units constituting the acrylic polymer. More preferably, it is 0.5 parts by weight to 10 parts by weight. If it is within this range, the dissipation of moisture from the adhesive layer can be appropriately adjusted and the moisture content can be better adjusted to form an adhesive layer. In addition, an adhesive layer with moderate cohesiveness and less paste residue can be formed. The hydroxyl group may be an alcoholic hydroxyl group or an acidic hydroxyl group such as a carboxyl group.

上述丙烯酸系黏著劑可視需要包含任意適當之添加劑。作為該添加劑，例如可例舉：交聯劑、黏著賦予劑、塑化劑(例如偏苯三甲酸酯系塑化劑、均苯四甲酸酯系塑化劑等)、顏料、染料、填充劑、抗老化劑、導電材、抗靜電劑、紫外線吸收劑、光穩定劑、剝離調整劑、軟化劑、界面活性劑、阻燃劑、抗氧化劑等。The above-mentioned acrylic adhesive may contain any appropriate additives if necessary. Examples of the additive include cross-linking agents, adhesion-imparting agents, plasticizers (such as trimellitate-based plasticizers, pyromellitate-based plasticizers, etc.), pigments, dyes, and fillers. Agents, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, peeling adjusters, softeners, surfactants, flame retardants, antioxidants, etc.

作為上述丙烯酸系黏著劑中所包含之交聯劑，例如可例舉：異氰酸酯系交聯劑、環氧系交聯劑、三聚氰胺系交聯劑、過氧化物系交聯劑、以及脲系交聯劑、金屬烷氧化物系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、碳二醯亞胺系交聯劑、㗁唑啉系交聯劑、氮丙啶系交聯劑、胺系交聯劑等。Examples of the cross-linking agent contained in the acrylic adhesive include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, and urea-based cross-linking agents. Linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal salt-based cross-linking agents, carbodiimide-based cross-linking agents, tetrazoline-based cross-linking agents, aziridine-based cross-linking agents Cross-linking agents, amine cross-linking agents, etc.

於一個實施方式中，交聯劑相對於丙烯酸系聚合物(預聚物)之羧基之調配量較佳為0.08莫耳當量～2莫耳當量，更佳為0.1莫耳當量～1莫耳當量。若為此種範圍，則可形成交聯密度較高之丙烯酸系黏著劑，黏著劑層/密封樹脂間之成分轉移被較佳地防止。此處之交聯劑之調配量意指丙烯酸系聚合物交聯之前之交聯劑之含量。In one embodiment, the blending amount of the cross-linking agent relative to the carboxyl groups of the acrylic polymer (prepolymer) is preferably 0.08 molar equivalent to 2 molar equivalent, more preferably 0.1 molar equivalent to 1 molar equivalent. . If it is within this range, an acrylic adhesive with a high cross-linking density can be formed, and component transfer between the adhesive layer/sealing resin can be better prevented. The compounding amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.

作為上述丙烯酸系黏著劑中所包含之上述異氰酸酯系交聯劑之具體例，可例舉：伸丁基二異氰酸酯、六亞甲基二異氰酸酯等低級脂肪族聚異氰酸酯類；伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛酮二異氰酸酯等脂環族異氰酸酯類；2,4-甲苯二異氰酸酯、4,4'-二苯甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族異氰酸酯類；三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物(日本聚氨酯工業公司製造，商品名「Coronate L」)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物(日本聚氨酯工業公司製造，商品名「Coronate HL」)、六亞甲基二異氰酸酯之異氰尿酸酯體(日本聚氨酯工業公司製造，商品名「Coronate HX」)等異氰酸酯加成物等。異氰酸酯系交聯劑之調配量可根據所需黏著力設定為任意適當之量，相對於丙烯酸系聚合物100重量份，代表性而言為0.1重量份～20重量份，更佳為0.1重量份～10重量份。若為此種範圍，則可獲得黏著劑層中之成分之殘存羧基較少之黏著片材。此處之交聯劑之調配量意指丙烯酸系聚合物交聯之前之交聯劑之含量。Specific examples of the isocyanate cross-linking agent contained in the acrylic adhesive include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate , Cyclohexyl diisocyanate, isophorone diisocyanate and other alicyclic isocyanates; 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and other aromatic isocyanates; Trimethylolpropane/toluene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct (Japan) Isocyanate adducts such as the isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL"), isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HX"), etc. The amount of the isocyanate cross-linking agent can be set to any appropriate amount according to the required adhesion. It is typically 0.1 to 20 parts by weight relative to 100 parts by weight of the acrylic polymer, and more preferably 0.1 part by weight. ~10 parts by weight. If it is within this range, an adhesive sheet can be obtained in which the remaining carboxyl groups of the components in the adhesive layer are small. The compounding amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.

作為上述丙烯酸系黏著劑中所包含之上述環氧系交聯劑，例如可例舉：N,N,N',N'-四縮水甘油基-間苯二甲胺、二縮水甘油基苯胺、1,3-雙(N,N-縮水甘油基胺基甲基)環己烷(三菱瓦斯化學公司製造，商品名「Tetrad C」)、1,6-己二醇二縮水甘油醚(共榮社化學公司製造，商品名「Epolight1600」)、新戊二醇二縮水甘油醚(共榮社化學公司製造，商品名「Epolight1500NP」)、乙二醇二縮水甘油醚(共榮社化學公司製造，商品名「Epolight40E」)、丙二醇二縮水甘油醚(共榮社化學公司製造，商品名「Epolight70P」)、聚乙二醇二縮水甘油醚(日本油脂公司製造，商品名「EPIOL E-400」)、聚丙二醇二縮水甘油醚(日本油脂公司製造，商品名「EPIOL P-200」)、山梨糖醇聚縮水甘油醚(Nagase chemteX公司製造，商品名「Denacol EX-611」)、甘油聚縮水甘油醚(Nagase chemteX公司製造，商品名「Denacol EX-314」)、季戊四醇聚縮水甘油醚、聚甘油聚縮水甘油醚(Nagase chemteX公司製造，商品名「Denacol EX-512」)、山梨糖醇酐聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、己二酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、三(2-羥基乙基)異氰尿酸三縮水甘油酯、間苯二酚二縮水甘油醚、雙酚-S-二縮水甘油醚、分子內具有2個以上之環氧基之環氧系樹脂等。環氧系交聯劑之調配量可根據所需黏著力設定為任意適當之量，相對於丙烯酸系聚合物100重量份，代表性而言為0.01重量份～50重量份，更佳為0.6重量份～15重量份，進而較佳為2重量份～13重量份，尤佳為3重量份～10重量份。若為此種範圍，則可獲得黏著劑層中之成分之殘存羧基較少之黏著片材。此處之交聯劑之調配量意指丙烯酸系聚合物交聯之前之交聯劑之含量。Examples of the epoxy cross-linking agent contained in the acrylic adhesive include: N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidyl aniline, 1,3-bis(N,N-glycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C"), 1,6-hexanediol diglycidyl ether (Kyoei Neopentyl glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 1600"), neopentyl glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 1500NP"), ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., Trade name "Epolight40E"), propylene glycol diglycidyl ether (manufactured by Kyeisha Chemical Co., Ltd., trade name "Epolight70P"), polyethylene glycol diglycidyl ether (manufactured by Nippon Oils and Fats Co., Ltd., trade name "EPIOL E-400") , polypropylene glycol diglycidyl ether (manufactured by Nippon Oils and Fats Co., Ltd., trade name "EPIOL P-200"), sorbitol polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name "Denacol EX-611"), glycerol polyglycidol Ether (manufactured by Nagase chemteX Company, trade name "Denacol EX-314"), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (manufactured by Nagase chemteX Company, trade name "Denacol EX-512"), sorbitol polyglycidyl ether Glycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, tris(2-hydroxyethyl)triglycidyl isocyanurate, isophthalic acid Phenol diglycidyl ether, bisphenol-S-diglycidyl ether, epoxy resins with two or more epoxy groups in the molecule, etc. The amount of the epoxy cross-linking agent can be set to any appropriate amount according to the required adhesion. It is typically 0.01 to 50 parts by weight relative to 100 parts by weight of the acrylic polymer, and more preferably 0.6 parts by weight. parts to 15 parts by weight, more preferably 2 to 13 parts by weight, and particularly preferably 3 to 10 parts by weight. If it is within this range, an adhesive sheet can be obtained in which the remaining carboxyl groups of the components in the adhesive layer are small. The compounding amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.

C. 基材作為上述基材，例如可例舉：樹脂片材、不織布、紙、金屬箔、機織布、橡膠片材、發泡片材、該等之積層體(尤其是包含樹脂片材之積層體)等。作為構成樹脂片材之樹脂，例如可例舉：聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)、聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物(EVA)、聚醯胺(尼龍)、全芳香族聚醯胺(芳香族聚醯胺)、聚醯亞胺(PI)、聚氯乙烯(PVC)、聚苯硫醚(PPS)、氟系樹脂、聚醚醚酮(PEEK)等。作為不織布，可例舉：包含馬尼拉麻之不織布等具有耐熱性之藉由天然纖維所得之不織布；聚丙烯樹脂不織布、聚乙烯樹脂不織布、酯系樹脂不織布等合成樹脂不織布等。作為金屬箔，可例舉：銅箔、不鏽鋼箔、鋁箔等。作為紙，可例舉和紙、牛皮紙等。 C. Base Material Examples of the base material include resin sheets, nonwoven fabrics, paper, metal foils, woven fabrics, rubber sheets, foam sheets, and laminates of these (especially resin sheets). laminated body) etc. Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polyethylene. (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), polyamide (nylon), fully aromatic polyamide (aromatic polyamide), polyamide Imine (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluorine resin, polyether ether ketone (PEEK), etc. Examples of nonwoven fabrics include heat-resistant nonwoven fabrics made from natural fibers such as abaca-based nonwoven fabrics; synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabrics, polyethylene resin nonwoven fabrics, and ester resin nonwoven fabrics. Examples of the metal foil include copper foil, stainless steel foil, aluminum foil, and the like. Examples of paper include Japanese paper, kraft paper, and the like.

於一個實施方式中，可適宜使用包含玻璃轉移溫度(Tg)為60℃～450℃(較佳為65℃～430℃、更佳為80℃～420℃)之樹脂之樹脂片材作為基材。若使用此種樹脂片材，則即便於加熱時(例如密封步驟時之加熱)，構成基材之分子之分子運動亦不會變得過激，可適度抑制水分之散逸性。又，可獲得柔軟性優異之黏著片材。作為構成此種樹脂片材之樹脂，例如可例舉：聚對苯二甲酸乙二酯、聚醯亞胺、聚萘二甲酸乙二酯等。In one embodiment, a resin sheet containing a resin with a glass transition temperature (Tg) of 60°C to 450°C (preferably 65°C to 430°C, more preferably 80°C to 420°C) can be suitably used as the base material. . If such a resin sheet is used, even when heated (for example, during the sealing step), the molecular motion of the molecules constituting the base material will not become excessive, and the dissipation of moisture can be moderately suppressed. In addition, an adhesive sheet excellent in flexibility can be obtained. Examples of the resin constituting the resin sheet include polyethylene terephthalate, polyimide, polyethylene naphthalate, and the like.

於一個實施方式中，上述基材包含芳香族性聚醯亞胺系樹脂。由於芳香族性聚醯亞胺系樹脂之醯亞胺基為極性官能基，又，容易藉由胺基之供電子性與羰基之拉電子性調整水分率，可於樹脂密封步驟所需之較高之加工溫度之廣泛區域內維持蒸氣散逸能，故較佳。又，由於包含大量芳香族官能基(苯基、伸苯基、萘基、伸萘基等)，故聚合物分子之分子運動性較低，膠帶表面形狀維持平滑。因此，亦容易使樹脂流動一致，因此尤其適合解決本發明之課題。作為芳香族性聚醯亞胺，可例舉：主鏈骨架具有醚鍵之醚系聚鄰苯二甲醯亞胺類、該具有酮鍵之酮系聚鄰苯二甲醯亞胺類、該具有源自雙酚之骨架之雙酚系聚鄰苯二甲醯亞胺類等。亦可使用宇部興產公司製造之「Upilex」、三井化學公司製造之「LARC-TPI」、GE公司製造之「ULTEM」等市售品。尤其是主鏈骨架具有醚鍵之醚系均苯四甲醯亞胺由於重複單體殘基之每單位重量之醯亞胺基存在數增大，故可較佳地使用。作為此種樹脂，亦可使用杜邦公司製造之「Kapton」、Kaneka公司製造之「Apical」、三井化學公司製造之「Aurum」等市售品。In one embodiment, the base material includes an aromatic polyimide resin. Since the imine group of the aromatic polyimide resin is a polar functional group, and it is easy to adjust the moisture content through the electron donating property of the amine group and the electron withdrawing property of the carbonyl group, the required ratio can be achieved in the resin sealing step. It is better to maintain vapor dissipation energy in a wide range of high processing temperatures. In addition, because it contains a large number of aromatic functional groups (phenyl, phenyl, naphthyl, naphthylene, etc.), the molecular mobility of the polymer molecules is low, and the surface shape of the tape remains smooth. Therefore, it is easy to make the resin flow uniformly, so it is particularly suitable for solving the problems of the present invention. Examples of aromatic polyimides include ether polyphthalimines having an ether bond in the main chain skeleton, ketone polyphthalimines having a ketone bond, and Bisphenol-based polyphthalimides having a skeleton derived from bisphenol, etc. Commercially available products such as "Upilex" manufactured by Ube Kosan, "LARC-TPI" manufactured by Mitsui Chemicals, and "ULTEM" manufactured by GE can also be used. In particular, ether-based pyromellitic imines whose main chain skeleton has an ether bond can be preferably used because the number of pyromethylene imine groups present per unit weight of repeating monomer residues increases. As such resin, commercially available products such as "Kapton" manufactured by DuPont, "Apical" manufactured by Kaneka, and "Aurum" manufactured by Mitsui Chemicals Co., Ltd. can also be used.

上述基材之厚度可根據所需強度或柔軟性、以及使用目的等設定為任意適當之厚度。基材之厚度較佳為1000 μm以下，更佳為25 μm～1000 μm，進而較佳為40 μm～500 μm。The thickness of the above-mentioned base material can be set to any appropriate thickness according to required strength or flexibility, purpose of use, etc. The thickness of the base material is preferably 1000 μm or less, more preferably 25 μm to 1000 μm, and further preferably 40 μm to 500 μm.

上述基材亦可實施表面處理。作為表面處理，例如可例舉：電暈處理、鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、離子化輻射處理、藉由底塗劑進行之塗佈處理等。The above-mentioned base material may also be subjected to surface treatment. Examples of surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, and coating treatment with a primer.

作為上述有機塗佈材料，例如可例舉塑膠硬塗材料II(CMC出版、(2004))中所記載之材料。較佳為使用胺基甲酸酯系聚合物，更佳為使用聚丙烯酸胺基甲酸酯、聚酯胺基甲酸酯或該等之前驅物。其原因在於對基材之塗敷・塗佈簡便，且就工業方面而言可選擇多種材料，且可廉價地獲取。該胺基甲酸酯系聚合物例如係包含異氰酸酯單體與含醇性羥基單體(例如含羥基之丙烯酸化合物或含羥基之酯化合物)之反應混合物之聚合物。有機塗佈材料亦可包含聚胺等鏈延長劑、抗老化劑、氧化穩定劑等作為任意添加劑。有機塗佈層之厚度並無特別限定，例如較合適為0.1 μm～10 μm左右，較佳為0.1 μm～5 μm左右，更佳為0.5 μm～5 μm左右。Examples of the organic coating material include those described in Plastic Hard Coat Material II (CMC Publishing, (2004)). It is preferable to use a urethane polymer, and more preferably to use polyacrylic urethane, polyester urethane or these precursors. The reason for this is that it is easy to apply and coat the base material, and from an industrial perspective, a variety of materials can be selected and can be obtained at low cost. The urethane polymer is, for example, a polymer including a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl-containing monomer (such as a hydroxyl-containing acrylic compound or a hydroxyl-containing ester compound). The organic coating material may also contain chain extenders such as polyamine, anti-aging agents, oxidation stabilizers, etc. as optional additives. The thickness of the organic coating layer is not particularly limited. For example, it is preferably about 0.1 μm to 10 μm, more preferably about 0.1 μm to 5 μm, and more preferably about 0.5 μm to 5 μm.

D. 第 2 黏著劑層上述第2黏著劑層可為包含任意適當之黏著劑之黏著劑層。於一個實施方式中，如上所述，第2黏著劑層進而包含熱膨脹性微球。 D. Second Adhesive Layer The above-mentioned second adhesive layer may be an adhesive layer containing any appropriate adhesive. In one embodiment, as mentioned above, the second adhesive layer further includes thermally expandable microspheres.

上述第2黏著劑層中所包含之黏著劑可為硬化型黏著劑(例如活性能量線硬化型黏著劑)，亦可為感壓型黏著劑。作為感壓型黏著劑，例如可例舉丙烯酸系黏著劑、橡膠系黏著劑等。第2黏著劑層中所包含之黏著劑之詳細內容例如可參照日本專利特開2018-009050號公報之記載。該公報將其整體記載作為參考援用至本說明書中。於一個實施方式中，第2黏著劑層中所包含之黏著劑可為上述B項中所說明之丙烯酸系黏著劑。於一個實施方式中，如上述B項中所說明，丙烯酸系黏著劑中所包含之丙烯酸系聚合物(預聚物)包含源自含羥基單體之結構單元。源自含羥基單體之結構單元之含量相對於構成丙烯酸系聚合物之總結構單元100重量份，較佳為0.1重量份～20重量份，更佳為0.1重量份～10重量份。更佳為0.5重量份～10重量份。The adhesive contained in the above-mentioned second adhesive layer may be a hardening adhesive (such as an active energy ray hardening adhesive) or a pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive include acrylic adhesives, rubber adhesives, and the like. For details on the adhesive contained in the second adhesive layer, refer to the description of Japanese Patent Application Laid-Open No. 2018-009050, for example. The entire description of this publication is incorporated into this specification by reference. In one embodiment, the adhesive included in the second adhesive layer may be the acrylic adhesive described in item B above. In one embodiment, as described in item B above, the acrylic polymer (prepolymer) contained in the acrylic adhesive contains structural units derived from hydroxyl-containing monomers. The content of the structural unit derived from the hydroxyl-containing monomer is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the total structural units constituting the acrylic polymer. More preferably, it is 0.5 parts by weight to 10 parts by weight.

作為上述熱膨脹性微球，只要為藉由加熱能夠膨脹或發泡之微球即可，可使用任意適當之熱膨脹性微球。作為上述熱膨脹性微球，例如可使用使藉由加熱容易膨脹之物質(有機溶劑等揮發性物質)內包於具有彈性之殼內而成之微球。此種熱膨脹性微球可藉由任意適當之方法、例如凝聚法、界面聚合法等製造。As the heat-expandable microspheres, any appropriate heat-expandable microspheres can be used as long as they are microspheres that can expand or foam by heating. As the heat-expandable microspheres, for example, microspheres in which a substance that is easily expanded by heating (volatile substances such as organic solvents) are enclosed in an elastic shell can be used. Such thermally expandable microspheres can be produced by any appropriate method, such as agglomeration method, interfacial polymerization method, etc.

作為藉由加熱容易膨脹之物質，例如可例舉：丙烷、丙烯、丁烯、正丁烷、異丁烷、異戊烷、新戊烷、正戊烷、正己烷、異己烷、庚烷、辛烷、石油醚、甲烷之鹵化物、四烷基矽烷等低沸點液體；藉由熱分解氣化之偶氮二甲醯胺等。Examples of substances that easily expand by heating include propane, propylene, butylene, n-butane, isobutane, isopentane, neopentane, n-pentane, n-hexane, isohexane, and heptane, Low boiling point liquids such as octane, petroleum ether, methane halides, tetraalkyl silanes, etc.; azodimethylamide gasified by thermal decomposition, etc.

作為構成上述殼之物質，例如可例舉包含：丙烯腈、甲基丙烯腈、α-氯丙烯腈、α-乙氧基丙烯腈、反丁烯二腈等腈單體；丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、反丁烯二酸、檸康酸等羧酸單體；偏二氯乙烯；乙酸乙烯酯；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異𦯉酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、β-丙烯酸羧基乙酯等(甲基)丙烯酸酯；苯乙烯、α-甲基苯乙烯、氯苯乙烯等苯乙烯單體；丙烯醯胺、經取代之丙烯醯胺、甲基丙烯醯胺、經取代之甲基丙烯醯胺等醯胺單體等之聚合物。包含該等單體之聚合物可為均聚物，亦可為共聚物。作為該共聚物，例如可例舉：偏二氯乙烯-甲基丙烯酸甲酯-丙烯腈共聚物、甲基丙烯酸甲酯-丙烯腈-甲基丙烯腈共聚物、甲基丙烯酸甲酯-丙烯腈共聚物、丙烯腈-甲基丙烯腈-伊康酸共聚物等。Examples of substances constituting the shell include: nitrile monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, and fumaronitrile; acrylic acid, methacrylic acid , itaconic acid, maleic acid, fumaric acid, citraconic acid and other carboxylic acid monomers; vinylidene chloride; vinyl acetate; methyl (meth)acrylate, ethyl (meth)acrylate , n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylate ) (meth)acrylates such as benzyl acrylate and β-carboxyethyl acrylate; styrene monomers such as styrene, α-methylstyrene and chlorostyrene; acrylamide, substituted acrylamide, methyl Polymers of amide monomers such as acrylamide and substituted methacrylamide. The polymer containing these monomers may be a homopolymer or a copolymer. Examples of the copolymer include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, and methyl methacrylate-acrylonitrile. Copolymer, acrylonitrile-methacrylonitrile-itaconic acid copolymer, etc.

構成上述殼之聚合物中，源自含羧基單體之結構單元相對於構成殼之聚合物100重量份，較佳為80重量份以下，更佳為70重量份以下。若為此種範圍，則可形成含水率被適度調整之第2黏著劑層。In the polymer constituting the shell, the structural unit derived from the carboxyl group-containing monomer is preferably 80 parts by weight or less, more preferably 70 parts by weight or less based on 100 parts by weight of the polymer constituting the shell. If it is within this range, the second adhesive layer with the moisture content appropriately adjusted can be formed.

構成熱膨脹性微球之「藉由加熱容易膨脹之物質」及「殼」之詳細內容例如亦記載於日本專利特開2018-141086號公報中。該文獻係作為參考被援用至本說明書中。Details of the "substance easily expanded by heating" and the "shell" constituting the thermally expandable microspheres are also described in Japanese Patent Application Laid-Open No. 2018-141086, for example. This document is incorporated into this specification as a reference.

作為上述熱膨脹性微球，可使用無機系發泡劑或有機系發泡劑。作為無機系發泡劑，例如可例舉：碳酸銨、碳酸氫銨、碳酸氫鈉、亞硝酸銨、氫氧化硼鈉、各種疊氮化物類等。又，作為有機系發泡劑，例如可例舉：三氯單氟甲烷、二氯單氟甲烷等氟氯化烷烴系化合物；偶氮二異丁腈、偶氮二甲醯胺、鋇偶氮二羧酸酯等偶氮系化合物；對甲苯磺醯肼、二苯基碸-3,3'-二磺醯基醯肼、4,4'-氧基雙(苯磺醯肼)、烯丙基雙(磺醯基醯肼)等肼系化合物；對甲苯磺醯胺基脲、4,4'-氧基雙(苯磺醯基胺脲)等胺脲系化合物；5-嗎啉基-1,2,3,4-噻***等***系化合物；N,N'-二亞硝基五亞甲基四胺、N,N'-二甲基-N,N'-二亞硝基對苯二甲醯胺醯胺等N-亞硝基系化合物等。As the heat-expandable microspheres, an inorganic foaming agent or an organic foaming agent can be used. Examples of the inorganic foaming agent include ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium boron hydroxide, various azides, and the like. Examples of the organic foaming agent include: fluorochloroalkane compounds such as trichloromonofluoromethane and dichloromonofluoromethane; azobisisobutyronitrile, azodimethylamide, barium azo Azo compounds such as dicarboxylic acid esters; p-toluenesulfonylhydrazine, diphenylsulfonylhydrazine, 4,4'-oxybis(benzenesulfonylhydrazine), allyl Hydrazine compounds such as methyl bis(sulfonyl acyl hydrazine); amidourea compounds such as p-toluene sulfonyl acyl urea and 4,4'-oxybis(benzenesulfonyl acyl hydrazine); 5-morpholinyl- Triazole compounds such as 1,2,3,4-thitriazole; N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitroso N-nitroso compounds such as terephthalamide amide, etc.

上述熱膨脹性微球亦可使用市售品。作為市售品之熱膨脹性微球之具體例，可例舉：松本油脂製藥公司製造之商品名「Matsumoto Microsphere 」(等級：F-30、F-30D、F-36D、F-36LV、F-50、F-50D、F-65、F-65D、FN-100SS、FN-100SSD、FN-180SS、FN-180SSD、F-190D、F-260D、F-2800D)、Nippon Phyllite公司製造之商品名「EXPANCEL」(等級：053-40、031-40、920-40、909-80、930-120)、吳羽化學工業公司製造之「DAIFOAM」(等級：H750、H850、H1100、S2320D、S2640D、M330、M430、M520)、積水化學工業公司製造之「ADVANCELL」(等級：EML101、EMH204、EHM301、EHM302、EHM303、EM304、EHM401、EM403、EM501)等。Commercially available products can also be used as the thermally expandable microspheres. Specific examples of commercially available heat-expandable microspheres include: "Matsumoto Microsphere" manufactured by Matsumoto Oil Pharmaceutical Co., Ltd. (grade: F-30, F-30D, F-36D, F-36LV, F- 50. F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-180SS, FN-180SSD, F-190D, F-260D, F-2800D), product name manufactured by Nippon Phyllite Company "EXPANCEL" (Grade: 053-40, 031-40, 920-40, 909-80, 930-120), "DAIFOAM" manufactured by Kureha Chemical Industry Co., Ltd. (Grade: H750, H850, H1100, S2320D, S2640D, M330, M430, M520), "ADVANCELL" manufactured by Sekisui Chemical Industry Co., Ltd. (Grade: EML101, EMH204, EHM301, EHM302, EHM303, EM304, EHM401, EM403, EM501), etc.

上述熱膨脹性微球之加熱前之平均粒徑(數量基準)較佳為1 μm～40 μm，更佳為5 μm～40 μm，進而較佳為10 μm～40 μm。上述粒徑與平均粒徑係藉由雷射散射法中之粒度分佈測定法而求出之值。The average particle diameter (number basis) of the thermally expandable microspheres before heating is preferably 1 μm to 40 μm, more preferably 5 μm to 40 μm, and still more preferably 10 μm to 40 μm. The above-mentioned particle diameter and average particle diameter are values determined by the particle size distribution measurement method in the laser scattering method.

上述熱膨脹性微球較佳為具有在體積膨脹率成為較佳為5倍以上、更佳為7倍以上、進而較佳為10倍以上之前均不會破裂之適度之強度。於使用此種熱膨脹性微球之情形時，可藉由加熱處理高效率地使黏著力降低。The thermally expandable microspheres preferably have a moderate strength that does not break until the volume expansion rate becomes preferably 5 times or more, more preferably 7 times or more, and still more preferably 10 times or more. When using such heat-expandable microspheres, the adhesive force can be efficiently reduced by heat treatment.

上述第2黏著劑層中之熱膨脹性微球之含有比率可根據所需黏著力之降低性等適當地設定。熱膨脹性微球之含有比率相對於形成第2黏著劑層之基礎聚合物100重量份，例如為1重量份～150重量份，較佳為10重量份～130重量份，進而較佳為25重量份～100重量份。The content ratio of the heat-expandable microspheres in the second adhesive layer can be appropriately set depending on the required reduction in adhesive force. The content ratio of the heat-expandable microspheres relative to 100 parts by weight of the base polymer forming the second adhesive layer is, for example, 1 to 150 parts by weight, preferably 10 to 130 parts by weight, and further preferably 25 parts by weight. parts to 100 parts by weight.

熱膨脹性微球膨脹之前(即加熱前)之第2黏著劑層之算術表面粗糙度Ra較佳為500 nm以下，更佳為400 nm以下，進而較佳為300 nm以下。若為此種範圍，則可獲得對被黏著體之密接性優異之黏著片材。The arithmetic surface roughness Ra of the second adhesive layer before the thermally expandable microspheres expand (that is, before heating) is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 300 nm or less. If it is within this range, an adhesive sheet having excellent adhesion to the adherend can be obtained.

(底塗層) 於上述黏著片材具備第2黏著劑層之情形時，亦可於基材與第2黏著層之間設置底塗層。上述底塗層包含任意適當之黏著劑。作為構成底塗層之黏著劑，可例舉：丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑等。其中，可較佳地使用丙烯酸系黏著劑。又，作為黏著劑，亦可使用活性能量線硬化型丙烯酸系黏著劑(以下稱為活性能量線硬化型黏著劑)。作為構成底塗層之黏著劑，較佳為使用與構成上述第2黏著劑層之黏著劑相同之黏著劑。 (base coat) When the above-mentioned adhesive sheet has a second adhesive layer, a primer layer can also be provided between the base material and the second adhesive layer. The above-mentioned base coat contains any suitable adhesive. Examples of adhesives constituting the base coat include acrylic adhesives, rubber adhesives, and silicone adhesives. Among them, an acrylic adhesive can be preferably used. Furthermore, as the adhesive, an active energy ray-curable acrylic adhesive (hereinafter referred to as an active energy ray-curable adhesive) may be used. As the adhesive constituting the base coat layer, it is preferable to use the same adhesive as the adhesive constituting the second adhesive layer.

上述底塗層之厚度較佳為1 μm～40 μm，更佳為5 μm～35 μm，進而較佳為10 μm～30 μm。The thickness of the above-mentioned primer layer is preferably 1 μm to 40 μm, more preferably 5 μm to 35 μm, and further preferably 10 μm to 30 μm.

E. 黏著片材之製造方法本發明之黏著片材可藉由任意適當之方法製造。作為獲得本發明之黏著片材之方法，例如可例舉：將包含黏著劑(例如丙烯酸系黏著劑)之組合物直接塗佈於基材上之方法；或將包含黏著劑之組合物塗佈於任意適當之基體上並將所形成之塗佈層轉印至基材之方法等。包含丙烯酸系黏著劑之組合物可包含任意適當之溶劑。 E. Manufacturing method of adhesive sheet The adhesive sheet of the present invention can be manufactured by any appropriate method. Examples of methods for obtaining the adhesive sheet of the present invention include: a method of directly applying a composition containing an adhesive (such as an acrylic adhesive) to a base material; or applying a composition containing an adhesive. On any appropriate substrate and transfer the formed coating layer to the substrate, etc. Compositions containing acrylic adhesives may contain any suitable solvent.

包含上述黏著劑之組合物可包含任意適當之溶劑。該溶劑中之水分率較佳為0.003重量%～0.3重量%。The composition containing the above-mentioned adhesive may contain any suitable solvent. The moisture content in the solvent is preferably 0.003% by weight to 0.3% by weight.

於形成包含熱膨脹性微球之黏著劑層(第2黏著劑層)之情形時，可將包含熱膨脹性微球、黏著劑及任意適當之溶劑的組合物塗佈於基材而形成該黏著劑層。或者亦可於將熱膨脹性微球於黏著劑塗佈層鋪開後，使用層壓機等將該熱膨脹性微球埋入黏著劑中來形成包含熱膨脹性微球之黏著劑層。When forming an adhesive layer (second adhesive layer) containing heat-expandable microspheres, a composition containing heat-expandable microspheres, an adhesive, and any appropriate solvent can be coated on the base material to form the adhesive. layer. Alternatively, after spreading the heat-expandable microspheres on the adhesive coating layer, the heat-expandable microspheres can be embedded in the adhesive using a laminator to form an adhesive layer containing heat-expandable microspheres.

作為上述黏著劑及各組合物之塗佈方法，可採用任意適當之塗佈方法。例如可於塗佈後進行乾燥來形成各層。作為塗佈方法，例如可例舉使用多功能塗佈機、模嘴塗佈機、凹版塗佈機、敷料器等之塗佈方法。作為乾燥方法，例如可例舉自然乾燥、加熱乾燥等。加熱乾燥之情形時之加熱溫度可根據成為乾燥對象之物質之特性設定為任意適當之溫度。As the coating method of the above-mentioned adhesive and each composition, any appropriate coating method can be used. For example, each layer can be formed by drying after coating. Examples of the coating method include a coating method using a multifunctional coater, a die coater, a gravure coater, an applicator, and the like. Examples of the drying method include natural drying, heat drying, and the like. In the case of heat drying, the heating temperature can be set to any appropriate temperature according to the characteristics of the substance to be dried.

於一個實施方式中，可於基材上形成包含黏著劑之組合物之塗佈層後，於該塗佈層面上配置襯墊而獲得積層體(附襯墊之黏著片材前驅物)，並經過將該積層體(附襯墊之黏著片材前驅物)於溫度及濕度受到管理之環境下放置特定加濕熱時間(例如2小時～7天)之步驟(加濕熱步驟)來獲得黏著片材。藉由進行加濕熱步驟，可較佳地調整黏著片材之含水率。該步驟中之溫度例如為40℃～120℃。又，濕度例如為1%RH～100%RH。再者，於黏著片材為雙面黏著片材之情形時，可將於黏著劑之塗佈層面兩面(即形成黏著劑層之黏著劑之塗佈層面、及形成第2黏著劑層之黏著劑之塗佈層面)配置襯墊(第1襯墊及第2襯墊)所獲得之積層體供於上述加濕熱步驟。襯墊之詳細內容於下文中進行說明。In one embodiment, after forming a coating layer of a composition containing an adhesive on a substrate, a liner is disposed on the coating layer to obtain a laminate (adhesive sheet precursor with liner), and The adhesive sheet is obtained through a step (humidification heat step) of placing the laminated body (adhesive sheet precursor with a liner) in an environment with controlled temperature and humidity for a specific humidification heat time (for example, 2 hours to 7 days). . By performing the humidification and heat step, the moisture content of the adhesive sheet can be better adjusted. The temperature in this step is, for example, 40°C to 120°C. Moreover, the humidity is, for example, 1%RH to 100%RH. Furthermore, when the adhesive sheet is a double-sided adhesive sheet, the adhesive can be applied on both sides of the adhesive coating layer (i.e., the adhesive coating layer forming the adhesive layer and the adhesive layer forming the second adhesive layer). The laminate obtained by arranging liners (the first liner and the second liner) on the coating layer of the agent is used in the above-mentioned humidification and heat step. The details of the pad are explained below.

加濕熱步驟中之加濕熱時間、溫度及濕度之乘積較佳為100～300000℃・RH%・h，更佳為180～265000℃・RH%・h。若為此種範圍，則可較佳地調整黏著片材之含水率。The product of humidification heat time, temperature and humidity in the humidification heat step is preferably 100~300000℃·RH%·h, more preferably 180~265000℃·RH%·h. If it is within this range, the moisture content of the adhesive sheet can be better adjusted.

F. 附襯墊之雙面黏著片材圖3係本發明之一實施方式之附襯墊之雙面黏著片材之概略剖視圖。附襯墊之雙面黏著片材110具備雙面黏著片材200、可剝離地直接配置於黏著片材200之一面之第1襯墊40、及可剝離地直接配置於雙面黏著片材200之另一面之第2襯墊50。藉由配置第1襯墊40及第2襯墊50，可保護黏著劑層免受污染等，且可防止捲筒狀或片狀之雙面黏著片材黏連。代表性而言，上述第1襯墊及第2襯墊具備襯墊基材、及配置於襯墊基材之至少單面之剝離處理層。第1襯墊及第2襯墊係以上述剝離處理層成為雙面黏著片材側之方式配置。 F. Double-sided adhesive sheet with liner. Figure 3 is a schematic cross-sectional view of a double-sided adhesive sheet with liner according to one embodiment of the present invention. The double-sided adhesive sheet 110 with a liner is provided with a double-sided adhesive sheet 200, a first liner 40 directly disposed on one side of the adhesive sheet 200 and releasably disposed directly on the double-sided adhesive sheet 200. The second pad 50 on the other side. By disposing the first liner 40 and the second liner 50, the adhesive layer can be protected from contamination and the like, and the roll-shaped or sheet-shaped double-sided adhesive sheet can be prevented from sticking. Typically, the first liner and the second liner include a liner base material and a release treatment layer arranged on at least one side of the liner base material. The first liner and the second liner are arranged so that the release-treated layer becomes the double-sided adhesive sheet side.

雙面黏著片材200可為上述黏著片材、即具備黏著劑層20、基材10、及第2黏著劑層30之黏著片材。The double-sided adhesive sheet 200 may be the above-mentioned adhesive sheet, that is, an adhesive sheet having an adhesive layer 20 , a base material 10 , and a second adhesive layer 30 .

第1襯墊20與第2襯墊30可為異質。「異質」例如可為厚度不同(例如厚度之差之絕對值為1 μm以上(較佳為5 μm以上、更佳為10 μm以上))、顏色不同、構成材料不同等之態樣。再者，第1襯墊20與第2襯墊30之厚度之差較佳為70 μm以下，更佳為50 μm以下，進而較佳為25 μm以下。The first liner 20 and the second liner 30 may be heterogeneous. "Heterogeneity" can be, for example, different thicknesses (for example, the absolute value of the thickness difference is 1 μm or more (preferably 5 μm or more, more preferably 10 μm or more)), different colors, different constituent materials, etc. Furthermore, the thickness difference between the first liner 20 and the second liner 30 is preferably 70 μm or less, more preferably 50 μm or less, and further preferably 25 μm or less.

於一個實施方式中，使用上述附襯墊之雙面黏著片材時，將第1襯墊先剝離。更詳細而言，上述附襯墊之雙面黏著片材可以如下方式使用：將第1襯墊先剝離，將被黏著體(例如電子零件)貼合於露出之黏著面(例如第1黏著劑層表面)，其後，將第2襯墊剝離，將第2黏著劑層表面貼合於另一被黏著體(例如台座)。於此種實施方式中，經由黏著片材將被黏著體(例如電子零件)暫時固定於台座；將該被黏著體供於特定加工；其後，藉由加熱使第2黏著劑層之黏著力降低，將附被黏著體之黏著片材自台座剝離。如上所述，只要第1襯墊與第2襯墊異質，則容易於特定之時時點出應剝離之襯墊。In one embodiment, when using the double-sided adhesive sheet with a liner, the first liner is peeled off first. In more detail, the double-sided adhesive sheet with a liner can be used as follows: peel off the first liner first, and then attach the adherend (such as an electronic component) to the exposed adhesive surface (such as the first adhesive). layer surface), and then peel off the second liner, and attach the second adhesive layer surface to another adherend (such as a base). In this embodiment, the adherend (such as an electronic component) is temporarily fixed to the base via an adhesive sheet; the adherend is subjected to a specific process; and then the adhesive force of the second adhesive layer is increased by heating. Lower it and peel the adhesive sheet attached to the adherend from the base. As described above, as long as the first liner and the second liner are different from each other, it is easy to identify the liner that should be peeled off at a specific time.

第1襯墊對雙面黏著片材之剝離力較佳為0.001 N/50 mm～2 N/50 mm，更佳為0.01 N/50 mm～1.5 N/50 mm，進而較佳為0.05 N/50 mm～1 N/50 mm，尤佳為0.1 N/50 mm～0.8 N/50 mm。第1襯墊對雙面黏著片材之剝離力(及第2襯墊對雙面黏著片材之剝離力)意指於23℃之環境下，將襯墊自附襯墊之雙面黏著片材之雙面黏著片材剝離(剝離角度：180°、剝離速度(拉伸速度)：300 mm/min)並進行測定所得之黏著力。襯墊對雙面黏著片材之剝離力可藉由黏著劑層之組陳、襯墊之種類、對襯墊實施之表面處理等任意適當之方法進行調整。The peeling force of the first liner to the double-sided adhesive sheet is preferably 0.001 N/50 mm to 2 N/50 mm, more preferably 0.01 N/50 mm to 1.5 N/50 mm, and further preferably 0.05 N/ 50 mm～1 N/50 mm, preferably 0.1 N/50 mm～0.8 N/50 mm. The peeling force of the first liner to the double-sided adhesive sheet (and the peeling force of the second liner to the double-sided adhesive sheet) means that the liner is separated from the double-sided adhesive sheet of the liner in an environment of 23°C The double-sided adhesive sheet was peeled off (peeling angle: 180°, peeling speed (stretch speed): 300 mm/min) and the resulting adhesive force was measured. The peeling force of the liner to the double-sided adhesive sheet can be adjusted by any appropriate method such as the composition of the adhesive layer, the type of liner, and the surface treatment of the liner.

第2襯墊對雙面黏著片材之剝離力較佳為0.001 N/50 mm～2 N/50 mm，更佳為0.01 N/50 mm～1.5 N/50 mm，進而較佳為0.05 N/50 mm～1 N/50 mm，尤佳為0.1 N/50 mm～0.8 N/50 mm。The peeling force of the second liner to the double-sided adhesive sheet is preferably 0.001 N/50 mm to 2 N/50 mm, more preferably 0.01 N/50 mm to 1.5 N/50 mm, and further preferably 0.05 N/ 50 mm～1 N/50 mm, preferably 0.1 N/50 mm～0.8 N/50 mm.

上述第1襯墊之厚度較佳為5 μm～250 μm，更佳為10 μm～200 μm，進而較佳為、20～150 μm，最佳為30～100 μm。上述第2襯墊之厚度較佳為5 μm～250 μm，更佳為10 μm～200 μm，進而較佳為、20～150 μm，最佳為30～100 μm。The thickness of the first liner is preferably 5 μm to 250 μm, more preferably 10 μm to 200 μm, further preferably 20 to 150 μm, and most preferably 30 to 100 μm. The thickness of the second liner is preferably 5 μm to 250 μm, more preferably 10 μm to 200 μm, further preferably 20 to 150 μm, and most preferably 30 to 100 μm.

上述襯墊基材可含有任意適當之材料。襯墊基材例如除塑膠膜、塑膠片以外，亦可使用紙、布、不織布、金屬箔或者其等之塑膠層壓體、塑膠彼此之積層體等各種片狀物。其中，就操作性或成本之觀點而言，最佳為塑膠膜或塑膠片(以下稱為塑膠膜)。作為塑膠膜之原材料，就強度、耐熱性等觀點而言，可視需要選擇。例如可例舉：聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物(EVA)等將α-烯烴作為單體成分之烯烴系樹脂；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；聚氯乙烯(PVC)；聚苯硫醚(PPS)；聚醯胺(尼龍)、全芳香族聚醯胺(芳香族聚醯胺)等醯胺系樹脂；聚醚醚酮(PEEK)、聚醯亞胺、聚醚醯亞胺、聚苯乙烯、丙烯酸系樹脂等。該等原材料可單獨使用或將2種以上組合使用。又，作為塑膠膜，可使用未延伸膜、單軸配向膜、雙軸配向膜之任一者。又，該等膜亦可為包含2層以上之膜層之積層膜，就操作性之觀點而言，亦可使用適當添加惰性粒子等潤滑劑之膜。The above-mentioned liner base material may contain any suitable material. For example, in addition to plastic films and plastic sheets, various sheet-like materials such as paper, cloth, non-woven fabric, metal foil, plastic laminates thereof, and laminates of plastics can also be used as the pad base material. Among them, from the viewpoint of workability and cost, a plastic film or a plastic sheet (hereinafter referred to as a plastic film) is most preferred. As a raw material for plastic film, it can be selected according to needs in terms of strength, heat resistance, etc. Examples include: olefin-based resins containing α-olefin as a monomer component such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA); polyparaphenylene Polyesters such as ethylene dicarboxylate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); Polyamide (nylon), fully aromatic polyamide (aromatic polyamide) and other amide-based resins; polyetheretherketone (PEEK), polyamideimide, polyetherimide, polystyrene, acrylic System resin, etc. These raw materials can be used alone or in combination of two or more types. In addition, as the plastic film, any of an unstretched film, a uniaxial alignment film, and a biaxial alignment film can be used. Moreover, these films may be a laminated film containing two or more film layers, and from the viewpoint of operability, a film to which a lubricant such as inert particles and the like is appropriately added may be used.

作為用以形成上述剝離處理層之處理，可採用任意適當之處理。於一個實施方式中，剝離處理層係聚矽氧處理層。作為聚矽氧，可較佳地使用主成分為二甲基聚矽氧烷類且具有交聯(硬化)所需之官能基之反應性聚矽氧系化合物。其原因在於可以低分子狀態塗佈於膜，且塗佈後能夠藉由使其硬化而製成耐摩擦等之剝離處理層。作為反應性聚矽氧化合物之官能基，例如可例舉乙烯基、環氧基、烷氧基、異氰酸基等。As a process for forming the above-mentioned release treatment layer, any appropriate process can be adopted. In one embodiment, the release treatment layer is a polysiloxane treatment layer. As the polysiloxane, a reactive polysiloxane compound whose main component is dimethylpolysiloxane and has a functional group required for crosslinking (hardening) can be preferably used. The reason for this is that it can be applied to a film in a low molecular state and can be cured after application to form a peel-off treatment layer that is resistant to friction or the like. Examples of functional groups of the reactive polysiloxy compound include vinyl groups, epoxy groups, alkoxy groups, isocyanate groups, and the like.

聚矽氧處理層例如可藉由將上述反應性聚矽氧系化合物稀釋至溶劑等中進行濃度調整，並利用凹版塗佈機等進行塗佈、加熱而形成。藉由進行加熱，促進溶劑乾燥與硬化反應。此處，較佳為併用促進硬化反應之觸媒。作為觸媒，例如可利用鉑、鈀、銠、鋯、錫等金屬錯合物或胺等有機鹼、乙酸等有機酸。The polysiloxane-treated layer can be formed by diluting the above-mentioned reactive polysiloxane-based compound into a solvent or the like, adjusting the concentration, and applying and heating the mixture using a gravure coater or the like. By heating, the drying and hardening reaction of the solvent is promoted. Here, it is preferable to use a catalyst that accelerates the hardening reaction in combination. As the catalyst, for example, metal complexes such as platinum, palladium, rhodium, zirconium, and tin, organic bases such as amines, and organic acids such as acetic acid can be used.

於一個實施方式中，上述第1襯墊及/或第2襯墊(實質上為各襯墊之剝離處理層)藉由螢光X射線分析所得之Si-Kα射線之強度為0.01～500 kcps(較佳為0.5～250 kcps、更佳為1.0～150 kcps、進而較佳為1.05～100 kcps，尤佳為10～30 kcps)。若為此種範圍，則可以較小之力將襯墊自黏著劑層剝離。又，襯墊/黏著劑層間之密接性變得充分，可防止襯墊之不必要之剝離。上述藉由螢光X射線分析所得之Si-Kα射線之強度係如下值：藉由螢光X射線分析分別測定剝離處理劑層與非剝離處理劑層之Si強度，自剝離處理劑層之強度減去非剝離處理劑層之強度而求出。再者，強度例如可藉由控制剝離處理劑之塗佈量、濃度、塗佈速度、乾燥等剝離處理層形成條件進行調整。In one embodiment, the Si-Kα ray intensity obtained by fluorescence X-ray analysis of the first liner and/or the second liner (essentially the release treatment layer of each liner) is 0.01 to 500 kcps. (0.5 to 250 kcps is preferred, 1.0 to 150 kcps is more preferred, 1.05 to 100 kcps is more preferred, and 10 to 30 kcps is particularly preferred). If it is within this range, the liner can be peeled off from the adhesive layer with a small force. In addition, the adhesion between the liner/adhesive layer becomes sufficient and unnecessary peeling of the liner can be prevented. The intensity of Si-Kα rays obtained by fluorescence X-ray analysis is as follows: the Si intensity of the peeling treatment agent layer and the non-peeling treatment agent layer are measured by fluorescence X-ray analysis, and the intensity of the self-peeling treatment agent layer is measured. It was calculated by subtracting the strength of the non-peeling treatment agent layer. Furthermore, the strength can be adjusted, for example, by controlling the peeling treatment layer formation conditions such as the coating amount, concentration, coating speed, and drying of the peeling treatment agent.

於一個實施方式中，上述第1襯墊與第2襯墊為不同顏色。以如上方式構成之附襯墊之雙面黏著片材例如可藉由使任一襯墊(例如襯墊基材)著色而獲得。若使兩襯墊為不同顏色，則附襯墊之雙面黏著片材之正反變得明確，容易識別出應剝離之襯墊。In one embodiment, the first liner and the second liner are of different colors. The double-sided adhesive sheet with a liner configured as above can be obtained, for example, by coloring any liner (for example, a liner base material). If the two liners are of different colors, the front and back of the double-sided adhesive sheet with the liner become clear, making it easier to identify the liner that should be peeled off.

G. 用途上述黏著片材及上述附襯墊之雙面黏著片材可適宜用作對任意適當之構件(例如半導體晶片等電子零件)進行加工時之暫時固定用片材。於一個實施方式中，上述附襯墊之雙面黏著片材係於製造CSP(Chip Size/Scale Package)或WLP(Wafer Level Package)時可用作暫時固定半導體晶片之片材。於一個實施方式中，上述附襯墊之雙面黏著片材用於包括將上述第2襯墊先剝離之步驟之加工。於一個實施方式中，上述半導體晶片係藉由上述密封樹脂密封，樹脂密封時之加工溫度為100℃以上。 G. Usage The above-mentioned adhesive sheet and the above-mentioned double-sided adhesive sheet with a liner can be suitably used as a sheet for temporary fixation when processing any suitable components (such as semiconductor chips and other electronic components). In one embodiment, the above-mentioned double-sided adhesive sheet with liner can be used as a sheet for temporarily fixing semiconductor chips when manufacturing CSP (Chip Size/Scale Package) or WLP (Wafer Level Package). In one embodiment, the double-sided adhesive sheet with a liner is used for a process including peeling off the second liner. In one embodiment, the semiconductor chip is sealed with the sealing resin, and the processing temperature during resin sealing is 100° C. or higher.

於一個實施方式中，上述附襯墊之雙面黏著片材係捲筒狀。 [實施例] In one embodiment, the double-sided adhesive sheet with a liner is in the form of a roll. [Example]

以下，藉由實施例對本發明具體地進行說明，但本發明並不受該等實施例限定。於實施例中，只要未特別明確記載，則「份」及「%」為重量基準。Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the examples, unless otherwise stated clearly, "parts" and "%" are based on weight.

[製造例1]丙烯酸系聚合物1之製備 向甲苯中添加丙烯酸乙酯70份、丙烯酸丁酯3份、丙烯酸2-乙基己酯30份、甲基丙烯酸甲酯5份、丙烯酸2-羥基乙酯3.5份、及作為聚合起始劑之過氧化苯甲醯0.2份後進行加熱，獲得丙烯酸系聚合物1之甲苯溶液。再者，此處之源自構成丙烯酸系聚合物1之單體之重複單元中之3.1重量%係源自具有活性氫基之單體之重複單元。 [Production Example 1] Preparation of acrylic polymer 1 To toluene, add 70 parts of ethyl acrylate, 3 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 5 parts of methyl methacrylate, 3.5 parts of 2-hydroxyethyl acrylate, and as a polymerization initiator After adding 0.2 part of benzoyl peroxide, the mixture was heated to obtain a toluene solution of acrylic polymer 1. Furthermore, 3.1% by weight of the repeating units derived from the monomers constituting the acrylic polymer 1 here are repeating units derived from the monomers having active hydrogen groups.

[製造例2]丙烯酸系聚合物2之製備 向甲苯中添加丙烯酸丁酯50份、丙烯酸乙酯50份、丙烯酸0.5份、丙烯酸2-羥基乙酯0.1份、及作為聚合起始劑之過氧化苯甲醯0.2份後進行加熱，獲得丙烯酸系聚合物2之甲苯溶液。再者，此處之源自構成丙烯酸系聚合物2之單體之重複單元中之0.60重量%係源自具有活性氫基之單體之重複單元。 [Production Example 2] Preparation of Acrylic Polymer 2 Add 50 parts of butyl acrylate, 50 parts of ethyl acrylate, 0.5 part of acrylic acid, 0.1 part of 2-hydroxyethyl acrylate, and 0.2 part of benzoyl peroxide as a polymerization initiator to toluene, and then heat to obtain an acrylic system. Polymer 2 in toluene solution. Furthermore, 0.60% by weight of the repeating units derived from the monomers constituting the acrylic polymer 2 here are repeating units derived from the monomers having active hydrogen groups.

[製造例3]丙烯酸系聚合物3之製備 向乙酸乙酯中添加丙烯酸甲酯70份、丙烯酸丁酯2份、丙烯酸2-乙基己酯30份、丙烯酸10份、及作為聚合起始劑之過氧化苯甲醯0.2份後進行加熱，獲得丙烯酸系聚合物3之乙酸乙酯溶液。再者，此處之源自構成丙烯酸系聚合物3之單體之重複單元中之8.9重量%係源自具有活性氫基之單體之重複單元。 [Production Example 3] Preparation of Acrylic Polymer 3 To ethyl acetate, add 70 parts of methyl acrylate, 2 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 10 parts of acrylic acid, and 0.2 part of benzoyl peroxide as a polymerization initiator, and then heat. An ethyl acetate solution of acrylic polymer 3 was obtained. Furthermore, 8.9% by weight of the repeating units derived from the monomers constituting the acrylic polymer 3 here are repeating units derived from the monomers having active hydrogen groups.

[實施例1] 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)3重量份、及塑化劑(DIC公司製造，商品名「Monocizer W700」10重量份加以混合，製備黏著劑。 於襯墊(PET膜，厚度：38 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-38」)之剝離處理面塗佈(塗佈・乾燥)上述黏著劑，形成黏著劑層(厚度：10 μm)。 將附上述黏著劑層之襯墊貼合於基材(聚酯膜、東麗公司製造，商品名「Lumirror S10」，厚度：50 μm)，獲得附襯墊之黏著片材前驅物。再者，襯墊(商品名「MRF-38」)之Si-Kα射線之強度為18(kcps)。Si-Kα射線之強度之測定方法如下。 將附襯墊之黏著片材前驅物於溫度40℃、濕度20%之環境下放置5天(加濕熱步驟)，獲得包含襯墊/黏著劑層(第1黏著劑層)/基材之附襯墊之黏著片材。 ·襯墊之Si-Kα射線強度測定 對在襯墊表面(剝離處理面)中隨機抽取之100個部位進行螢光X射線分析。更詳細而言，測定襯墊之與黏接著劑層相接之面(塗佈有剝離處理劑之面)之Si-Kα射線之強度(i)及不與黏接著劑層相接之面(未塗佈剝離處理劑之面)之Si-Kα射線之強度(ii)，求出(i)之值減去(ii)之值所得之值之絕對值，將該值之測定100個部位所得之平均值作為襯墊之Si-Kα射線強度。 再者，Si-Kα射線之強度係於利用下述裝置而進行之測定中波長7.125埃下之強度。 裝置：Rigaku製造 ZSX100e 分析面積：30 mm 分析元素：Si 分析結晶：RX4 輸出：50 kV、70 mA [Example 1] A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and plasticized 10 parts by weight of the agent (manufactured by DIC Corporation, trade name "Monocizer W700") was mixed to prepare an adhesive. On a liner (PET film, thickness: 38 μm, polysiloxane release-treated product, manufactured by Mitsubishi Plastics Co., Ltd., trade name " The above-mentioned adhesive is applied (coated and dried) to the release-treated surface of MRF-38" to form an adhesive layer (thickness: 10 μm). The liner with the above-mentioned adhesive layer is attached to the base material (polyester film , produced by Toray Corporation, trade name "Lumirror S10", thickness: 50 μm), an adhesive sheet precursor with a liner was obtained. Furthermore, the Si-Kα ray of the liner (trade name "MRF-38") was The intensity is 18 (kcps). The method for measuring the intensity of Si-Kα rays is as follows. The adhesive sheet precursor with a liner is placed in an environment with a temperature of 40°C and a humidity of 20% for 5 days (humidification heat step) to obtain a sample containing Pad/adhesive layer (first adhesive layer)/adhesive sheet with liner attached to the base material. · Si-Kα ray intensity measurement of the liner on 100 randomly selected samples from the liner surface (peeled surface) A fluorescent For the intensity (ii) of Si-Kα rays on the surface where the adhesive layer is in contact (the surface without the peeling treatment agent), find the absolute value of the value obtained by subtracting the value of (ii) from the value of (i). The average value of this value measured at 100 locations was used as the Si-Kα ray intensity of the pad. In addition, the intensity of the Si-Kα ray is based on the intensity at a wavelength of 7.125 angstroms measured using the following device. Device : ZSX100e manufactured by Rigaku Analysis area: 30 mm Analytical element: Si Analytical crystal: RX4 Output: 50 kV, 70 mA

[實施例2] 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)，交聯劑(東曹公司製造，商品名「Coronate L」)3重量份、及塑化劑(DIC公司製造，商品名「Monocizer W700」)10重量份加以混合，製備黏著劑。 於襯墊(PET膜，厚度：38 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-38」)之剝離處理面塗佈上述黏著劑，形成黏著劑層(厚度：10 μm)。 將附上述黏著劑層之襯墊貼合於基材(聚萘二甲酸乙二酯膜、杜邦帝人薄膜股份有限公司製造，商品名「Teonex Q51」，厚度：50 μm)，獲得附襯墊之黏著片材前驅物。 將附襯墊之黏著片材前驅物於溫度40℃、濕度20%之環境下放置5天，獲得包含襯墊/黏著劑層(第1黏著劑層)/基材之附襯墊之黏著片材。 [Example 2] A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and a plasticizer (manufactured by DIC Corporation , trade name "Monocizer W700") 10 parts by weight were mixed to prepare an adhesive. The above-mentioned adhesive is coated on the release-treated surface of the liner (PET film, thickness: 38 μm, silicone release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-38") to form an adhesive layer (thickness: 10 μm). The liner with the above adhesive layer was bonded to the base material (polyethylene naphthalate film, manufactured by DuPont Teijin Film Co., Ltd., trade name "Teonex Q51", thickness: 50 μm) to obtain a liner with a liner Adhesive sheet precursor. The liner-attached adhesive sheet precursor was placed in an environment with a temperature of 40°C and a humidity of 20% for 5 days to obtain a liner-attached adhesive sheet including a liner/adhesive layer (first adhesive layer)/substrate material.

[實施例3] 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)3重量份、及塑化劑(DIC公司製造，商品名「Monocizer W700」)10重量份加以混合，製備黏著劑。 於襯墊(PET膜，厚度：38 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-38」)之剝離處理面塗佈上述黏著劑，形成黏著劑層(厚度：10 μm)。 將附上述黏著劑層之襯墊貼合於基材(芳香族性聚醯亞胺膜，宇部興產公司製造，商品名「Upilex-R」，厚度：50 μm)，獲得附襯墊之黏著片材前驅物。 將附襯墊之黏著片材前驅物於溫度40℃、濕度20%之環境下放置5天，獲得包含襯墊/黏著劑層(第1黏著劑層)/基材之附襯墊之黏著片材。 [Example 3] A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and a plasticizer (manufactured by DIC Corporation , trade name "Monocizer W700") 10 parts by weight were mixed to prepare an adhesive. The above-mentioned adhesive is coated on the release-treated surface of the liner (PET film, thickness: 38 μm, silicone release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-38") to form an adhesive layer (thickness: 10 μm). The liner with the above adhesive layer was bonded to the base material (aromatic polyimide film, manufactured by Ube Kosan Co., Ltd., trade name "Upilex-R", thickness: 50 μm) to obtain adhesion with the liner Sheet precursors. The liner-attached adhesive sheet precursor was placed in an environment with a temperature of 40°C and a humidity of 20% for 5 days to obtain a liner-attached adhesive sheet including a liner/adhesive layer (first adhesive layer)/substrate material.

[實施例4] 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)3重量份、及塑化劑(DIC公司製造，商品名「Monocizer W700」)10重量份加以混合，製備黏著劑a1。 於襯墊(PET膜，厚度：38 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-38」)之剝離處理面塗佈上述黏著劑a1，形成黏著劑層(厚度：7 μm)。 將附上述黏著劑層之襯墊貼合於基材(芳香族性聚醯亞胺膜，杜邦公司製造，商品名「Kapton 200H」，厚度：50 μm)，獲得附襯墊之黏著片材前驅物。 將附襯墊之黏著片材前驅物於溫度40℃、濕度20%之環境下放置5天，獲得包含襯墊/黏著劑層(第1黏著劑層)/基材之附襯墊之黏著片材。 [Example 4] A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and a plasticizer (manufactured by DIC Corporation , trade name "Monocizer W700") 10 parts by weight were mixed to prepare adhesive a1. The above-mentioned adhesive a1 is coated on the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Co., Ltd., trade name "MRF-38") to form an adhesive layer (thickness :7 μm). The liner with the above adhesive layer is bonded to the base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 μm) to obtain a precursor of the adhesive sheet with liner things. The liner-attached adhesive sheet precursor was placed in an environment with a temperature of 40°C and a humidity of 20% for 5 days to obtain a liner-attached adhesive sheet including a liner/adhesive layer (first adhesive layer)/substrate material.

[實施例5] 將黏著劑層之厚度設為2 μm，除此以外，以與實施例4相同之方式獲得附襯墊之黏著片材。 [Example 5] A liner-attached adhesive sheet was obtained in the same manner as in Example 4 except that the thickness of the adhesive layer was set to 2 μm.

[實施例6] 將黏著劑層之厚度設為15 μm，除此以外，以與實施例4相同之方式獲得附襯墊之黏著片材。 [Example 6] A liner-attached adhesive sheet was obtained in the same manner as in Example 4 except that the thickness of the adhesive layer was set to 15 μm.

[實施例7] (附襯墊之黏著片材a2) 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)3重量份、及塑化劑(DIC公司製造，商品名「Monocizer W700」)10重量份加以混合，製備黏著劑a1。 於襯墊(PET膜，厚度：38 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-38」)之剝離處理面塗佈上述黏著劑a1，形成黏著劑層(厚度：7 μm)。 將附上述黏著劑層之襯墊貼合於基材(芳香族性聚醯亞胺膜，杜邦公司製造，商品名「Kapton 200H」，厚度：50 μm)，獲得包含襯墊(第1襯墊)/黏著劑層(第1黏著劑層)/基材之附襯墊之黏著片材a2。 (附襯墊之黏著片材a2/底塗層積層體) 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、及交聯劑(東曹公司製造，商品名「Coronate L」)3重量份加以混合，製備黏著劑b。 於附襯墊之黏著片材a2之基材塗佈黏著劑b，形成包含附襯墊之黏著片材a2/底塗層(厚度：13 μm)之積層體。 (附襯墊之雙面黏著片材b) 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)1.5重量份、黏著賦予樹脂(住友電木公司製造，商品名「Sumilite PR12603」)10重量份、熱膨脹性微球(松本油脂製藥公司製造，商品名「Matsumoto Microsphere FN-180SSD」)30重量份、及著色劑(大日精化公司製造，商品名「DYMICS SZ7510 GREEN」)0.5重量份加以混合，製備第2黏著劑層形成用組合物。 將該第2黏著劑層形成用組合物塗佈於襯墊(PET膜，厚度：50 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-50」)之剝離處理面，形成第2黏著劑層(厚度：35 μm)。再者，襯墊(商品名「MRF-50」)之Si-Kα射線之強度為28(kcps)。 將附第2黏著劑層之襯墊與包含附襯墊之黏著片材a2/底塗層之積層體貼合，獲得附襯墊之雙面黏著片材前驅物。 將附襯墊之雙面黏著片材前驅物於溫度40℃、濕度20%之環境下放置5天，獲得包含第1襯墊/第1黏著劑層/基材/底塗層/第2黏著劑層/第2襯墊之附襯墊之雙面黏著片材。 [Example 7] (Adhesive sheet with liner a2) A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and a plasticizer (manufactured by DIC Corporation , trade name "Monocizer W700") 10 parts by weight were mixed to prepare adhesive a1. The above-mentioned adhesive a1 is coated on the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Co., Ltd., trade name "MRF-38") to form an adhesive layer (thickness :7 μm). The liner with the above adhesive layer was bonded to the base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 μm) to obtain a liner (first liner). )/adhesive layer (first adhesive layer)/adhesive sheet a2 of the base material with liner. (Adhesive sheet with liner a2/primer coating laminate) The toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (trade name "Coronate L" manufactured by Tosoh Corporation) were mixed to prepare an adhesive b. The adhesive b is applied to the base material of the adhesive sheet with a liner a2 to form a laminate including the adhesive sheet with a liner a2/primer layer (thickness: 13 μm). (Double-sided adhesive sheet with pad b) A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 1.5 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and an adhesion-imparting resin (Sumitomo Bakelite Co., Ltd. Manufactured by, trade name "Sumilite PR12603") 10 parts by weight of heat-expandable microspheres (manufactured by Matsumoto Oils & Fats Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD"), and colorant (manufactured by Dainichi Seika Co., Ltd., trade name "DYMICS SZ7510 GREEN") 0.5 parts by weight were mixed to prepare a second adhesive layer forming composition. The second adhesive layer-forming composition was applied to the release-treated surface of the liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-50") , forming the second adhesive layer (thickness: 35 μm). Furthermore, the Si-Kα ray intensity of the liner (trade name "MRF-50") is 28 (kcps). The liner with the second adhesive layer is bonded to a laminate including the liner-attached adhesive sheet a2/primer coating layer to obtain a liner-attached double-sided adhesive sheet precursor. The double-sided adhesive sheet precursor with a liner is placed in an environment with a temperature of 40°C and a humidity of 20% for 5 days to obtain the first liner/first adhesive layer/base material/primer coating/second adhesive layer. Double-sided adhesive sheet with liner attached to the agent layer/second liner.

[實施例8] (附襯墊之黏著片材a2) 以與實施例7相同之方式獲得附襯墊之黏著片材a2(襯墊(第1襯墊)/黏著劑層(第1黏著劑層)/基材)。 (附襯墊之黏著片材a2/底塗層積層體) 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、及交聯劑(東曹公司製造，商品名「Coronate L」)3重量份加以混合，製備黏著劑b。 於附襯墊之黏著片材a2之基材塗佈黏著劑b，形成包含附襯墊之黏著片材a2/底塗層(厚度：13 μm)之積層體。 (附襯墊之雙面黏著片材b') 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)1.5重量份、黏著賦予樹脂(住友電木公司製造，商品名「Sumilite PR12603」)10重量份、熱膨脹性微球(松本油脂製藥公司製造，商品名「Matsumoto Microsphere FN-180SSD」)30重量份、及著色劑(大日精化公司製造，商品名「DYMICS SZ7510 GREEN」)0.5重量份加以混合，製備第2黏著劑層形成用組合物。 將該第2黏著劑層形成用組合物塗佈於襯墊(PET膜，厚度：50 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-50」)之剝離處理面，形成第2黏著劑層(厚度：35 μm)。 將附第2黏著劑層之襯墊與包含附襯墊之黏著片材a2/底塗層之積層體貼合，獲得附襯墊之雙面黏著片材前驅物。 將附襯墊之雙面黏著片材前驅物於溫度90℃、濕度1%RH之環境下放置2小時，獲得包含第1襯墊/第1黏著劑層/基材/底塗層/第2黏著劑層/第2襯墊之附襯墊之雙面黏著片材。 [Example 8] (Adhesive sheet with liner a2) A liner-attached adhesive sheet a2 (liner (first liner)/adhesive layer (first adhesive layer)/base material) was obtained in the same manner as in Example 7. (Adhesive sheet with liner a2/primer coating laminate) The toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (trade name "Coronate L" manufactured by Tosoh Corporation) were mixed to prepare an adhesive b. The adhesive b is applied to the base material of the adhesive sheet with a liner a2 to form a laminate including the adhesive sheet with a liner a2/primer layer (thickness: 13 μm). (Double-sided adhesive sheet with liner b') A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 1.5 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and an adhesion-imparting resin (Sumitomo Bakelite Co., Ltd. Manufactured by, trade name "Sumilite PR12603") 10 parts by weight of heat-expandable microspheres (manufactured by Matsumoto Oils & Fats Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD"), and colorant (manufactured by Dainichi Seika Co., Ltd., trade name "DYMICS SZ7510 GREEN") 0.5 parts by weight were mixed to prepare a second adhesive layer forming composition. The second adhesive layer-forming composition was applied to the release-treated surface of the liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-50") , forming the second adhesive layer (thickness: 35 μm). The liner with the second adhesive layer is bonded to a laminate including the liner-attached adhesive sheet a2/primer coating layer to obtain a liner-attached double-sided adhesive sheet precursor. Place the double-sided adhesive sheet precursor with a liner in an environment with a temperature of 90°C and a humidity of 1% RH for 2 hours to obtain the first liner/first adhesive layer/base material/primer coating/second Adhesive layer/second liner double-sided adhesive sheet with liner.

[實施例9] (附襯墊之黏著片材a2) 以與實施例7相同之方式獲得附襯墊之黏著片材a2(襯墊(第1襯墊)/黏著劑層(第1黏著劑層)/基材)。 (附襯墊之黏著片材a2/底塗層積層體) 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、及交聯劑(東曹公司製造，商品名「Coronate L」)3重量份加以混合，製備黏著劑b。 於附襯墊之黏著片材a2之基材塗佈黏著劑b，形成包含附襯墊之黏著片材a2/底塗層(厚度：13 μm)之積層體。 (附襯墊之雙面黏著片材b'') 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)1.5重量份、黏著賦予樹脂(住友電木公司製造，商品名「Sumilite PR12603」)10重量份、熱膨脹性微球(松本油脂製藥公司製造，商品名「Matsumoto Microsphere FN-180SSD」)60重量份、及著色劑(大日精化公司製造，商品名「DYMICS SZ7510 GREEN」)0.5重量份加以混合，製備第2黏著劑層形成用組合物。 將該第2黏著劑層形成用組合物塗佈於襯墊(PET膜，厚度：50 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-50」)之剝離處理面，形成第2黏著劑層(厚度：35 μm)。 將附第2黏著劑層之襯墊與包含襯墊之黏著片材a/底塗層之積層體貼合，獲得附襯墊之雙面黏著片材前驅物。 將附襯墊之雙面黏著片材前驅物於溫度40℃、濕度92%RH之環境下放置3天，獲得包含第1襯墊/第1黏著劑層/基材/底塗層/第2黏著劑層/第2襯墊之附襯墊之雙面黏著片材。 [Example 9] (Adhesive sheet with liner a2) A liner-attached adhesive sheet a2 (liner (first liner)/adhesive layer (first adhesive layer)/base material) was obtained in the same manner as in Example 7. (Adhesive sheet with liner a2/primer coating laminate) The toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (trade name "Coronate L" manufactured by Tosoh Corporation) were mixed to prepare an adhesive b. The adhesive b is applied to the base material of the adhesive sheet with a liner a2 to form a laminate including the adhesive sheet with a liner a2/primer layer (thickness: 13 μm). (Double-sided adhesive sheet with pad b'') A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 1.5 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and an adhesion-imparting resin (Sumitomo Bakelite Co., Ltd. 10 parts by weight of thermally expandable microspheres (trade name "Sumilite PR12603"), 60 parts by weight of heat-expandable microspheres (trade name "Matsumoto Microsphere FN-180SSD"), and a colorant (trade name manufactured by Dainichi Seika Co., Ltd. "DYMICS SZ7510 GREEN") 0.5 parts by weight were mixed to prepare a second adhesive layer forming composition. The second adhesive layer-forming composition was applied to the release-treated surface of the liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-50") , forming the second adhesive layer (thickness: 35 μm). The liner with the second adhesive layer is bonded to a laminate including the adhesive sheet a/primer layer of the liner to obtain a double-sided adhesive sheet precursor with a liner. The double-sided adhesive sheet precursor with a liner was placed in an environment with a temperature of 40°C and a humidity of 92% RH for 3 days to obtain the first liner/first adhesive layer/base material/primer coating/second Adhesive layer/second liner double-sided adhesive sheet with liner.

[實施例10] (附襯墊之黏著片材a3) 將上述丙烯酸系聚合物2之甲苯溶液(丙烯酸系聚合物2：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)3重量份、及黏著賦予樹脂(荒川化學工業公司製造，商品名「TAMANOL 200N」)15重量份加以混合，製備黏著劑a'。 於襯墊(PET膜，厚度：38 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-38」)之剝離處理面塗佈上述黏著劑a'，形成黏著劑層(厚度：5 μm)。 將附上述黏著劑層之襯墊貼合於基材(芳香族性聚醯亞胺膜、杜邦公司製造，商品名「Kapton 200H」，厚度：50 μm)，獲得包含襯墊(第1襯墊)/黏著劑層(第1黏著劑層)/基材之附襯墊之黏著片材a3。 (附襯墊之黏著片材a3/底塗層積層體) 將上述丙烯酸系聚合物2之甲苯溶液(丙烯酸系聚合物2：100重量份)、及交聯劑(東曹公司製造，商品名「Coronate L」)3重量份加以混合，製備黏著劑b'。 於附襯墊之黏著片材a3之基材塗佈黏著劑b'，形成包含附襯墊之黏著片材a3/底塗層(厚度：13 μm)之積層體。 (附襯墊之雙面黏著片材b2) 將上述丙烯酸系聚合物2之甲苯溶液(丙烯酸系聚合物2：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)1.5重量份、黏著賦予樹脂(住友電木公司製造，商品名「Sumilite PR12603」)10重量份、熱膨脹性微球(松本油脂製藥公司製造，商品名「Matsumoto Microsphere FN-180SSD」)30重量份、及著色劑(大日精化公司製造，商品名「DYMICS SZ7510 GREEN」)0.5重量份加以混合，製備第2黏著劑層形成用組合物。 將該第2黏著劑層形成用組合物塗佈於襯墊(PET膜，厚度：50 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-50」)之剝離處理面，形成第2黏著劑層(厚度：35 μm)。 將附第2黏著劑層之襯墊與包含附襯墊之黏著片材a3/底塗層之積層體貼合，獲得附襯墊之雙面黏著片材前驅物。 將附襯墊之雙面黏著片材前驅物於溫度40℃、濕度20%RH之環境下放置5天，獲得包含第1襯墊/第1黏著劑層/基材/底塗層/第2黏著劑層/第2襯墊之附襯墊之雙面黏著片材。 [Example 10] (Adhesive sheet with liner a3) A toluene solution of the above-mentioned acrylic polymer 2 (acrylic polymer 2: 100 parts by weight), 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and an adhesion-imparting resin (Arakawa Chemical Industry Co., Ltd. Manufactured by the company, trade name "TAMANOL 200N") 15 parts by weight were mixed to prepare adhesive a'. The above-mentioned adhesive a' is coated on the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Co., Ltd., trade name "MRF-38") to form an adhesive layer ( Thickness: 5 μm). The liner with the above adhesive layer was bonded to a base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 μm) to obtain a liner (first liner). )/adhesive layer (first adhesive layer)/adhesive sheet a3 of the base material with liner. (Adhesive sheet with liner a3/primer coating laminate) The toluene solution of the above-mentioned acrylic polymer 2 (acrylic polymer 2: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were mixed to prepare adhesive b' . The adhesive b' is applied to the base material of the adhesive sheet with a liner a3 to form a laminate including the adhesive sheet with a liner a3/primer layer (thickness: 13 μm). (Double-sided adhesive sheet with pad b2) A toluene solution of the above-mentioned acrylic polymer 2 (acrylic polymer 2: 100 parts by weight), 1.5 parts by weight of a cross-linking agent (trade name "Coronate L" manufactured by Tosoh Corporation), and an adhesion-imparting resin (Sumitomo Bakelite Co., Ltd. Manufactured by, trade name "Sumilite PR12603") 10 parts by weight of heat-expandable microspheres (manufactured by Matsumoto Oils & Fats Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD"), and colorant (manufactured by Dainichi Seika Co., Ltd., trade name "DYMICS SZ7510 GREEN") 0.5 parts by weight were mixed to prepare a second adhesive layer forming composition. The second adhesive layer-forming composition was applied to the release-treated surface of the liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-50") , forming the second adhesive layer (thickness: 35 μm). The liner with the second adhesive layer is bonded to a laminate including the liner-attached adhesive sheet a3/primer coating layer to obtain a liner-attached double-sided adhesive sheet precursor. The double-sided adhesive sheet precursor with a liner was placed in an environment with a temperature of 40°C and a humidity of 20% RH for 5 days to obtain the first liner/first adhesive layer/base material/primer coating/second Adhesive layer/second liner double-sided adhesive sheet with liner.

[實施例11] (附襯墊之黏著片材a4) 將上述丙烯酸系聚合物3之甲苯溶液(丙烯酸系聚合物3：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)3重量份、黏著賦予樹脂(荒川化學工業公司製造，商品名「TAMANOL 200N」)15重量份加以混合，製備黏著劑a''。 於襯墊(PET膜，厚度：38 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-38」)之剝離處理面塗佈上述黏著劑a'，形成黏著劑層(厚度：5 μm)。 將附上述黏著劑層之襯墊貼合於基材(芳香族性聚醯亞胺膜，杜邦公司製造，商品名「Kapton 200H」，厚度：50 μm)，獲得包含襯墊(第1襯墊)/黏著劑層(第1黏著劑層)/基材之附襯墊之黏著片材a4。 (附襯墊之黏著片材a4/底塗層積層體) 將上述丙烯酸系聚合物3之甲苯溶液(丙烯酸系聚合物3：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)3重量份加以混合，製備黏著劑b''。 於附襯墊之黏著片材a4之基材塗佈黏著劑b''，形成包含附襯墊之黏著片材a4/底塗層(厚度：13 μm)之積層體。 (附襯墊之雙面黏著片材b3) 將上述丙烯酸系聚合物3之甲苯溶液(丙烯酸系聚合物3：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)1.5重量份、黏著賦予樹脂(住友電木公司製造，商品名「Sumilite PR12603」)10重量份、熱膨脹性微球(松本油脂製藥公司製造，商品名「Matsumoto Microsphere FN-180SSD」)30重量份、著色劑(大日精化公司製造，商品名「DYMICS SZ7510 GREEN」)0.5重量份加以混合，製備第2黏著劑層形成用組合物。 將該第2黏著劑層形成用組合物塗佈於襯墊(PET膜，厚度：50 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-50」)之剝離處理面，形成第2黏著劑層(厚度：35 μm)。 將附第2黏著劑層之襯墊與包含附襯墊之黏著片材a4/底塗層之積層體貼合，獲得附襯墊之雙面黏著片材前驅物。 將附襯墊之雙面黏著片材前驅物於溫度40℃、濕度20%RH之環境下放置5天，獲得包含第1襯墊/第1黏著劑層/基材/底塗層/第2黏著劑層/第2襯墊之附襯墊之雙面黏著片材。 [Example 11] (Adhesive sheet with liner a4) A toluene solution of the above-mentioned acrylic polymer 3 (acrylic polymer 3: 100 parts by weight), 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and a tackifying resin (Arakawa Chemical Industry Co., Ltd. Manufactured under the trade name "TAMANOL 200N") and 15 parts by weight were mixed to prepare adhesive a''. The above-mentioned adhesive a' is coated on the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Co., Ltd., trade name "MRF-38") to form an adhesive layer ( Thickness: 5 μm). The liner with the above adhesive layer was bonded to the base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 μm) to obtain a liner (first liner). )/adhesive layer (first adhesive layer)/adhesive sheet a4 of the base material with liner. (Adhesive sheet with liner a4/primer coating laminate) Mix the toluene solution of the above-mentioned acrylic polymer 3 (acrylic polymer 3: 100 parts by weight) and 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L") to prepare adhesive b'' . The adhesive b'' is applied to the base material of the adhesive sheet with liner a4, and a laminate including the adhesive sheet with liner a4/primer coating (thickness: 13 μm) is formed. (Double-sided adhesive sheet with liner b3) A toluene solution of the above-mentioned acrylic polymer 3 (acrylic polymer 3: 100 parts by weight), 1.5 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and an adhesive resin (Sumitomo Bakelite Co., Ltd. Manufactured, trade name "Sumilite PR12603") 10 parts by weight of heat-expandable microspheres (manufactured by Matsumoto Oils & Fats Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD"), colorant (manufactured by Dainichi Seika Co., Ltd., trade name " 0.5 part by weight of DYMICS SZ7510 GREEN") was mixed to prepare a second adhesive layer forming composition. The second adhesive layer-forming composition was applied to the release-treated surface of the liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-50") , forming the second adhesive layer (thickness: 35 μm). The liner with the second adhesive layer is bonded to a laminate including the liner-attached adhesive sheet a4/primer coat, to obtain a liner-attached double-sided adhesive sheet precursor. The double-sided adhesive sheet precursor with a liner was placed in an environment with a temperature of 40°C and a humidity of 20% RH for 5 days to obtain the first liner/first adhesive layer/base material/primer coating/second Adhesive layer/second liner double-sided adhesive sheet with liner.

[比較例1] 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)3重量份、塑化劑(DIC公司製造，商品名「Monocizer W700」)10重量份加以混合，製備黏著劑a1。 於襯墊(PET膜，厚度：38 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-38」)之剝離處理面塗佈上述黏著劑a，形成黏著劑層(厚度：7 μm)。 將附上述黏著劑層之襯墊貼合於基材(芳香族性聚醯亞胺膜，杜邦公司製造，商品名「Kapton 200H」，厚度：50 μm)，獲得附襯墊之黏著片材前驅物。 將附襯墊之黏著片材前驅物於溫度200℃、濕度0.1%RH之環境下放置4小時，獲得包含襯墊/黏著劑層(第1黏著劑層)/基材之附襯墊之黏著片材。 [Comparative example 1] A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and a plasticizer (manufactured by DIC Corporation, Trade name "Monocizer W700") 10 parts by weight were mixed to prepare adhesive a1. The above-mentioned adhesive a is coated on the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-38") to form an adhesive layer (thickness :7 μm). The liner with the above adhesive layer is bonded to the base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 μm) to obtain a precursor of the adhesive sheet with liner things. The liner-attached adhesive sheet precursor was placed in an environment with a temperature of 200°C and a humidity of 0.1% RH for 4 hours to obtain the liner-attached adhesion including the liner/adhesive layer (first adhesive layer)/substrate Sheet.

[比較例2] (附襯墊之黏著片材a2) 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)3重量份、及塑化劑(DIC公司製造，商品名「Monocizer W700」)10重量份加以混合，製備黏著劑a1。 於襯墊(PET膜，厚度：38 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-38」)之剝離處理面塗佈上述黏著劑a，形成黏著劑層(厚度：7 μm)。 將附上述黏著劑層之襯墊貼合於基材(芳香族性聚醯亞胺膜、杜邦公司製造，商品名「Kapton 200H」，厚度：50 μm)，獲得包含襯墊(第1襯墊)/黏著劑層(第1黏著劑層)/基材之附襯墊之黏著片材a2。 (附襯墊之黏著片材a2/底塗層積層體) 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、及交聯劑(東曹公司製造，商品名「Coronate L」)3重量份加以混合，製備黏著劑b。 於附襯墊之黏著片材a2之基材塗佈黏著劑b，形成包含附襯墊之黏著片材a2/底塗層(厚度：13 μm)之積層體。 (附襯墊之黏著片材) 將上述丙烯酸系聚合物1之甲苯溶液(丙烯酸系聚合物1：100重量份)、交聯劑(東曹公司製造，商品名「Coronate L」)1.5重量份、黏著賦予樹脂(住友電木公司製造，商品名「Sumilite PR12603」)10重量份、熱膨脹性微球(松本油脂製藥公司製造，商品名「Matsumoto Microsphere FN-180SSD」)30重量份、著色劑(大日精化公司製造，商品名「DYMICS SZ7510 GREEN」)0.5重量份加以混合，製備第2黏著劑層形成用組合物。 將該第2黏著劑層形成用組合物塗佈於襯墊(PET膜，厚度：50 μm，聚矽氧系剝離處理品，三菱樹脂公司製造，商品名「MRF-50」)之剝離處理面，形成第2黏著劑層(厚度：35 μm)。 將附第2黏著劑層之襯墊與包含附襯墊之黏著片材a2/底塗層之積層體貼合，獲得附襯墊之雙面黏著片材前驅物。 將附襯墊之雙面黏著片材前驅物於溫度85℃、濕度92%RH之環境下放置7天，獲得包含第1襯墊/第1黏著劑層/基材/底塗層/第2黏著劑層/第2襯墊之附襯墊之雙面黏著片材。 [Comparative example 2] (Adhesive sheet with liner a2) A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 3 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and a plasticizer (manufactured by DIC Corporation , trade name "Monocizer W700") 10 parts by weight were mixed to prepare adhesive a1. The above-mentioned adhesive a is coated on the release-treated surface of the liner (PET film, thickness: 38 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-38") to form an adhesive layer (thickness :7 μm). The liner with the above adhesive layer was bonded to a base material (aromatic polyimide film, manufactured by DuPont, trade name "Kapton 200H", thickness: 50 μm) to obtain a liner (first liner). )/adhesive layer (first adhesive layer)/adhesive sheet a2 of the base material with liner. (Adhesive sheet with liner a2/primer coating laminate) The toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight) and 3 parts by weight of a cross-linking agent (trade name "Coronate L" manufactured by Tosoh Corporation) were mixed to prepare an adhesive b. The adhesive b is applied to the base material of the adhesive sheet with a liner a2 to form a laminate including the adhesive sheet with a liner a2/primer layer (thickness: 13 μm). (adhesive sheet with liner) A toluene solution of the above-mentioned acrylic polymer 1 (acrylic polymer 1: 100 parts by weight), 1.5 parts by weight of a cross-linking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and an adhesion-imparting resin (Sumitomo Bakelite Co., Ltd. Manufactured, trade name "Sumilite PR12603") 10 parts by weight of heat-expandable microspheres (manufactured by Matsumoto Oils & Fats Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere FN-180SSD"), colorant (manufactured by Dainichi Seika Co., Ltd., trade name " 0.5 part by weight of DYMICS SZ7510 GREEN") was mixed to prepare a second adhesive layer forming composition. The second adhesive layer-forming composition was applied to the release-treated surface of the liner (PET film, thickness: 50 μm, silicone-based release-treated product, manufactured by Mitsubishi Plastics Corporation, trade name "MRF-50") , forming the second adhesive layer (thickness: 35 μm). The liner with the second adhesive layer is bonded to a laminate including the liner-attached adhesive sheet a2/primer coating layer to obtain a liner-attached double-sided adhesive sheet precursor. The double-sided adhesive sheet precursor with a liner was placed in an environment with a temperature of 85°C and a humidity of 92% RH for 7 days to obtain the first liner/first adhesive layer/base material/primer coating/second Adhesive layer/second liner double-sided adhesive sheet with liner.

[評價] 將實施例及比較例中所獲得之黏著片材供於以下評價。將結果示於表1中。 (1)黏著力 將第1襯墊自實施例及比較例中所獲得之附襯墊之黏著片材剝離，將黏著片材切斷成寬：20 mm、長：140 mm之尺寸，依據JIS Z 0237(2000年)，於溫度：23℃及濕度：65RH之氛圍下，使2 kg之輥於聚對苯二甲酸乙二酯膜(東麗公司製造，商品名「Lumirror S-10」，厚度：25 μm、寬：20 mm)上往返1次而使其壓接並貼合於第1黏著劑層，製作評價樣品。 將該評價樣品設置於附設定為23℃之恆溫槽之拉伸試驗機(島津製作所公司製造，商品名「島津Autograph AG-120kN」)並放置30分鐘。 放置後，於23℃之溫度下測定將聚對苯二甲酸乙二酯於剝離角度：180°、剝離速度(拉伸速度)：300 mm/min之條件自黏著片材剝離時之荷重，求出此時之最大荷重(測定初期之峰頂除外之荷重之最大值)，將該最大荷重作為黏著力(N/20 mm)。 (2)含水率 將襯墊自實施例及比較例中所獲得之附襯墊之黏著片材剝離，並藉由卡氏滴定法測定黏著片材之含水率。測定裝置及測定條件之詳細內容如下。 測定裝置：電量滴定式水分測定裝置(三菱化學公司製造，CA-06)、加熱氣化裝置(三菱化學公司製造，VA-06) 測定條件：加熱氣化法(150℃加熱) 陽極液：Aquamicron AKX(API Corporation公司製造) 陰極液：Aquamicron CXU(API Corporation公司製造) (3)接觸角 將第1襯墊自實施例及比較例中所獲得之附襯墊之黏著片材剝離，測定第1黏著劑層中之水之接觸角。 使用接觸角計(協和界面公司製造，商品名「CX-A型」)於23℃/50%RH環境下將2 μl純水滴加至第1黏著劑層之表面，滴加5秒後測定液滴之接觸角，將該操作重複進行5次，求出其平均值。 (4)凝膠分率 利用網狀片材包住第1黏著劑層0.1 g，於室溫下於甲苯50 ml中靜置1週，使該樣品浸漬於甲苯中。其後，取出甲苯不溶分，並於70℃下歷時2小時使之乾燥後，對乾燥後之甲苯不溶分進行稱量。 根據甲苯浸漬前之樣品重量與甲苯不溶分之重量，並藉由下述式算出樹脂層之凝膠分率。 凝膠分率(%)＝[(甲苯不溶分之重量)/(甲苯浸漬前之樣品重量)]×100 (5)密封樹脂前驅物之流動性評價 將襯墊自實施例及比較例中所獲得之附襯墊之黏著片材剝離，並將第2黏著劑層側貼合於板玻璃。 將開有直徑3 mm之孔之厚度130 μm聚四氟乙烯(PTFE)片材放置於第1黏著劑層上。使密封樹脂前驅物(環氧樹脂、Nagase chemteX公司製造，商品名「R4212」)流入該PTFE片材之孔中，形成直徑3 mm、厚度130 μm之密封樹脂前驅物之柱狀體。 去除PTFE片材，將附密封樹脂前驅物之柱狀體之黏著片材作為試樣設置於附高溫載台之光學顯微鏡，於23℃下放置1分鐘後加熱至130℃。 針對藉由加熱而流動之密封樹脂前驅物，測量上述柱狀體形成位置之外緣與流動後之密封樹脂前驅物外緣之最短距離成為30 μm之時間。 將上述測量進行10次，根據最長時間與最短時間之差，並藉由以下基準對密封樹脂前驅物之流動性之變動進行評價。 優(表中○)：上述差未達60秒 合格(表中△)：上述差為60秒～180秒 不合格(表中×)：上述差超過180秒 [evaluation] The adhesive sheets obtained in Examples and Comparative Examples were used for the following evaluation. The results are shown in Table 1. (1)Adhesion The first liner was peeled off from the adhesive sheet with the liner obtained in the Examples and Comparative Examples, and the adhesive sheet was cut into dimensions of width: 20 mm and length: 140 mm, in accordance with JIS Z 0237 (2000) ), in an atmosphere of temperature: 23°C and humidity: 65RH, apply a 2 kg roller to a polyethylene terephthalate film (manufactured by Toray, trade name "Lumirror S-10", thickness: 25 μm, Width: 20 mm), go back and forth once to press and bond it to the first adhesive layer, and prepare an evaluation sample. This evaluation sample was placed in a tensile testing machine (manufactured by Shimadzu Corporation, trade name "Shimadzu Autograph AG-120kN") with a thermostat set at 23°C and left to stand for 30 minutes. After standing, measure the load when peeling off the polyethylene terephthalate from the adhesive sheet under the conditions of peeling angle: 180° and peeling speed (stretch speed): 300 mm/min at a temperature of 23°C. Find out Find the maximum load at this time (the maximum value of the load excluding the peak at the initial stage of measurement), and use this maximum load as the adhesive force (N/20 mm). (2)Moisture content The liner was peeled off from the liner-attached adhesive sheet obtained in the Examples and Comparative Examples, and the moisture content of the adhesive sheet was measured by Karl Fischer titration. Details of the measurement device and measurement conditions are as follows. Measuring device: coulometric titration moisture measuring device (manufactured by Mitsubishi Chemical Corporation, CA-06), heating and gasification device (manufactured by Mitsubishi Chemical Corporation, VA-06) Measurement conditions: Heating and vaporization method (heating at 150°C) Anolyte: Aquamicron AKX (manufactured by API Corporation) Catholyte: Aquamicron CXU (manufactured by API Corporation) (3) Contact angle The first liner was peeled off from the adhesive sheet with the liner obtained in Examples and Comparative Examples, and the contact angle of water in the first adhesive layer was measured. Use a contact angle meter (manufactured by Kyowa Interface Co., Ltd., trade name "CX-A") to drop 2 μl of pure water onto the surface of the first adhesive layer in a 23°C/50%RH environment, and measure the solution after 5 seconds. The contact angle of the drop was repeated 5 times and the average value was obtained. (4) Gel fraction Wrap 0.1 g of the first adhesive layer with a mesh sheet and let it stand in 50 ml of toluene at room temperature for 1 week to immerse the sample in toluene. Thereafter, the toluene-insoluble fraction was taken out and dried at 70° C. for 2 hours, and then the dried toluene-insoluble fraction was weighed. Based on the weight of the sample before toluene immersion and the weight of the toluene-insoluble part, the gel fraction of the resin layer was calculated by the following formula. Gel fraction (%) = [(weight of toluene-insoluble fraction)/(weight of sample before toluene immersion)] × 100 (5) Evaluation of fluidity of sealing resin precursor The liner was peeled off from the adhesive sheet with the liner obtained in the Examples and Comparative Examples, and the second adhesive layer side was bonded to the plate glass. Place a polytetrafluoroethylene (PTFE) sheet with a thickness of 130 μm and a hole of 3 mm diameter on the first adhesive layer. The sealing resin precursor (epoxy resin, manufactured by Nagase ChemteX Co., Ltd., trade name "R4212") was flowed into the hole of the PTFE sheet to form a columnar body of the sealing resin precursor with a diameter of 3 mm and a thickness of 130 μm. Remove the PTFE sheet, place the adhesive sheet with the columnar body of the sealing resin precursor as a sample on an optical microscope with a high-temperature stage, place it at 23°C for 1 minute, and then heat it to 130°C. For the sealing resin precursor that flows by heating, the time until the shortest distance between the outer edge of the columnar body formation position and the outer edge of the flowed sealing resin precursor becomes 30 μm is measured. The above measurement was performed 10 times, and the change in fluidity of the sealing resin precursor was evaluated based on the difference between the longest time and the shortest time based on the following criteria. Excellent (○ in the table): The above difference does not reach 60 seconds Passed (△ in the table): The above difference is 60 seconds to 180 seconds Unsatisfactory (× in the table): The above difference exceeds 180 seconds

[表1]    實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 比較例1 比較例2 黏著片材之含水率 (重量%) 0.2 0.2 0.5 0.7 0.8 0.7 1.2 0.1 5.8 1.1 1.2 0.045 6.2 黏著劑層(第1黏著劑層) 黏著力 (N/20 mm) 1 0.98 0.98 0.6 0.2 1.5 0.6 0.6 0.6 5 7.5 0.6 0.6 基礎聚合物之SP值 (cal/cm 3) 1/2 8.807 8.807 8.807 8.807 8.807 8.807 8.807 8.807 8.807 8.848 9.015 8.807 8.807 水之接觸角 (°) 98 98 98 98 98 98 98 98 98 105 85 98 98 厚度 (μm) 10 10 10 7 2 15 7 7 7 5 5 7 7 凝膠分率 (%) 80 80 80 80 80 80 80 80 80 67 98 80 80 基材 Tg (℃) 69 118 285 410 410 410 410 410 410 410 410 410 410 加濕熱步驟中之時間、溫度及濕度之乘積 96000 96000 96000 96000 96000 96000 96000 180 264960 96000 96000 80 1313760 密封樹脂前驅物之流動性評價 △ △ ○ ○ ○ ○ ○ ○ ○ ○ ○ × × [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative example 1 Comparative example 2 Moisture content of adhesive sheet (weight%) 0.2 0.2 0.5 0.7 0.8 0.7 1.2 0.1 5.8 1.1 1.2 0.045 6.2 Adhesive layer (1st adhesive layer) Adhesion (N/20 mm) 1 0.98 0.98 0.6 0.2 1.5 0.6 0.6 0.6 5 7.5 0.6 0.6 SP value of base polymer (cal/cm 3 ) 1/2 8.807 8.807 8.807 8.807 8.807 8.807 8.807 8.807 8.807 8.848 9.015 8.807 8.807 water contact angle (°) 98 98 98 98 98 98 98 98 98 105 85 98 98 thickness (μm) 10 10 10 7 2 15 7 7 7 5 5 7 7 gel fraction (%) 80 80 80 80 80 80 80 80 80 67 98 80 80 base material Tg (℃) 69 118 285 410 410 410 410 410 410 410 410 410 410 The product of time, temperature and humidity in the humidification heat step 96000 96000 96000 96000 96000 96000 96000 180 264960 96000 96000 80 1313760 Evaluation of fluidity of sealing resin precursors △ △ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ×

10:基材 20:黏著劑層 30:第2黏著劑層 40:第1襯墊 50:第2襯墊 100,200:黏著片材 110:附襯墊之雙面黏著片材 10:Substrate 20: Adhesive layer 30: 2nd adhesive layer 40: 1st pad 50: 2nd pad 100,200: Adhesive sheet 110:Double-sided adhesive sheet with pad

圖1係本發明之一實施方式之黏著片材之概略剖視圖。 圖2係本發明之另一實施方式之黏著片材之概略剖視圖。 圖3係本發明之一實施方式之附襯墊之雙面黏著片材之概略剖視圖。 FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention. 3 is a schematic cross-sectional view of a double-sided adhesive sheet with a liner according to one embodiment of the present invention.

10:基材 10:Substrate

20:黏著劑層 20: Adhesive layer

100:黏著片材 100:Adhesive sheet

Claims (10)

一種黏著片材，其係具備基材、及配置於該基材之至少單側之黏著劑層者，且將該黏著劑層貼合於聚對苯二甲酸乙二酯時之23℃下之黏著力為0.1N/20mm~8N/20mm，該黏著劑層含有包含基礎聚合物之黏著劑，該基礎聚合物之sp值為7(cal/cm3)1/2~10(cal/cm3)1/2，該黏著片材之含水率為0.05重量%~6重量%，該黏著劑層之水之接觸角為70°~120°。 An adhesive sheet having a base material and an adhesive layer disposed on at least one side of the base material, and the adhesive layer is bonded to polyethylene terephthalate at 23°C. The adhesive force is 0.1N/20mm~8N/20mm. The adhesive layer contains an adhesive containing a base polymer. The sp value of the base polymer is 7(cal/cm 3 ) 1/2 ~10(cal/cm 3 ) 1/2 , the moisture content of the adhesive sheet is 0.05%~6% by weight, and the contact angle of water in the adhesive layer is 70°~120°. 如請求項1之黏著片材，其中上述基材係包含玻璃轉移溫度(Tg)為60℃~450℃之樹脂的樹脂片材。 The adhesive sheet of claim 1, wherein the base material is a resin sheet containing a resin with a glass transition temperature (Tg) of 60°C to 450°C. 如請求項1或2之黏著片材，其中上述基材包含芳香族性聚醯亞胺系樹脂。 The adhesive sheet of claim 1 or 2, wherein the base material includes aromatic polyimide resin. 如請求項1或2之黏著片材，其中上述黏著劑層之厚度為2μm~15μm。 For example, the adhesive sheet of claim 1 or 2, wherein the thickness of the adhesive layer is 2 μm~15 μm. 如請求項1或2之黏著片材，其中上述黏著劑層之凝膠分率為60%~100%。 For example, the adhesive sheet of claim 1 or 2, wherein the gel fraction of the adhesive layer is 60% to 100%. 如請求項1或2之黏著片材，其中上述基礎聚合物係丙烯酸系聚合物，該丙烯酸系聚合物包含源自含羥基單體之結構單元，該源自含羥基單體之結構單元之含量相對於構成該丙烯酸系聚合物之總結構單元100重量份為0.1重量份~20重量份。 The adhesive sheet of claim 1 or 2, wherein the base polymer is an acrylic polymer, the acrylic polymer contains structural units derived from hydroxyl-containing monomers, and the content of the structural units derived from hydroxyl-containing monomers The amount is 0.1 to 20 parts by weight relative to 100 parts by weight of the total structural units constituting the acrylic polymer. 如請求項1或2之黏著片材，其於上述基材之與上述黏著劑層相反側進而具備第2黏著劑層。 The adhesive sheet according to claim 1 or 2 further includes a second adhesive layer on the side of the base material opposite to the adhesive layer. 如請求項1或2之黏著片材，其於製造CSP(Chip Size/Scale Package)或WLP(Wafer Level Package)時用作暫時固定半導體晶片之片材。 For example, the adhesive sheet of claim 1 or 2 is used as a sheet for temporarily fixing semiconductor chips when manufacturing CSP (Chip Size/Scale Package) or WLP (Wafer Level Package). 如請求項8之黏著片材，其中上述半導體晶片係經密封樹脂密封，該樹脂密封時之加工溫度為100℃以上。 For example, the adhesive sheet of claim 8, wherein the semiconductor chip is sealed with a sealing resin, and the processing temperature during sealing of the resin is above 100°C. 一種如請求項1至9中任一項之黏著片材之製造方法，其包括：於基材上形成包含黏著劑之組合物之塗佈層之步驟；於該塗佈層面上配置襯墊而形成積層體之步驟；及將該積層體於溫度及濕度受到管理之環境下放置特定加濕熱時間(例如2小時~7天)之加濕熱步驟；且加濕熱步驟中之加濕熱時間、溫度及濕度之乘積為100~300000℃‧RH%‧h。 A method for manufacturing an adhesive sheet according to any one of claims 1 to 9, which includes: forming a coating layer of a composition containing an adhesive on a substrate; and arranging a liner on the coating layer. The step of forming the laminated body; and the humidifying heat step of placing the laminated body in an environment where the temperature and humidity are controlled for a specific humidifying heat time (for example, 2 hours to 7 days); and the humidifying heat time, temperature and The product of humidity is 100~300000℃‧RH%‧h.
TW111101660A 2021-03-05 2022-01-14 adhesive sheet TWI815278B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021035436 2021-03-05
JP2021-035436 2021-03-05

Publications (2)

Publication Number Publication Date
TW202239907A TW202239907A (en) 2022-10-16
TWI815278B true TWI815278B (en) 2023-09-11

Family

ID=83154242

Family Applications (1)

Application Number Title Priority Date Filing Date
TW111101660A TWI815278B (en) 2021-03-05 2022-01-14 adhesive sheet

Country Status (5)

Country Link
JP (1) JPWO2022185611A1 (en)
KR (1) KR20230141837A (en)
CN (1) CN116917432A (en)
TW (1) TWI815278B (en)
WO (1) WO2022185611A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201540803A (en) * 2014-03-05 2015-11-01 Nitto Denko Corp Adhesive sheet
TW202022065A (en) * 2018-12-07 2020-06-16 長興材料工業股份有限公司 Cross-linkable copolymer and uses of the same
TW202024263A (en) * 2013-03-15 2020-07-01 日商日東電工股份有限公司 Adhesive sheet

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4403631B2 (en) 2000-04-24 2010-01-27 ソニー株式会社 Manufacturing method of chip-shaped electronic component and manufacturing method of pseudo wafer used for manufacturing the same
JP2001313350A (en) 2000-04-28 2001-11-09 Sony Corp Chip-shaped electronic component and its manufacturing method, and pseudo-wafer used for manufacture of chip- shaped electronic component and its manufacturing method
JP5520785B2 (en) * 2010-11-10 2014-06-11 日東電工株式会社 Insulating tape
CN107109144A (en) * 2014-10-20 2017-08-29 积水化成品工业株式会社 With the bonding cohesive gel film of purposes, its manufacture method, a pair of adherends fixing means and composite
JP6673078B2 (en) * 2016-07-27 2020-03-25 東洋インキＳｃホールディングス株式会社 Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW202024263A (en) * 2013-03-15 2020-07-01 日商日東電工股份有限公司 Adhesive sheet
TW201540803A (en) * 2014-03-05 2015-11-01 Nitto Denko Corp Adhesive sheet
TW202022065A (en) * 2018-12-07 2020-06-16 長興材料工業股份有限公司 Cross-linkable copolymer and uses of the same

Also Published As

Publication number Publication date
JPWO2022185611A1 (en) 2022-09-09
TW202239907A (en) 2022-10-16
CN116917432A (en) 2023-10-20
WO2022185611A1 (en) 2022-09-09
KR20230141837A (en) 2023-10-10

Similar Documents

Publication Publication Date Title
TWI686458B (en) Adhesive sheet
TWI506111B (en) And then peeling off the adhesive composition, adhesive sheet, and electronic parts of the cutting process
TWI439529B (en) Dicing die-bonding film and process for producing semiconductor device
TWI608073B (en) Heat strip type adhesive tape and cutting method for electronic parts
TW200305624A (en) Heat-peelable pressure-sensitive adhesive sheet for electronic part, method of processing electronic part, and electronic part
KR20100059735A (en) Dicing die-bonding film and process for producing semiconductor device
TWI521040B (en) Method of cutting off hot peeling adhesive tape and electronic parts
JP6768038B2 (en) Adhesive sheet
TW202233778A (en) adhesive sheet
JP7155210B2 (en) Adhesive sheet
TW202113002A (en) Adhesive tape
JP2021006634A (en) Adhesive sheet
JP6151679B2 (en) Re-peeling adhesive composition, adhesive sheet and tape
TWI815278B (en) adhesive sheet
TWI802118B (en) Adhesive sheet
TWI806256B (en) Adhesive sheet
TWI809659B (en) Double-sided adhesive sheet with backing
WO2023021773A1 (en) Pressure-sensitive adhesive sheet
TWI845858B (en) Adhesive Sheet
TW202317727A (en) Pressure-sensitive adhesive sheet
TW202338049A (en) adhesive sheet
TW202311480A (en) Pressure-sensitive adhesive sheet
TW202116943A (en) Adhesive tape