TWI730394B - 黏著片材 - Google Patents
黏著片材 Download PDFInfo
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- TWI730394B TWI730394B TW108131669A TW108131669A TWI730394B TW I730394 B TWI730394 B TW I730394B TW 108131669 A TW108131669 A TW 108131669A TW 108131669 A TW108131669 A TW 108131669A TW I730394 B TWI730394 B TW I730394B
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- Prior art keywords
- adhesive layer
- adhesive
- adhesive sheet
- substrate
- thickness
- Prior art date
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- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
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- 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
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Abstract
本發明提供一種黏著片材,其係於硬脆基板之背面研磨步驟中可用於硬脆基板之研削者,且低污染性、生產性、研削精度及剝離性均優異。
本發明之黏著片材係具備黏著劑層者,且該黏著劑層之厚度為1 μm~300 μm,該黏著劑層於25℃下之壓痕硬度H(Pa)與黏著劑層之厚度hA
(μm)滿足下述式(1)之關係。
logH≧1.9385×loghA
+4.2611 (1)
Description
本發明係關於一種黏著片材。
近年來,精度良好地製造白色LED(Light Emitting Diode,發光二極體)用基板、SOS(Silicon on Sapphire,矽藍寶石)等電子裝置或智慧型手機或時鐘之覆蓋玻璃等中所使用之藍寶石基板、作為功率半導體用基板而為人所期待之碳化矽基板、氮化鎵基板、氧化鎵基板、金剛石基板、可用作功率半導體用之散熱電路基板材料之氮化矽基板、氮化氧化鋁基板、玻璃或透鏡之石英晶體振子等中所使用之石英基板等堅硬且較脆之陶瓷基板(以下,總稱為硬脆基板)之需求不斷提高。作為製造此種基板之步驟之代表例,可列舉將基板(晶圓)之背面研削至所需之厚度之背面研磨步驟,於該步驟中,為了固定基板,使用蠟或黏著片材(背面研磨膠帶)作為固定材。其中,黏著片材與蠟相比,不易污染基板,又,就生產性之觀點而言亦可有利地使用。
另一方面,基板(硬脆基板)為高硬度,於對高硬度之基板(硬脆基板)進行研削之情形時,必須一面將以金剛石等為材質之固定研磨粒或游離研磨粒於高荷重下壓抵於被研削體(硬脆基板)一面使研磨機旋轉,將該被研削體薄化。此時,對固定材施加較高之垂直壓力,於先前之黏著片材中,有容易發生產生黏著劑層之變形、被研削體之振動等研削性之問題之傾向。又,謀求該等問題之消除而設計之固定材進行重剝離化,於背面研磨步驟後於自固定材剝離被研削體時,產生污染被研削體之問題。如此,於對硬脆基板進行研削時,於先前之固定材中不易同時實現研削性與剝離性。
[先前技術文獻]
[專利文獻]
專利文獻1:日本專利特開2011-151163號公報
[發明所欲解決之問題]
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,其係於硬脆基板之背面研磨步驟中可用於硬脆基板之研削者,且低污染性、生產性、研削精度及剝離性均優異。
[解決問題之技術手段]
本發明之黏著片材係具備黏著劑層者,且該黏著劑層之厚度為1 μm~300 μm,該黏著劑層於25℃下之壓痕硬度H(Pa)與黏著劑層之厚度hA
(μm)滿足下述式(1)之關係。
logH≧1.9385×loghA
+4.2611 (1)
於一實施形態中,將上述黏著片材之黏著面貼合於矽晶片之情形時之25℃之環境溫度下的剪切接著強度為1.0 MPa以上。
於一實施形態中,將上述黏著片材之黏著面貼合於SUS304BA時之80℃之環境溫度下之剝離黏著力為15 N/20 mm以下。
於一實施形態中,上述黏著劑層於25℃下之壓痕硬度H為10 MPa~1 GPa。
於一實施形態中,上述黏著劑層係包含含有基礎聚合物之黏著劑,且該基礎聚合物為熱塑性彈性體。
於一實施形態中,上述熱塑性彈性體為苯乙烯系彈性體或乙烯-乙酸乙烯酯系彈性體。
於一實施形態中,上述黏著劑進而包含黏著賦予樹脂。
於一實施形態中,上述黏著賦予樹脂之含量相對於上述基礎聚合物100重量份,為1重量份~350重量份。
於一實施形態中,進而具備配置於上述黏著劑層之至少單側之基材。
於一實施形態中,進而具備配置於上述黏著劑層之至少單側之另一黏著劑層。
於一實施形態中,上述基材於25℃下之拉伸彈性模數為1×107
Pa~1×1010
Pa。
於一實施形態中,上述黏著片材係用作半導體製造步驟中之基板加工時之暫時固定材。
根據本發明之另一態樣,提供一種基板之研削方法。該基板之研削方法包括如下步驟:於具備黏著劑層之黏著片材之該黏著劑層上載置基板,進行固定後,對該基板之與黏著劑層側相反之側之面進行研削;且該黏著劑層之厚度為1 μm~300 μm,該黏著劑層於25℃下之壓痕硬度H(Pa)與黏著劑層之厚度hA
(μm)滿足下述式(1)之關係。
根據本發明之進而另一態樣,提供一種基板之製造方法。該基板之製造方法包括如下之研削步驟:於具備黏著劑層之黏著片材之該黏著劑層上載置基板,於進行固定後,對該基板之與黏著劑層側相反之側之面進行研削;且該黏著劑層之厚度為1 μm~300 μm,該黏著劑層於25℃下之壓痕硬度H(Pa)與黏著劑層之厚度hA
(μm)滿足下述式(1)之關係。
[發明之效果]
根據本發明,可提供一種黏著片材,其係於硬脆基板之背面研磨步驟中可用於硬脆基板之研削者,且低污染性、生產性、研削精度及剝離性中之任一者均優異。
A. 黏著片材之概要
圖1(a)為本發明之一實施形態之黏著片材之概略剖視圖。黏著片材100具備黏著劑層10。本發明之黏著片材可僅由黏著劑層10構成,亦可除該黏著劑層以外,進而具備任意之適當之層。
圖1(b)為本發明之另一實施形態之黏著片材之概略剖視圖。黏著片材200具備黏著劑層10、及配置於黏著劑層10之至少單側之基材20。圖1(c)為本發明之又一實施形態之黏著片材之概略剖視圖。黏著片材300具備黏著劑層10、及配置於黏著劑層10之至少單側之另一黏著劑層30。可如圖示例般於黏著劑層10與另一黏著劑層30之間配置基材20,雖然未圖示,但亦可省略基材而由黏著劑層與另一黏著劑層構成黏著片材。又,雖然未圖示,但上述黏著片材可進而具備可對上述黏著片材賦予彈性之彈性層(下述E項)、可剝離地配置於黏著劑層上之隔片(下述F項)等作為黏著劑層以外之層。
於本發明之黏著片材中所具備之黏著劑層中,黏著劑層於25℃下之壓痕硬度H(Pa)與黏著劑層之厚度hA
(μm)滿足下述式(1)之關係。又,上述黏著劑層之厚度hA
為1 μm~300 μm。
logH≧1.9385×loghA
+4.2611 (1)
於本發明中,藉由以將厚度hA
設為1 μm~300 μm後,使壓痕硬度H與厚度hA
滿足上述關係之方式構成黏著劑層,可獲得對於背面研磨步驟中之研削時之負載(即,垂直方向上之負載及剪切方向上之負載),不易顯著地變形之黏著片材。又,滿足上述關係之黏著劑層於高溫下(例如80℃~120℃),在保持彈性變形之狀態下變軟,因此本發明之黏著片材於對基板進行研削後可表現出優異之剝離性。具有此種特性之本發明之黏著片材可適宜地用作半導體製造步驟中之基板加工時之暫時固定材,可尤佳地用作於對硬脆基板進行研削時之暫時固定材。更詳細而言,於對高硬度之硬脆基板進行研削時,必須一面於高荷重下壓抵於被研削體(藍寶石)一面使研磨機旋轉,結果如上所述,若使用對於研削時之負載不易變形之黏著片材,則可精度良好地對硬脆基板進行研削。又,本發明之黏著片材由於剝離性優異,故而於剝離時,黏著劑層成分不易殘留於被接著體,就該方面而言,亦作為硬脆基板之暫時固定材有用。於一實施形態中,可使用藍寶石晶圓作為硬脆基板。
黏著劑層於25℃下之壓痕硬度H(Pa)與黏著劑層之厚度hA
(μm)較佳為進而滿足下述式(2)之關係,進而較佳為滿足下述式(2)'之關係。
1.9385×loghA
+9≧logH (2)
1.9385×loghA
+7≧logH (2)'
若壓痕硬度H與厚度hA
滿足上述關係,則可獲得剝離性更優異之黏著片材。
將本發明之黏著片材之黏著面貼合於矽晶片之情形時之於25℃之環境溫度下之剪切接著強度較佳為1.0 MPa以上,更佳為1.5 MPa以上,進而較佳為2 MPa以上,尤佳為2.3 MPa以上,最佳為3 MPa以上。25℃環境溫度下之上述剪切接著強度之上限例如為8 MPa。於本說明書中,剪切接著強度可藉由如下方法進行測定:將黏著劑層表面作為貼合面,利用熱壓機於100℃、0.1 MPa之貼合條件下熱壓接1分鐘而將矽晶片固定,使用Nordson公司製造之dage4000,於距貼附面之高度50 μm位置上安裝測定端子,以剪切速率500 μm/sec.在與晶片水平之方向上施加外力,藉此獲得荷重-位移曲線,自所獲得之荷重-位移曲線讀取最大破壞荷重。於成為對象之樣品為單面膠帶之情形時,利用日東電工公司製造之雙面膠帶NO.585將基材之背面(與黏著劑層相反之側之面)貼附於特定之基座並進行固定而進行上述測定。黏著片材之剪切接著強度可根據黏著劑層中所含之黏著劑之種類、構成黏著劑之基礎聚合物之結構、添加至黏著劑中之添加劑之種類、量等而進行調整。
將本發明之黏著片材之黏著面貼合於SUS304BA時之80℃之環境溫度下之剝離黏著力較佳為15 N/20 mm以下,更佳為12 N/20 mm以下,進而較佳為10 N/20 mm以下,尤佳為8 N/20 mm以下。若為此種範圍,則可製成藉由加熱可剝離之黏著片材。藉由形成具有上述範圍之剝離黏著力之黏著劑層,可製成剝離性優異,不易污染硬脆基板(例如藍寶石晶圓),且生產性優異之黏著片材。於本說明書中,所謂剝離黏著力係指於利用手壓輥將黏著片材(20 mm寬)之黏著面(黏著劑層面)貼附於SUS304BA而形成積層體後,利用預先將該積層體預熱至80℃之熱壓機,於0.3 MPa之壓力下進行壓接1分鐘而製作樣品,對該樣品,於剝離角度180°、剝離速度300 mm/min之條件下將黏著片材自SUS304BA剝離而測定之黏著力。於該黏著片材為不具有基材之黏著片材之情形時,可於與黏著劑層面相反之側之面貼附日東電工股份有限公司製造之膠帶No.315後,製作上述樣品,並測定剝離黏著力。黏著片材之剝離黏著力可根據黏著劑層中所含之黏著劑之種類、構成黏著劑之基礎聚合物之構造、添加至黏著劑中之添加劑之種類、量等而進行調整。
本發明之黏著片材可於貼合於被加工物之狀態下,供於背面研磨步驟、樹脂密封步驟、蒸鍍、濺鍍等基板(晶圓)背面(研削面)之處理步驟、切晶步驟、斷裂步驟之單一步驟或其組合步驟。
本發明之黏著片材之厚度較佳為10 μm~500 μm,更佳為20 μm~300 μm。
根據本發明之另一態樣,提供一種使用上述黏著片材之基板之研削方法。該方法例如包括如下步驟:於黏著片材之上述黏著劑層上載置基板,進行固定後,對該基板之與黏著劑層側相反之側之面進行研削。基板之研削可採用任意之適當之方法。該研削例如可為了將基板設為所需之厚度而進行。於一實施形態中,作為基板,可使用圓形或定向平面形狀之晶圓。又,作為上述基板,例如可使用藍寶石基板(藍寶石晶圓)等硬脆基板(晶圓)。
根據本發明之進而另一態樣,提供一種使用上述黏著片材之晶片之製造方法。該製造方法例如包括如下之研削步驟:於黏著片材之上述黏著劑層上載置基板,進行固定後,對該基板之與黏著劑層側相反之側之面進行研削。作為基板,例如可使用圓形或定向平面形狀之晶圓。又,上述製造方法除研削步驟以外,可包括任意之適當之步驟。例如可包括切斷基板(晶圓)之切晶步驟、於切晶後分割被切斷體而進行晶片化之斷裂步驟、蒸鍍、濺鍍等晶片背面(研削面)之處理步驟、對晶片進行密封之密封步驟等。作為上述晶片,例如可列舉將藍寶石晶圓等硬脆晶圓作為支持體之LED晶片等。
B. 黏著劑層
上述黏著劑層包含用以賦予黏著性之黏著劑。
上述黏著劑層於25℃下之壓痕硬度H較佳為10 MPa~1 GPa,更佳為12 MPa~0.8 GPa,進而較佳為15 MPa~0.4 GPa。若為此種範圍,則可獲得能夠以優異之研削精度進行背面研磨之黏著片材。若為此種範圍,則可獲得能夠以優異之研削精度進行硬脆基板(例如藍寶石晶圓)之背面研磨之黏著片材。壓痕硬度H可藉由如下方法而獲得:利用測定裝置附帶之軟體(triboscan),對藉由將金剛石製造之Berkovich型(三稜錐型)探針垂直地抵壓於黏著劑層之表面而獲得之位移-荷重遲滯曲線進行數值處理。於本說明書中,所謂壓痕硬度H,係使用奈米壓痕儀(Hysitron Inc公司製造之Triboindenter TI-950),藉由特定溫度(25℃)下之單一壓入法,於壓入速度約500 nm/sec、壓入深度約3000 nm之測定條件下測定之壓痕硬度H。再者,黏著劑層之壓痕硬度H可根據黏著劑層中所含之黏著劑之種類、構成黏著劑之基礎聚合物之構造、添加至黏著劑中之添加劑之種類、量等而進行調整。
上述黏著劑層之厚度較佳為1 μm~300 μm,更佳為1 μm~250 μm,進而較佳為1 μm~100 μm,尤佳為1 μm~50 μm。
B-1. 黏著劑
作為構成上述黏著劑層之黏著劑,只要可獲得本發明之效果,則可使用任意之適當之黏著劑。作為上述黏著劑,例如可列舉包含熱塑性彈性體、丙烯酸系樹脂、聚矽氧系樹脂、乙烯基烷基醚系樹脂、聚酯系樹脂、聚醯胺系樹脂、胺基甲酸酯系樹脂、氟化樹脂等作為基礎聚合物(黏著性樹脂)之黏著劑。較佳為上述黏著劑包含熱塑性樹脂作為基礎聚合物。若使用熱塑性樹脂,則可容易地獲得具有滿足上述關係式(1)之黏著劑層,且藉由加熱可表現出優異之剝離性之黏著片材。較佳為使用包含丙烯酸系樹脂或熱塑性彈性體之黏著劑作為基礎聚合物,可更佳地使用熱塑性彈性體。作為熱塑性彈性體,可較佳地使用苯乙烯系彈性體或乙烯-乙酸乙烯酯系彈性體,可更佳地使用苯乙烯系彈性體。例如,若使用苯乙烯系彈性體,則藉由苯乙烯單元比率之調整,可容易地控制上述接著性及壓痕硬度H。
作為苯乙烯系彈性體,可列舉:苯乙烯-丁二烯共聚物(SB)、苯乙烯-異戊二烯共聚物(SI)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-異丁烯-苯乙烯共聚物(SIBS)、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-乙烯-丙烯嵌段共聚物(SEP)、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)、該等之改性體等。其中,較佳為SEBS、SBS、SIS、SIBS。該等共聚物較佳為嵌段共聚物。
上述苯乙烯系彈性體中,關於源自苯乙烯之結構單元之含有比率,相對於苯乙烯系彈性體100重量份,較佳為10重量份~75重量份,更佳為20重量份~70重量份,進而較佳為20重量份~50重量份。若為此種範圍,則可獲得能夠形成具有適度之彈性,且黏著性優異之黏著劑層,以優異之研削精度進行背面研磨之黏著片材。
於一實施形態中,作為上述苯乙烯系彈性體,可使用經酸改性之苯乙烯系彈性體(較佳為經酸改性之SEBS、SBS、SIS或SIBS)。作為上述酸改性中所使用之酸,例如可列舉順丁烯二酸、順丁烯二酸酐等,較佳為順丁烯二酸改性。藉由使用經酸改性之苯乙烯系彈性體,藉由併用交聯劑(例如環氧系交聯劑),可調整分子量、或形成交聯結構,藉此黏著劑層可構成為於高溫區域中仍保持彈性變形而進行軟化,可控制於高溫下之剝離力。經酸改性之苯乙烯系彈性體之酸值較佳為5 mg(CH3
ONa)/g以上,更佳為7 mg(CH3
ONa)/g以上,進而較佳為7 mg(CH3
ONa)/g~25(CH3
ONa)/g。再者,此處之酸值係指中和基礎聚合物1 g之甲醇鈉(CH3
ONa)之重量(mg)。又,基礎聚合物之酸值可依據JIS K0070:1992而進行測定。
上述乙烯-乙酸乙烯酯系彈性體中,關於源自乙酸乙烯酯之結構單元之含有比率,相對於乙烯-乙酸乙烯酯系彈性體100重量份,較佳為5重量份~50重量份,更佳為10重量份~45重量份。若為此種範圍,則可獲得能夠形成具有適度之彈性,且黏著性優異之黏著劑層,以優異之研削精度進行背面研磨之黏著片材。
作為上述丙烯酸系樹脂,例如可使用將(甲基)丙烯酸烷基酯之1種或2種以上作為單體成分而構成之丙烯酸系樹脂。作為(甲基)丙烯酸烷基酯之具體例,可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(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,可較佳地使用具有碳數為4~18之直鏈狀或者支鏈狀之烷基之(甲基)丙烯酸烷基酯。
上述丙烯酸系聚合物為了凝聚力、耐熱性、交聯性等之改質,視需要亦可含有與可與上述(甲基)丙烯酸烷基酯共聚之其他單體成分對應之單元。作為此種單體成分,例如可列舉:丙烯酸、甲基丙烯酸、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、丁烯酸等含羧基之單體;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)丙烯酸羥丙酯、(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基己酯、(甲基)丙烯酸羥基辛酯、(甲基)丙烯酸羥基癸酯、(甲基)丙烯酸羥基月桂酯、甲基丙烯酸(4-羥基甲基環己基)甲酯等含羥基之單體;苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基之單體;(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等(甲基)丙烯酸胺基烷基酯系單體;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體;N-環己基順丁烯二醯亞胺、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-甲基醯亞胺、N-乙基醯亞胺、N-丁基醯亞胺、N-辛基醯亞胺、N-2-乙基己基醯亞胺、N-環己基醯亞胺、N-月桂基醯亞胺等醯亞胺系單體;N-(甲基)丙烯醯氧基亞甲基丁二醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基丁二醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基丁二醯亞胺等丁二醯亞胺系單體;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、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌𠯤、乙烯基吡𠯤、乙烯基吡咯、乙烯基咪唑、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基系單體;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之丙烯酸系單體;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酯、甲氧基聚丙二醇(甲基)丙烯酸酯等二醇系丙烯酸酯單體;(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯等等具有雜環、鹵素原子、矽原子之丙烯酸酯系單體;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、丙烯酸胺基甲酸酯等多官能單體;異戊二烯、丁二烯、異丁烯等烯烴系單體;乙烯醚等乙烯醚系單體等。該等單體成分可單獨使用、或組合兩種以上而使用。
上述黏著劑視需要可包含任意之適當之添加劑。作為該添加劑,例如可列舉:黏著賦予樹脂、塑化劑、顏料、染料、填充劑、抗老化劑、導電材、防靜電劑、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、交聯劑等。
於一實施形態中,上述黏著劑包含黏著賦予樹脂。尤其是於黏著劑包含苯乙烯系彈性體之情形時,較佳為併用該彈性體與黏著賦予樹脂。藉由併用黏著賦予樹脂,可形成黏著性優異之黏著劑層。
作為上述黏著賦予樹脂,只要可獲得本發明之效果,則可使用任意之適當之黏著賦予樹脂。作為黏著賦予樹脂之具體例,可列舉:松脂系黏著賦予樹脂(例如未改性松脂、改性松脂、松脂酚系樹脂、松脂酯系樹脂等)、萜烯系黏著賦予樹脂(例如萜烯系樹脂、萜酚系樹脂、苯乙烯改性萜烯系樹脂、芳香族改性萜烯系樹脂、氫化萜烯系樹脂)、烴系黏著賦予樹脂(例如脂肪族系烴樹脂、脂肪族系環狀烴樹脂、脂環族系烴樹脂(例如苯乙烯系樹脂、二甲苯系樹脂等)、脂肪族/芳香族系石油樹脂、脂肪族/脂環族系石油樹脂、氫化烴樹脂、薰草咔系樹脂、薰草咔茚系樹脂等)、酚系黏著賦予樹脂(例如烷基酚系樹脂、二甲苯甲醛系樹脂、可溶酚醛、酚醛清漆等)、酮系黏著賦予樹脂、聚醯胺系黏著賦予樹脂、環氧系黏著賦予樹脂、彈性體系黏著賦予樹脂等。其中,較佳為萜烯系黏著賦予樹脂、松脂系黏著賦予樹脂或烴系黏著賦予樹脂(較佳為脂環族系飽和烴樹脂)。黏著賦予樹脂可單獨使用、或組合兩種以上而使用。
關於上述黏著賦予樹脂之含量,相對於基礎聚合物100重量份,較佳為0重量份~350重量份,更佳為1重量份~350重量份,進而較佳為1重量份~300重量份,尤佳為20重量份~250重量份。若為此種範圍,則可形成黏著性優異之黏著劑層。於黏著賦予樹脂之含量過多之情形時,有黏著劑層變脆之虞。
於一實施形態中,上述黏著劑包含界面活性劑。若使用包含界面活性劑之黏著劑,則於黏著劑層中,藉由由加熱所引起之界面活性劑之偏析形成輕剝離層,可獲得剝離性優異之黏著片材。
作為上述界面活性劑,只要可獲得本發明之效果,則可使用任意之適當之界面活性劑。作為上述界面活性劑,例如可列舉:非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑或兩離子性界面活性劑等。其中,較佳為使用非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑,更佳為使用非離子性界面活性劑、或陽離子性界面活性劑。上述界面活性劑可單獨使用或組合兩種以上而使用。
作為上述非離子性界面活性劑,可列舉:聚氧乙烯月桂醚、聚氧乙烯硬脂醚等聚氧乙烯烷基醚;聚氧乙烯辛基苯醚、聚氧乙烯壬基苯醚等聚氧乙烯烷基苯醚;山梨醇酐單月桂酸酯、山梨醇酐單硬脂酸酯、聚氧乙烯山梨醇酐單月桂酸酯等山梨醇酐脂肪酸酯;聚氧乙烯甘油醚脂肪酸酯;聚氧乙烯-聚氧丙烯嵌段共聚物;辛酸乙酯、癸酸乙酯、月桂酸甲酯、月桂酸丁酯、肉豆蔻酸甲酯、肉豆蔻酸異丙酯、棕櫚酸甲酯、棕櫚酸異丙酯、硬脂酸甲酯、硬脂酸丁酯、山萮酸甲酯、月桂酸丁酯、硬脂酸丁酯、肉豆蔻酸異丙酯、棕櫚酸異丙酯等飽和脂肪酸酯;月桂醯胺、棕櫚醯胺、硬脂醯胺、山萮醯胺等脂肪醯胺等。
於一實施形態中,使用磷酸酯化合物作為界面活性劑(非離子性界面活性劑)。作為磷酸酯化合物,例如可列舉:異丙基磷酸及月桂基磷酸等烷基磷酸;聚氧伸烷基烷基醚磷酸;該等之鹽等。其中,較佳為聚氧伸烷基烷基醚磷酸。
作為磷酸酯系化合物為鹽之情形時之構成鹽之抗衡離子,例如可列舉:鹼金屬、銨、有機銨之陽離子等。作為鹼金屬,例如可列舉:鈉、鉀、鋰等。作為有機銨,例如可列舉:甲基胺、乙基胺等烷基胺;單乙醇胺、二乙醇胺、三乙醇胺等烷醇胺等。
例如,作為聚氧伸烷基烷基醚磷酸,例如可列舉:聚氧乙烯辛醚磷酸、聚氧乙烯癸醚磷酸、聚氧乙烯月桂醚磷酸、聚氧乙烯十三烷基醚磷酸、聚氧乙烯肉豆蔻醚磷酸、聚氧乙烯十五烷基醚磷酸、及聚氧乙烯硬脂醚磷酸等。於聚氧伸烷基烷基醚磷酸為鹽之情形時,作為構成鹽之抗衡離子,例如較佳地選擇鈉、鉀、鋇、三乙醇胺等。
聚氧伸烷基烷基醚磷酸之環氧乙烷之加成莫耳數較佳為1~20,更佳為1~10,進而較佳為1~6,尤佳為1~4。
作為上述陰離子性界面活性劑,可列舉:月桂基硫酸鹽、十八烷基硫酸鹽等烷基硫酸鹽;脂肪酸鹽;壬基苯磺酸鹽、十二烷基苯磺酸鹽等烷基苯磺酸鹽;十二烷基萘磺酸鹽等萘磺酸鹽;十二烷基二苯醚二磺酸鹽等烷基二苯醚二磺酸鹽;聚氧乙烯十八烷基醚硫酸鹽、聚氧乙烯月桂醚硫酸鹽等聚氧乙烯烷基醚硫酸鹽;聚氧乙烯月桂基苯醚硫酸鹽等聚氧乙烯烷基苯醚硫酸鹽;聚氧乙烯苯乙烯化苯醚硫酸鹽;月桂基磺基琥珀酸鹽、聚氧乙烯月桂基磺基琥珀酸鹽、二辛基磺基琥珀酸鹽(二辛基磺基琥珀酸鈉)等磺基琥珀酸鹽;聚氧乙烯烷基醚磷酸鹽;聚氧乙烯烷基醚乙酸鹽等。於陰離子性界面活性劑形成鹽之情形時,該鹽例如可為鈉鹽、鉀鹽、鈣鹽、鎂鹽等金屬鹽(較佳為一價金屬之鹽)、銨鹽、胺鹽等。
作為上述陽離子性界面活性劑,可列舉:氯化烷基三甲基銨、氯化硬脂基三甲基銨、氯化月桂基三甲基銨、氯化鯨蠟基三甲基銨、氯化牛油烷基三甲基銨、氯化山萮基三甲基銨、溴化硬脂基三甲基銨、溴化山萮基三甲基銨、氯化二硬脂基二甲基銨、氯化二椰油醯基二甲基銨、氯化二辛基二甲基銨、氯化二(POE)油基甲基銨(2EO)、氯化苄烷銨、氯化烷基苄烷銨、氯化烷基二甲基苄烷銨、苄索氯銨、氯化硬脂基二甲基苄基銨、羊毛脂衍生四級銨鹽、硬脂酸二乙酯胺基乙基醯胺、硬脂酸二甲酯胺基丙基醯胺、氯化山萮醯胺丙基二甲基羥丙基銨、氯化硬脂醯基羥乙胺基甲醯基甲基吡啶鎓(Stearoyl colamino formyl methyl pyridinium chloride)、氯化鯨蠟基吡啶鎓、氯化妥爾油烷基苄基羥基乙基咪唑啉鎓、苄基銨鹽等。
作為上述界面活性劑,可使用市售品。作為市售品之界面活性劑,例如可列舉:東邦化學工業公司製造之商品名「Phosphanol RL210」等磷酸酯系界面活性劑;花王公司製造之商品名「EXEPARL IPP」、東京化成工業公司製造之棕櫚酸甲酯等脂肪酸酯系界面活性劑;東京化成工業公司製造之硬脂醯胺、月桂醯胺等脂肪醯胺系界面活性劑;東邦化學工業公司製造之商品名「Catinal MAPS」等脂肪酸胺基烷基醯胺系界面活性劑;東邦化學工業公司製造之商品名「Catinal STC-70ET」等氯化三甲基銨系界面活性劑;三洋化成公司製造之商品名「Cation S」等氯化二甲基苄基銨系界面活性劑;三洋化成工業公司製造之商品名「DSA」、「PDSA-DA」等琥珀酸酐系界面活性劑;三洋化成工業公司製造之商品名「Sansepara 100」等磺基琥珀酸鈉系界面活性劑等。
於一實施形態中,上述界面活性劑具有烷基作為疏水基。較佳為使用具有碳數為5~20(更佳為8~18、進而較佳為10~18)之直鏈狀或支鏈狀之(較佳為直鏈狀之)烷基之界面活性劑。若使用此種界面活性劑,則可獲得不損及常溫下之黏著性,於高溫下可發揮出優異之剝離性之黏著片材。
關於上述界面活性劑之含量,相對於基礎聚合物100重量份,較佳為0.001重量份~15重量份,更佳為0.01重量份~10重量份,進而較佳為0.1重量份~8重量份,尤佳為1重量份~5重量份。若為此種範圍,則可獲得於高溫下亦可發揮出優異之剝離性之黏著片材。
上述界面活性劑之分子量較佳為800以下,更佳為600以下,進而較佳為500以下。界面活性劑之分子量之下限例如為150。若為此種範圍,則可獲得於高溫下亦可發揮出優異之剝離性之黏著片材。
於一實施形態中,上述黏著劑包含交聯劑。若包含交聯劑,則可調整黏著劑層之凝聚力,可獲得具有常溫下之優異之接著性,並且高溫下之剝離性優異之黏著片材。
作為上述交聯劑,只要可獲得本發明之效果,則可使用任意之適當之交聯劑。作為上述交聯劑,例如,除環氧系交聯劑、異氰酸酯系交聯劑、三聚氰胺系交聯劑、過氧化物系交聯劑以外,可列舉: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。其中,較佳為環氧系交聯劑。
作為上述環氧系交聯劑,例如可列舉:N,N,N',N'-四縮水甘油基-間苯二甲胺、二縮水甘油基苯胺、1,3-雙(N,N-縮水甘油基胺基甲基)環己烷(三菱瓦斯化學公司製造,商品名「Tetrad C」)、1,6-己二醇二縮水甘油醚(共榮社化學公司製造,商品名「Epolight 1600」)、新戊二醇二縮水甘油醚(共榮社化學公司製造,商品名「Epolight 1500NP」)、乙二醇二縮水甘油醚(共榮社化學公司製造,商品名「Epolight 40E」)、丙二醇二縮水甘油醚(共榮社化學公司製造,商品名「Epolight 70P」)、聚乙二醇二縮水甘油醚(日本油脂公司製造,商品名「EPIOL E-400」)、聚丙二醇二縮水甘油醚(日本油脂公司製造,商品名「EPIOL P-200」)、山梨醇聚縮水甘油醚(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、異氰尿酸三縮水甘油基三(2-羥基乙基)酯、間苯二酚二縮水甘油醚、雙酚-S-二縮水甘油醚、分子內具有2個以上環氧基之環氧系樹脂等。環氧系交聯劑之含量可根據所需之黏著力、黏著劑層之彈性等,設定為任意之適當之量,相對於基礎聚合物100重量份,代表性地為0.01重量份~10重量份,更佳為0.03重量份~5重量份。
又,上述黏著劑層亦可包含任意之適當之發泡劑。發泡劑為可藉由加熱而發泡之添加劑。作為發泡劑,只要可獲得本發明之效果,則可使用任意之適當之發泡劑。就代表性而言,作為上述發泡劑,可使用熱膨脹性微球。具備包含熱膨脹性微球之黏著劑層之黏著片材藉由進行加熱,該熱膨脹性微球進行膨脹或發泡而於黏著面產生凹凸,其結果為,黏著力降低或消失。此種黏著片材可藉由進行加熱而容易地剝離。
上述發泡劑之發泡起始溫度較佳為90℃以上,較佳為90℃~220℃,更佳為100℃~190℃。於本說明書中,發泡起始溫度例如相當於黏著劑層之黏著力相對於該黏著劑層之常態黏著力(23℃下之對於PET(Polyethylene Terephthalate,聚對苯二甲酸乙二酯)膜之黏著力)成為10%以下之最低溫度。此時之黏著力係指藉由依據JIS Z 0237:2000之方法(貼合條件:2 kg輥往返一次、剝離速度:300 mm/min、剝離角度180°)所測得之黏著力。又,發泡起始溫度(及加熱後之測定樣品)下之黏著力係於使測定樣品恢復至常溫(23℃)後進行測定。再者,於發泡劑為熱膨脹性微球之情形時,該熱膨脹性微球開始膨脹之溫度相當於發泡起始溫度。
作為上述熱膨脹性微球,可使用任意之適當之熱膨脹性微球。作為上述熱膨脹性微球,例如可使用將藉由加熱容易膨脹之物質內包於具有彈性之殼內而成之微球。此種熱膨脹性微球可藉由任意之適當之方法、例如凝聚法、界面聚合法等進行製造。
作為藉由加熱容易膨脹之物質,例如可列舉:丙烷、丙烯、丁烯、正丁烷、異丁烷、異戊烷、新戊烷、正戊烷、正己烷、異己烷、庚烷、辛烷、石油醚、甲烷之鹵化物、四烷基矽烷等低沸點液體;藉由熱解而進行氣化之偶氮二甲醯胺等。
作為構成上述殼之物質,例如可列舉: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、丙烯酸β-羧基乙酯等(甲基)丙烯酸酯;苯乙烯、α-甲基苯乙烯、氯苯乙烯等苯乙烯單體;丙烯醯胺、取代丙烯醯胺、甲基丙烯醯胺、取代甲基丙烯醯胺等醯胺單體等之聚合物。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,例如可列舉: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。
上述熱膨脹性微球可使用市售品。作為市售品之熱膨脹性微球之具體例,可列舉:松本油脂製藥公司製造之商品名「Matsumoto Microsphere」(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)、JAPAN FILLITE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。
於25℃之環境溫度下,使上述熱膨脹性微球發泡前之該熱膨脹性微球之平均粒徑較佳為50 μm以下,更佳為1 μm~50 μm,進而較佳為3 μm~35 μm,尤佳為5 μm~35 μm。藉由使用平均粒徑為50 μm以下之熱膨脹性微球,可獲得於該熱膨脹性微球之發泡前(即,黏著劑層需要黏著性之狀況),不易於黏著劑層表面產生該熱膨脹性微球之影響,對被接著體之密接性較高,具有優異之黏著性之黏著片材。於上述範圍內,熱膨脹性微球之平均粒徑越大,則越於加熱時進一步膨脹,故而較佳,若使用平均粒徑為上述範圍之熱膨脹性微球,則可獲得剝離性優異之黏著片材。上述熱膨脹性微球之平均粒徑例如可藉由使該熱膨脹性微球聚合時之條件(例如聚合時之攪拌葉轉數、聚合溫度)來進行控制。又,於使用市售之熱膨脹性微球之情形時,可藉由篩網處理、過濾器處理、離心分離處理等分級處理而加以控制。再者,於本說明書中,平均粒徑亦可藉由如下方式進行測定:使用光學顯微鏡或電子顯微鏡,對所使用之熱膨脹性微球、或自加熱前之黏著劑層取出之熱膨脹性微球進行觀察。又,平均粒徑可藉由雷射散射法中之粒度分佈測定法進行測定。更具體而言,平均粒徑可於使所使用之熱膨脹性微球分散於特定之溶劑(例如水)中後,使用粒度分佈測定裝置(例如島津製作所製造之商品名「SALD-2000J」)進行測定。
上述熱膨脹性微球較佳為具有至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倍以上為止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,可藉由加熱處理而高效率地降低黏著力。
上述黏著劑層中之熱膨脹性微球之含量可根據所需之黏著力之降低性等而適當加以設定。關於熱膨脹性微球之含量,相對於上述基礎聚合物100重量份,較佳為20重量份~210重量份,更佳為30重量份~200重量份,進而較佳為50重量份~150重量份。若為此種範圍,則可獲得於背面研磨時顯示出良好之接著性,且於加熱時可容易地剝離被接著體之黏著片材。
關於上述黏著劑層中之熱膨脹性微球之含有比率,相對於黏著劑層之重量,較佳為5重量%~80重量%,更佳為10重量%~70重量%,進而較佳為15重量%~65重量%。熱膨脹性微球之含有比率可根據利用X射線CT(Computed Tomography,電腦斷層攝影術)分析或SEM(Scanning Electron Microscope,掃描式電子顯微鏡)分析等獲得之熱膨脹性微球之體積填充率(發泡起始溫度以下(例如23℃)下之體積填充率)、熱膨脹性微球之比重及熱膨脹性微球以外之區域之比重而算出。於一實施形態中,可藉由將熱膨脹性微球之比重概算為1,且將熱膨脹性微球以外之區域之比重概算為1而算出,該情形時之熱膨脹性微球之含有比率為上述範圍。
關於上述黏著劑層中之熱膨脹性微球之含有比率,相對於黏著劑層之體積,較佳為5體積%~80體積%,更佳為10體積%~70體積%,進而較佳為15體積%~65體積%。體積基準之含有比率相當於上述體積填充率,如上所述,可藉由X射線CT分析或SEM分析等而進行測定。更具體而言,體積填充率可藉由以下之方法而進行測定。
<體積填充率測定方法>
i)於使加熱前之黏著片材之黏著劑層朝上之狀態下將試樣固定於保持器,利用X射線CT對0~180°對1601片之連續透過像進行拍攝。X射線CT係使用ZEISS、Xradia 520 Versa,於管電壓40 kV、管電流73 μA、像素尺寸0.3 μm/Pixel下進行測定。
ii)基於所獲得之全透過像進行重建而製作斷層像,使用分析軟體ImageJ.而製作三維重建像(TIF堆疊像)與重建剖面像(3面圖)。
iii)對所獲得之三維重建像(TIF堆疊像)實施圖像處理,而進行熱膨脹性微球之識別。根據識別結果,算出厚度方向之體積填充率、各發泡體之體積、及當量球徑。
再者,各試樣之黏著劑層厚度係藉由SEM剖面觀察進行測定,填充率係將除氣泡部分以外之值設為總體積而算出。
作為上述發泡劑,可使用無機系發泡劑或有機系發泡劑。作為無機系發泡劑,例如可列舉:碳酸銨、碳酸氫銨、碳酸氫鈉、亞硝酸銨、硼氫化鈉、各種疊氮類等。又,作為有機系發泡劑,例如可列舉:三氯單氟甲烷、二氯單氟甲烷等鹽氟化烷烴系化合物;偶氮二異丁腈、偶氮二甲醯胺、偶氮二羧酸鋇等偶氮系化合物;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1,2-二苯乙烯磺醯胺基脲、4,4'-氧基雙(苯磺醯胺基脲)等胺基脲系化合物;5-嗎啉基-1,2,3,4-噻三唑等三唑系化合物;N,N'-二亞硝基五亞甲基四胺、N,N'-二甲基-N,N'-二亞硝基對苯二甲醯胺等N-亞硝基系化合物等。
C. 基材
作為上述基材,例如可列舉:樹脂片材、不織布、紙、金屬箔、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,例如可列舉:聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)、聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物(EVA)、聚醯胺(尼龍)、全芳香族聚醯胺(芳族聚醯胺)、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,可列舉:包含馬尼拉麻之不織布等利用具有耐熱性之天然纖維之不織布;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,可列舉:銅箔、不鏽鋼箔、鋁箔等。作為紙,可列舉日本紙、牛皮紙等。上述基材可為單層,亦可為多層。於上述基材為多層之情形時,各層之構成可相同亦可不同。
上述基材之厚度可根據所需之強度或柔軟性、以及使用目的等,設定為任意之適當之厚度。基材之厚度較佳為1000 μm以下,更佳為1 μm~1000 μm,進而較佳為1 μm~500 μm,尤佳為3 μm~300 μm,最佳為5 μm~250 μm。
上述基材於25℃下之拉伸彈性模數為1×107
Pa~1×1010
Pa,更佳為5×107
Pa~5×109
Pa。若為此種範圍,則可獲得能夠精度良好地對硬脆基板(例如藍寶石晶圓)進行研削之黏著片材。
上述基材可實施表面處理。作為表面處理,例如可列舉:電暈處理、鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、離子化輻射處理、利用底塗劑進行之塗佈處理等。
作為上述有機塗佈材料,例如可列舉「塑膠硬塗材料II(CMC出版、(2004))」中所記載之材料。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、塗佈較簡便,且於工業上可選擇多種者,可廉價地獲取。該胺基甲酸酯系聚合物例如為包含異氰酸酯單體與含醇性羥基之單體(例如含羥基之丙烯基化合物或含羥基之酯化合物)之反應混合物的聚合物。有機塗佈材料可包含聚胺等鏈延長劑、抗老化劑、氧化穩定劑等作為任意之添加劑。有機塗層之厚度並無特別限定,例如較適宜為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。
D. 另一黏著劑層
作為上述另一黏著劑層,可形成任意之適當之黏著劑層。作為形成另一黏著劑層之黏著劑,例如可列舉:橡膠系黏著劑、丙烯酸系黏著劑、乙烯基烷基醚系黏著劑、聚矽氧系黏著劑、聚酯系黏著劑、聚醯胺系黏著劑、胺基甲酸酯系黏著劑、氟系黏著劑、苯乙烯-二烯嵌段共聚物系黏著劑等。於黏著劑中,例如可調配塑化劑、填充劑、界面活性劑、抗老化劑、黏著性賦予劑等公知或慣用之添加劑。
另一黏著劑層之厚度較佳為300 μm以下,更佳為1 μm~300 μm,進而較佳為5 μm~100 μm。
E. 彈性層
本發明之黏著片材可進而具備彈性層。彈性層可配置於黏著劑層之單面。於黏著片材具備基材之情形時,彈性層可配置於黏著劑層與基材之間。藉由具備彈性層,對於被接著體之追隨性提高。
上述彈性層包含基礎聚合物,作為該基礎聚合物,可使用作為構成上述黏著劑層之基礎聚合物所例示之聚合物。於一實施形態中,上述彈性層可包含天然橡膠、合成橡膠、合成樹脂等。作為該合成橡膠及合成樹脂,可列舉:腈系、二烯系、丙烯酸系之合成橡膠;聚烯烴系、聚酯系等熱塑性彈性體;乙烯-乙酸乙烯酯共聚物;聚胺基甲酸酯;聚丁二烯;軟質聚氯乙烯等。構成上述彈性層之基礎聚合物可與形成上述黏著劑層之基礎聚合物相同亦可不同。上述彈性層亦可為由上述基礎聚合物形成之發泡膜。該發泡膜可藉由任意之適當之方法而獲得。再者,彈性層與黏著劑層可基於基礎聚合物之不同而加以區別。
上述彈性層視需要可包含任意之適當之添加劑。作為該添加劑,例如可列舉:交聯劑、硫化劑、黏著賦予樹脂、塑化劑、柔軟劑、填充劑、抗老化劑等。於使用聚氯乙烯等硬質樹脂作為基礎聚合物之情形時,較佳為併用塑化劑及/或柔軟劑而形成具有所需之彈性之彈性層。
上述彈性層之厚度較佳為3 μm~200 μm,更佳為5 μm~100 μm。若為此種範圍,則可充分地發揮出彈性層之上述功能。
F. 隔片
本發明之黏著片材視需要可進而具備隔片。該隔片之至少一面成為剝離面,可為了保護上述黏著劑層而設置。隔片可包含任意之適當之材料。
G. 黏著片材之製造方法
本發明之黏著片材可藉由任意之適當方法進行製造。本發明之黏著片材例如可列舉:於基材(於獲得不含基材之黏著片材之情形時,為任意之適當之基體)上直接塗敷包含黏著劑之組合物之方法;或將於任意之適當之基體上塗敷包含黏著劑之組合物所形成之塗敷層轉印至基材之方法等。包含黏著劑之組合物可包含任意之適當之溶劑。
於黏著劑層具有上述彈性層之情形時,彈性層例如可於基材上或黏著劑層上塗敷用以形成彈性層之組合物而形成。
作為上述各組合物之塗敷方法,可採用任意之適當之塗敷方法。例如可於塗佈後進行乾燥而形成各層。作為塗佈方法,例如可列舉使用多層塗佈機、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,例如可列舉自然乾燥、加熱乾燥等。進行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而設定為任意之適當之溫度。
[實施例]
以下,藉由實施例具體地說明本發明,但本發明並不受該等實施例之限定。實施例中之評價方法係如下所述。再者,於下述評價中,使用已剝離隔片之黏著片材。又,於實施例中,只要未特別記載,則「份」及「%」為重量基準。
<評價方法>
於下述評價方法中,黏著劑層(及另一黏著劑層)之貼合係於剝離積層於貼合面之隔片後進行。
(1)剪切接著強度
將與黏著劑層相反之側之面貼附於特定之基座(例如20 mm×20 mm矽晶片)而對實施例及比較例中所獲得之黏著片材(尺寸:20 mm×20 mm)進行固定,於該黏著片材之黏著劑層表面配置5 mm×5 mm矽晶片,利用熱壓機於100℃、0.1 MPa之貼合條件下,對該矽晶片進行熱壓接1分鐘而製作評價用樣品。再者,不具備另一黏著劑層之黏著片材向基座之固定係使用日東電工股份有限公司製造之雙面膠帶No.585。
對該評價用樣品,於25℃之環境溫度下,使用Nordson公司製造之dage4000,於距貼附面之高度50 μm位置上於5 mm×5 mm矽晶片之側面安裝測定端子,藉由以剪切速率500 μm/sec.在與晶片水平之方向上施加外力而獲得之荷重-位移曲線,自所獲得之荷重-位移曲線讀取最大破壞荷重,並將其設為25℃環境溫度下之剪切接著強度。
又,於80℃之環境溫度下,與上述同樣地測定剪切接著強度。
表1中表示分別測定3次之平均值。
(2)壓痕硬度
利用測定裝置所附帶之軟體(triboscan),對藉由將金剛石製之Berkovich型(三稜錐型)探針垂直地抵壓於實施例及比較例中所獲得之黏著片材之黏著劑層表面而獲得之位移-荷重遲滯曲線進行數值處理,測定壓痕硬度H。壓痕硬度H係使用奈米壓痕儀(Hysitron Inc公司製造之Triboindenter TI-950),藉由25℃下之單一壓入法,於壓入速度約500 nm/sec、壓入深度約3000 nm之測定條件下進行測定。
又,根據壓痕硬度H,算出藉由1.9385×loghA+4.2611所計算之值。
(3)藍寶石研削性
於將厚度900 μm、4英吋尺寸之藍寶石晶圓配置於實施例及比較例中所獲得之黏著片材之黏著劑層上後,利用預先將該等預熱至90℃之熱壓機,於1.0 MPa之壓力下壓接5分鐘。將固定有藍寶石晶圓之黏著片材設置於DISCO股份有限公司製造之研磨機裝置DFG8540,進行研削直至晶圓厚度成為120 μm。研削性係基於以下之基準進行評價。
○:可進行背面研削直至晶圓厚度成為120 μm。
×:於晶圓厚度成為120 μm前晶圓破裂、或者晶圓端部缺損。(無法進行背面研削)
(4)剝離性
藉由目測觀察下述(5)中之黏著片材於80℃下之剝離黏著力評價後之被接著體SUS304BA。剝離性係基於以下之基準進行評價。
○:於SUS304BA上無凝聚破壞之黏著劑之殘留物,亦無貼附痕跡。
△:於SUS304BA上無凝聚破壞之黏著劑之殘留物,但可確認到貼附痕跡。
×:於SUS304BA上可確認到凝聚破壞之黏著劑之殘留物。
(5)80℃下之剝離黏著力
將實施例及比較例中所獲得之黏著片材切割為20 mm寬,利用手壓輥將該黏著片材之黏著面(黏著劑層面)貼附於SUS304BA而形成積層體。繼而,利用預先將該積層體預熱至80℃之熱壓機,於0.3 MPa之壓力下進行壓接1分鐘而製作樣品。對該樣品,於剝離角度180°、剝離速度300 mm/min之條件下將黏著片材自SUS304BA剝離而測定黏著力。
於該黏著片材為不具有基材之黏著片材(實施例28)之情形時,在與黏著劑層面相反之側之面貼附日東電工股份有限公司製造之膠帶No.315後,製作上述樣品,並測定剝離黏著力。
(6)基材之拉伸彈性模數
將黏著片材所使用之基材(寬10 mm)作為樣品,使用動態黏彈性測定裝置(TA Instrument公司製造,商品名「RSA-3」)測定於25℃下之拉伸彈性模數。再者,夾頭間距離設為20 mm,測定頻率設為1 Hz,初始應變設為0.05%,升溫速度設為5℃/min(-20℃~100℃)而進行測定。
[製造例1]樹脂組合物(I)之製備
混合順丁烯二酸改性苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(a)(SEBS:苯乙烯部位/乙烯-丁烯部位(重量比)=20/80,酸值:10(mg-CH3
ONa/g),旭化成化學公司製造,商品名「Tuftec M1943」)100重量份、萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar T80」,軟化點:80℃)20重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD-C」)3重量份、脂肪酸酯系界面活性劑(花王公司製造,商品名「EXEPARL IPP」,分子量:298.5,烷基之碳數:16)3重量份、及作為溶劑之甲苯,而製備樹脂組合物(I)(混合物)。
[製造例2-1]樹脂組合物(II-1)之製備
混合順丁烯二酸改性苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(b)(SEBS:苯乙烯部位/乙烯-丁烯部位(重量比)=30/70,酸值:10(mg-CH3
ONa/g),旭化成化學公司製造,商品名「Tuftec M1913」)100重量份、萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar T80」)50重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD-C」)3重量份、脂肪酸酯系界面活性劑(花王公司製造,商品名「EXEPARL IPP」,分子量:298.5,烷基之碳數:16)3重量份、及作為溶劑之甲苯,而製備樹脂組合物(II-1)(混合物)。
[製造例2-2~10]樹脂組合物(II-2~10)之製備
以表1所示之添加量使用表1所示之界面活性劑代替脂肪酸酯系界面活性劑(花王公司製造,商品名「EXEPARL IPP」,分子量:298.5,烷基之碳數:16)3重量份,除此以外,以與製造例2-1同樣之方式製備樹脂組合物(II-2~10)。再者,所使用之界面活性劑係如下所述。
製造例2-2(樹脂組合物(II-2)):磷酸酯系界面活性劑;東邦化學工業公司製造,商品名「Phosphanol RL210」,化學式:C22
H47
O5
P,烷基之碳數:18,分子量422.57
製造例2-3(樹脂組合物(II-3)):脂肪醯胺系界面活性劑;東京化成工業公司製造之硬脂醯胺,化學式:C18
H37
NO,烷基之碳數:18,分子量:283.49
製造例2-4(樹脂組合物(II-4)):脂肪醯胺系界面活性劑;東京化成工業公司製造之月桂醯胺,化學式:C12
H25
NO,烷基之碳數:12,分子量:199.33
製造例2-5(樹脂組合物(II-5)):脂肪酸胺基烷基醯胺系界面活性劑;東邦化學工業公司製造,商品名「Catinal MAPS」,化學式:C23
H38
N2
O,烷基之碳數:18,分子量:358.56
製造例2-6(樹脂組合物(II-6)):氯化三甲基銨系界面活性劑;東邦化學工業公司製造,商品名「Catinal STC-70ET」,化學式:C21
H46
ClN,烷基之碳數:16,分子量:348.04
製造例2-7(樹脂組合物(II-7)):氯化二甲基苄基銨系界面活性劑;三洋化成公司製造,商品名「Cation S」,化學式:C26
H48
ClN,烷基之碳數:18,分子量:410.11
製造例2-8(樹脂組合物(II-8)):琥珀酸酐系界面活性劑;三洋化成工業公司製造,商品名「DSA」,化學式:C16
H26
O3
,烷基之碳數:12,分子量:266.37
製造例2-9(樹脂組合物(II-9)):琥珀酸酐系界面活性劑;三洋化成工業公司製造,商品名「PDSA-DA」,化學式:C19
H32
O3
,烷基之碳數:15,分子量:308.45
製造例2-10(樹脂組合物(II-10)):磺基琥珀酸鈉系界面活性劑;三洋化成工業公司製造,商品名「Sansepara 100」,化學式:C20
H27
O7
SNa,烷基之碳數:6,分子量:434.48
[製造例3]樹脂組合物(III)之製備
使用萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar S145」,軟化點:145℃)代替萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar T80」),除此以外,以與製造例2同樣之方式製備樹脂組合物(III)。
[製造例4]樹脂組合物(IV)之製備
混合苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(c)(未酸改性品,旭化成化學公司製造,商品名「Tuftec H1043」)100重量份、萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar T80」)80重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD-C」)3重量份、磷酸酯系界面活性劑(東邦化學工業公司製造,商品名「Phosphanol RL210」,分子量422.57,烷基之碳數:18)3重量份、及作為溶劑之甲苯,而製備樹脂組合物(IV)(混合物)。
[製造例5]樹脂組合物(V)之製備
將萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar T80」)之添加量設為20重量份,除此以外,以與製造例4同樣之方式製備樹脂組合物(V)。
[製造例6]樹脂組合物(VI)之製備
將萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar T80」)之添加量設為100重量份,除此以外,以與製造例2同樣之方式製備樹脂組合物(VI)。
[製造例7]樹脂組合物(VII)之製備
將萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar T80」)之添加量設為125重量份,除此以外,以與製造例2同樣之方式製備樹脂組合物(VII)。
[製造例8]樹脂組合物(VIII)之製備
將萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar T80」)之添加量設為150重量份,除此以外,以與製造例2同樣之方式製備樹脂組合物(VIII)。
[製造例9]樹脂組合物(IX)之製備
將萜酚系黏著賦予樹脂(YASUHARA CHEMICAL公司製造,商品名「YS Polystar T80」)之添加量設為200重量份、及進而添加熱膨脹性微球(松本油脂製藥公司製造,商品名「Matsumoto Microsphere-F-50D」,發泡起始溫度120℃,平均粒徑14 μm)100重量份,除此以外,以與製造例2同樣之方式製備樹脂組合物(IX)。
[實施例1]
混合丙烯酸系樹脂(丙烯酸丁酯-丙烯酸共聚物,丙烯酸丁酯:丙烯酸(重量比)=100:5)100重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD-C」)3重量份、脂肪酸酯系界面活性劑(花王公司製造,商品名「EXEPARL IPP」,分子量:298.5,烷基之碳數:16)1重量份、及作為溶劑之甲苯,而製備樹脂組合物(A)。將該樹脂組合物(A)以乾燥後之厚度成為3 μm之方式塗佈於PET基材(厚度:50 μm)上,並進行乾燥而形成黏著劑層。進而,將隔片貼合於黏著劑層上,而製作具有PET基材/黏著劑層/隔片之層構成之黏著片材。將所獲得之黏著片材供於上述評價(1)~(5),將所得之結果示於表2。
[實施例2]
將製造例1中所製備之樹脂組合物(I)以乾燥後之厚度成為15 μm之方式塗佈於PET基材(厚度:50 μm)上,進行乾燥而形成黏著劑層。進而,將隔片貼合於黏著劑層上而製作具有PET基材/黏著劑層/隔片之層構成之黏著片材。將所獲得之黏著片材供於上述評價(1)~(5),將所得之結果示於表2。
[實施例3]
將黏著劑層之厚度設為20 μm,除此以外,以與實施例2同樣之方式製作黏著片材。將所獲得之黏著片材供於上述評價(1)~(5),將所得之結果示於表2。
[實施例4]
將黏著劑層之厚度設為25 μm,除此以外,以與實施例2同樣之方式製作黏著片材。將所獲得之黏著片材供於上述評價(1)~(5),將所得之結果示於表2。
[實施例5~11]
使用表2所示之樹脂組合物(製造例2-1及製造例3~5中所製備之樹脂組合物(II-1)及(III)~(V))代替樹脂組合物(I),將黏著劑層之厚度設為表2所示之厚度,除此以外,以與實施例2同樣之方式製作黏著片材。將所獲得之黏著片材供於上述評價(1)~(5)。將結果示於表2。
[實施例12]
混合乙烯-乙酸乙烯酯共聚樹脂(三菱化學公司製造,商品名「EV-40W」)100重量份、環氧系交聯劑(三菱瓦斯化學公司製造,商品名「TETRAD-C」)3重量份、脂肪酸酯系界面活性劑(花王公司製造,商品名「EXEPARL IPP」,分子量:298.5,烷基之碳數:16)3重量份、及作為溶劑之甲苯,而製備樹脂組合物(B)。將該樹脂組合物(B)以乾燥後之厚度成為15 μm之方式塗佈於PET基材(厚度:50 μm)上,並進行乾燥而形成黏著劑層。進而,將隔片貼合於黏著劑層上,而製作具有PET基材/黏著劑層/隔片之層構成之黏著片材。將所獲得之黏著片材供於上述評價(1)~(5),並將所得之結果示於表3。
[實施例13]
使用乙烯-乙酸乙烯酯共聚樹脂(三菱化學公司製造,商品名「EV-150」)代替乙烯-乙酸乙烯酯共聚樹脂(三菱化學公司製造,商品名「EV-40W」),除此以外,以與實施例12同樣之方式獲得黏著片材。將所獲得之黏著片材供於上述評價(1)~(5)。將結果示於表3。
[實施例14~25]
使用表2所示之樹脂組合物(樹脂組合物(VI)~(VIII)及(II-2)~(II-11)代替樹脂組合物(I),將黏著劑層之厚度設為表2所示之厚度,除此以外,以與實施例2同樣之方式製作黏著片材。將所獲得之黏著片材供於上述評價(1)~(5)。將結果示於表3。
[實施例26]
使用聚烯烴系基材(厚度:80 μm)代替PET基材(厚度:50 μm)、及將黏著劑層之厚度設為20 μm,除此以外,以與實施例5同樣之方式獲得黏著片材。將所獲得之黏著片材供於上述評價。將結果示於表4。
作為上述聚烯烴系基材,使用如下基材,其係將包含丙烯成分及乙烯丙烯橡膠成分之丙烯系熱塑性彈性體(三菱化學公司製造,商品名「ZELAS」)供於PLACO公司製造之T鑄模成形機(設定溫度:230℃),成形為厚度80 μm之膜狀而獲得。
[實施例27]
使用聚烯烴系基材(大倉工業公司製造,商品名「NSO#60」,厚度:60 μm)代替PET基材(厚度:50 μm)、及將黏著劑層之厚度設為20 μm,除此以外,以與實施例5同樣之方式獲得黏著片材。將所獲得之黏著片材供於上述評價。將結果示於表4。
[實施例28]
將製造例9中所製備之樹脂組合物(IX)以乾燥後之厚度成為40 μm之方式塗佈於隔片上,並進行乾燥而形成黏著劑層。進而,貼合隔片上之黏著劑層與另一隔片,而製作具有隔片/黏著劑層/隔片之層構成之黏著片材。將所獲得之黏著片材供於上述評價(1)~(5),並將所得之結果示於表4。
[比較例1]
將黏著劑層之厚度設為30 μm,除此以外,以與實施例2同樣之方式獲得黏著片材。將所獲得之黏著片材供於上述評價(1)~(5)。將結果示於表5。
[比較例2]
將黏著劑層之厚度設為70 μm,除此以外,以與實施例5同樣之方式獲得黏著片材。將所獲得之黏著片材供於上述評價(1)~(5)。將結果示於表5。
[比較例3]
將黏著劑層之厚度設為200 μm,除此以外,以與實施例8同樣之方式獲得黏著片材。將所獲得之黏著片材供於上述評價(1)~(5)。將結果示於表5。
[比較例4]
使用芳香族酯系界面活性劑(DIC公司製造,商品名「MONOCIZER W-700」,分子量:546.78,烷基之碳數:6)代替脂肪酸酯系界面活性劑(花王公司製造,商品名「EXEPARL IPP」,分子量:298.5,烷基之碳數:16)3重量份,將黏著劑層之厚度設為10 μm,除此以外,以與實施例1同樣之方式獲得黏著片材。將所獲得之黏著片材供於上述評價(1)~(5)。將結果示於表5。
10:黏著劑層
20:基材
30:另一黏著劑層
100:黏著片材
200:黏著片材
300:黏著片材
圖1(a)、(b)及(c)為本發明之一實施形態之黏著片材之概略剖視圖。
10:黏著劑層
20:基材
30:另一黏著劑層
100:黏著片材
200:黏著片材
300:黏著片材
Claims (14)
- 一種黏著片材,其係具備黏著劑層者,且該黏著劑層之厚度為1μm~300μm,該黏著劑層於25℃下之壓痕硬度H(Pa)與黏著劑層之厚度hA(μm)滿足下述式(1)之關係:logH≧1.9385×loghA+4.2611 (1)。
- 如請求項1之黏著片材,其中將上述黏著片材之黏著面貼合於矽晶片之情形時之25℃之環境溫度下的剪切接著強度為1.0MPa以上。
- 如請求項1或2之黏著片材,其中將上述黏著片材之黏著面貼合於SUS304BA時之80℃之環境溫度下之剝離黏著力為15N/20mm以下。
- 如請求項1或2之黏著片材,其中上述黏著劑層於25℃下之壓痕硬度H為10MPa~1GPa。
- 如請求項1或2之黏著片材,其中上述黏著劑層包含含有基礎聚合物之黏著劑,且該基礎聚合物為熱塑性彈性體。
- 如請求項5之黏著片材,其中上述熱塑性彈性體為苯乙烯系彈性體或乙烯-乙酸乙烯酯系彈性體。
- 如請求項5之黏著片材,其中上述黏著劑進而包含黏著賦予樹脂。
- 如請求項7之黏著片材,其中上述黏著賦予樹脂之含量相對於上述基礎聚合物100重量份,為1重量份~350重量份。
- 如請求項1或2之黏著片材,其進而具備配置於上述黏著劑層之至少單側之基材。
- 如請求項1或2之黏著片材,其進而具備配置於上述黏著劑層之至少單側之另一黏著劑層。
- 如請求項9之黏著片材,其中上述基材於25℃下之拉伸彈性模數為1×107Pa~1×1010Pa。
- 如請求項1或2之黏著片材,其係用作半導體製造步驟中之基板加工時之暫時固定材。
- 一種基板之研削方法,其包括如下步驟:於具備黏著劑層之黏著片材之該黏著劑層上載置基板,進行固定後,對該基板之與黏著劑層側相反之側之面進行研削;且該黏著劑層之厚度為1μm~300μm,該黏著劑層於25℃下之壓痕硬度H(Pa)與黏著劑層之厚度hA(μm)滿足 下述式(1)之關係:logH≧1.9385×loghA+4.2611 (1)。
- 一種晶片之製造方法,其包括如下之研削步驟:於具備黏著劑層之黏著片材之該黏著劑層上載置基板,進行固定後,對該基板之與黏著劑層側相反之側之面進行研削;且該黏著劑層之厚度為1μm~300μm,該黏著劑層於25℃下之壓痕硬度H(Pa)與黏著劑層之厚度hA(μm)滿足下述式(1)之關係:logH≧1.9385×loghA+4.2611 (1)。
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