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TW201726778A - 聚烯烴系樹脂發泡片及黏著帶 - Google Patents

聚烯烴系樹脂發泡片及黏著帶 Download PDF

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Publication number
TW201726778A
TW201726778A TW105139352A TW105139352A TW201726778A TW 201726778 A TW201726778 A TW 201726778A TW 105139352 A TW105139352 A TW 105139352A TW 105139352 A TW105139352 A TW 105139352A TW 201726778 A TW201726778 A TW 201726778A
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TW
Taiwan
Prior art keywords
foamed sheet
polyolefin
less
mpa
based resin
Prior art date
Application number
TW105139352A
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English (en)
Other versions
TWI677522B (zh
Inventor
Kento Nagai
Shigeki Matsuki
Original Assignee
Sekisui Chemical Co Ltd
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Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=58796936&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=TW201726778(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Publication of TW201726778A publication Critical patent/TW201726778A/zh
Application granted granted Critical
Publication of TWI677522B publication Critical patent/TWI677522B/zh

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    • 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
    • C09J7/26—Porous or cellular plastics
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C44/5627—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
    • B29C44/5672—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching by stretching the foam, e.g. to open the cells
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    • B29C44/5681—Covering the foamed object with, e.g. a lining
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract

本發明之聚烯烴系樹脂發泡片係將聚烯烴系樹脂發泡而成者，且上述發泡片之發泡倍率為1.5~20cm3/g，上述發泡片之MD方向及TD方向之平均氣泡直徑為130μm以下，且滿足下述式(1)及式(2)。TM/D≧6 (1) TT/D≧5 (2)TM：90℃之MD方向之抗拉力TT：90℃之TD方向之抗拉力D：上述發泡片之密度(g/cm3)

Description

聚烯烴系樹脂發泡片及黏著帶
本發明係關於一種將聚烯烴系樹脂發泡而成之聚烯烴系樹脂發泡片、及使用其之黏著帶。
於智慧型手機或筆記型電腦等具有顯示畫面之電子機器中，於保護顯示畫面之面板與殼體之間設置有用以吸收衝擊來保護顯示畫面之緩衝材(例如專利文獻1)。並且，上述電子機器大多於將顯示畫面沿鉛直方向豎立之狀態下使用，故而要求上述緩衝材具有優異之剪切強度。進而，上述電子機器由於經高密度集成之電子零件會產生大量之熱，故而電子機器之內部容易變成高溫，又，由於存在「上述電子機器本身於氣溫較高之室外使用」之情況，故而期望上述緩衝材即便於高溫下亦具有優異之剪切強度。
[先前技術文獻]
[專利文獻]
專利文獻1：國際公開2013/099755號
於欲提高發泡片之剪切強度之情形時，必須使發泡片增厚，故而難以用於小型電子機器。
本發明係鑒於上述習知之情況而完成者，目的在於提供一種即便厚度較薄亦具有優異之剪切強度之聚烯烴系樹脂發泡片、及使用其之黏著帶。
本發明人等進行了努力研究，結果發現，若以使高溫下之發泡片之抗拉力與密度滿足一定關係之方式進行調整，則可解決上述課題，從而完成了本發明。
即，本發明之主旨在於以下之[1]~[2]。
[1]一種聚烯烴系樹脂發泡片，其係將聚烯烴系樹脂發泡而成者，上述發泡片之發泡倍率為1.5~20cm3/g，上述發泡片之MD方向及TD方向之平均氣泡直徑為130μm以下，且滿足下述式(1)及式(2)。
TM/D≧6 (1)
TT/D≧5 (2)
TM：90℃之MD方向之抗拉力
TT：90℃之TD方向之抗拉力
D：上述發泡片之密度(g/cm3)
[2]一種黏著帶，其係於上述[1]之聚烯烴系樹脂發泡片之至少一面設置有黏著劑層。
根據本發明，可提供一種即便厚度較薄亦具有優異之剪切強 度之聚烯烴系樹脂發泡片、及使用其之黏著帶。
[聚烯烴系樹脂發泡片]
本發明之聚烯烴系樹脂發泡片(以下亦稱為「發泡片」)係將聚烯烴系樹脂發泡而成之片材，且具有大量氣泡。
以下，對本發明之聚烯烴系樹脂發泡片更詳細地說明。
<發泡倍率>
關於本發明之發泡片之發泡倍率，就提高衝擊吸收性之觀點而言為1.5cm3/g以上，更佳為1.7cm3/g以上，進而較佳為1.9cm3/g以上，就提高發泡片之剪切強度之觀點而言為20cm3/g以下，較佳為18cm3/g以下，更佳為17cm3/g以下，進而較佳為15cm3/g以下，進而更佳為14cm3/g以下，進而更佳為12cm3/g以下，進而更佳為10cm3/g以下，進而更佳為8cm3/g以下，進而更佳為6cm3/g以下。
再者，本發明中之發泡倍率係指依據JIS K 7222所測得之發泡片之密度之倒數。
<平均氣泡直徑>
關於本發明之發泡片之MD方向之平均氣泡直徑，就提高發泡片之柔軟性、及階差追隨性之觀點而言，較佳為10μm以上，更佳為20μm以上， 進而較佳為30μm以上，進而更佳為35μm以上，進而更佳為40μm以上，進而更佳為45μm以上，進而更佳為50μm以上，就提高發泡片之剪切強度之觀點而言為130μm以下，較佳為120μm以下，更佳為110μm以下，進而較佳為100μm以下，進而更佳為90μm以下，進而更佳為80μm以下，進而更佳為70μm以下。
關於本發明之發泡片之TD方向之平均氣泡直徑，就提高發泡片之柔軟性、及階差追隨性之觀點而言，較佳為10μm以上，更佳為20μm以上，進而較佳為30μm以上，進而更佳為40μm以上，進而更佳為50μm以上，就提高發泡片之剪切強度之觀點而言為130μm以下，較佳為125μm以下，更佳為120μm以下，進而較佳為110μm以下，進而更佳為100μm以下，進而更佳為90μm以下，進而更佳為80μm以下，進而更佳為70μm以下。
再者，於本發明中，「MD」意指Machine Direction(加工方向)，係指與聚烯烴系樹脂發泡片之擠出方向等一致之方向。又，「TD」意指Transverse Direction(橫向方向)，係指與MD正交且與發泡片平行之方向。
再者，上述平均氣泡直徑可依據下述實施例之方法進行測定。
<發泡片之密度(D)與90℃之抗拉力之關係>
本發明之發泡片滿足下述式(i)及式(2)。
TM/D≧6 (1)
TT/D≧5 (2)
TM：90℃之MD方向之抗拉力
TT：90℃之TD方向之抗拉力
D：上述發泡片之密度(g/cm3)
再者，於本發明中，所謂「抗拉力」，係指於90℃之條件下依據JIS K 6767對將發泡片切斷成JIS K 62514.1所規定之1號啞鈴狀所得之試樣進行測定所得之MD方向及TD方向之強度。
關於式(1)中之TM/D，就提高發泡片之剪切強度之觀點而言為6以上，較佳為6.1以上，更佳為6.5以上，進而較佳為7.0以上，進而更佳為7.5以上，並且，較佳為48以下，更佳為20以下，進而較佳為16以下，進而更佳為14以下，進而更佳為12以下，進而更佳為10以下。
關於式(2)中之TT/D，就提高發泡片之剪切強度之觀點而言為5以上，較佳為5.2以上，更佳為5.4以上，進而較佳為5.6以上，進而更佳為5.8以上，並且，較佳為30以下，更佳為20以下，進而較佳為16以下，進而更佳為14以下，進而更佳為12以下，進而更佳為10以下，進而更佳為8以下。
<密度>
關於本發明之發泡片之密度，就提高發泡片之剪切強度之觀點、及提高材料強度之觀點而言，較佳為0.01g/cm3以上，更佳為0.03g/cm3以上，進而較佳為0.05g/cm3以上，就提高發泡片之柔軟性之觀點而言，較佳為1g/cm3以下，更佳為0.8g/cm3以下，進而較佳為0.6g/cm3以下。再者，密度係依據JIS K 7222所測得之值。
<90℃之MD方向之抗拉力>
關於本發明之發泡片之90℃之MD方向之抗拉力，就提高發泡片之剪切強度之觀點、及提高材料強度之觀點而言，較佳為0.1MPa以上，更佳為 0.3MPa以上，進而較佳為0.5MPa以上，進而更佳為0.7MPa以上，進而更佳為0.9MPa以上，就提高發泡片之加工性之觀點而言，較佳為10MPa以下，更佳為8MPa以下，進而較佳為6MPa以下，進而更佳為5MPa以下，進而更佳為4MPa以下。
再者，90℃之抗拉力可依據下述實施例所記載之方法進行測定。
<90℃之TD方向之抗拉力>
關於本發明之發泡片之90℃之TD方向之抗拉力，就提高發泡片之剪切強度之觀點、及提高材料強度之觀點而言，較佳為0.1MPa以上，更佳為0.3MPa以上，進而較佳為0.5MPa以上，進而更佳為0.7MPa以上，進而更佳為0.9MPa以上，就提高發泡片之加工性之觀點而言，較佳為10MPa以下，更佳為8MPa以下，進而較佳為6MPa以下，進而更佳為5MPa以下，進而更佳為4MPa以下。
<23℃之MD方向之抗拉力>
關於本發明之發泡片之23℃之MD方向之抗拉力，就提高發泡片之剪切強度之觀點、及提高材料強度之觀點而言，較佳為0.5MPa以上，更佳為1MPa以上，進而較佳為1.5MPa以上，進而更佳為2.0MPa以上，進而更佳為2.5MPa以上，就提高發泡片之加工性之觀點而言，較佳為35MPa以下，更佳為32MPa以下，進而較佳為30MPa以下，進而更佳為28MPa以下，進而更佳為26MPa以下，進而更佳為24MPa以下。
再者，23℃之抗拉力可依據下述實施例所記載之方法進行測定。
<23℃之TD方向之抗拉力>
關於本發明之發泡片之23℃之TD方向之抗拉力，就提高發泡片之剪 切強度之觀點、及提高材料強度之觀點而言，較佳為0.5MPa以上，更佳為1MPa以上，進而較佳為1.3MPa以上，進而更佳為1.7MPa以上，進而更佳為2.0MPa以上，就提高發泡片之加工性之觀點而言，較佳為30MPa以下，更佳為28MPa以下，進而較佳為26MPa以下，進而更佳為24MPa以下，進而更佳為22MPa以下，進而更佳為20MPa以下。
<90℃之剪切強度>
關於本發明之發泡片之90℃之剪切強度，就較佳地用作電子機器之顯示畫面之緩衝材之觀點而言，較佳為0.3MPa以上，更佳為0.6MPa以上，進而較佳為0.8MPa以上，進而更佳為0.9MPa以上，並且，較佳為10MPa以下，更佳為5MPa以下。
再者，90℃之剪切強度可依據下述實施例所記載之方法進行測定。
<厚度>
關於本發明之發泡片之厚度，就提高發泡片之剪切強度之觀點、及提高材料強度之觀點而言，較佳為0.02mm以上，更佳為0.05mm以上，進而較佳為0.08mm以上，進而更佳為0.1mm以上，就提高柔軟性、及階差追隨性之觀點、及用於薄型電子機器之內部之觀點而言，較佳為0.8mm以下，更佳為0.75mm以下，進而更佳為0.7mm以下，進而更佳為0.65mm以下。
<25%壓縮強度>
關於本發明之發泡片之25%壓縮強度，就提高發泡片之剪切強度、及衝擊吸收性之觀點而言，較佳為10kPa以上，更佳為15kPa以上，進而較佳為20kPa以上，進而更佳為25kPa以上，進而更佳為30kPa以上，進而更佳為35kPa以上，就提高發泡片之柔軟性之觀點、及提高階差追隨性之 觀點而言，較佳為1,000kPa以下，更佳為900kPa以下，進而較佳為850kPa以下，進而更佳為800kPa以下，進而更佳為750kPa以下，進而更佳為700kPa以下。於本發明中，可提供降低壓縮強度以使柔軟性良好並且剪切強度優異之發泡片。
再者，25%壓縮強度可依據下述實施例所記載之方法進行測定。
<凝膠分率(交聯度)>
就提高發泡片之剪切強度之觀點而言，本發明之發泡片較佳為交聯而成者，此情形時之凝膠分率(交聯度)較佳為5~60質量%。又，凝膠分率更佳為55質量%以下。又，凝膠分率更佳為25質量%以上，進而較佳為35質量%以上，進而更佳為40質量%以上。若凝膠分率(交聯度)為上述下限值以上，則會形成充分之交聯，藉由使其發泡而可獲得剪切強度優異之發泡片。再者，凝膠分率較高者容易提高剪切強度。又，若凝膠分率(交聯度)為上述上限值以下，則容易確保發泡片之柔軟性。
再者，凝膠分率(交聯度)可依據下述實施例所記載之方法進行測定。
<獨立氣泡率>
發泡片較佳為氣泡為獨立氣泡。所謂氣泡為獨立氣泡，意指獨立氣泡相對於總氣泡之比率(稱為獨立氣泡率)為70%以上。若氣泡為獨立氣泡，則受到衝擊時氣泡之變形量被抑制，藉此發泡片對衝擊之變形量亦受到抑制，故而更容易提高衝擊吸收性。
為了進一步提高衝擊吸收性，上述獨立氣泡率較佳為70~100%，更佳為80~100%，進而較佳為90~100%。
又，若獨立氣泡為上述範圍，則發泡片內部之空氣移動被限制，從而 可抑制空氣對流所產生之熱傳遞，而提高隔熱性。
再者，所謂獨立氣泡率，係指依據ASTM D2856(1998)所測得者。
[聚烯烴系樹脂]
作為用於形成發泡片之聚烯烴系樹脂，可列舉聚乙烯系樹脂、聚丙烯系樹脂、或該等之混合物。
<聚乙烯系樹脂>
聚乙烯系樹脂亦可為乙烯均聚物，較佳為藉由將乙烯與視需要之少量(例如總單體之30質量%以下，較佳為10質量%以下)之α-烯烴共聚合而得之聚乙烯系樹脂，其中，較佳為直鏈狀低密度聚乙烯。
作為構成聚乙烯系樹脂之α-烯烴，具體而言，可列舉：丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、及1-辛烯等。其中，較佳為碳數4~10之α-烯烴。
又，作為聚乙烯系樹脂，亦較佳為乙烯-乙酸乙烯酯共聚物。乙烯-乙酸乙烯酯共聚物通常係含有50質量%以上之乙烯單元之共聚物。乙烯-乙酸乙烯酯共聚物之乙酸乙烯酯含有率例如為5~50質量%，較佳為10~40質量%，更佳為15~35質量%。再者，乙酸乙烯酯含有率係依據JIS K6924-1所測得者。
為了提高發泡片之柔軟性以提高耐衝擊吸收性，聚乙烯系樹脂較佳為低密度。具體而言，聚乙烯系樹脂之密度較佳為0.920g/cm3以下，更佳為0.880~0.915g/cm3，進而較佳為0.885~0.910g/cm3。作為具有此種密度之聚乙烯系樹脂，可列舉直鏈狀低密度聚乙烯。再者，密度係依據ASTM D792所測得者。
<聚丙烯系樹脂>
作為聚丙烯系樹脂，例如可列舉丙烯均聚物、含有50質量%以上之丙烯單元之丙烯-乙烯共聚物、丙烯-乙烯-α-烯烴共聚物、及丙烯-α-烯烴共聚物等。該等可單獨使用1種，亦可將2種以上併用。
作為構成丙烯-α-烯烴共聚物之α-烯烴，具體而言，可列舉：1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、1-辛烯等，該等之中，較佳為碳數6~12之α-烯烴。
作為本發明中之聚烯烴系樹脂，就提高柔軟性、及衝擊吸收性之觀點而言，較佳為藉由將茂金屬化合物、齊格勒-納他化合物、氧化鉻化合物等用作觸媒進行聚合而成之聚乙烯系樹脂、聚丙烯系樹脂、或該等之混合物，聚乙烯系樹脂之中，更佳為直鏈狀低密度聚乙烯。
再者，於使用藉由將茂金屬化合物用作觸媒而獲得之聚乙烯系樹脂、乙烯-乙酸乙烯酯共聚物、或該等之混合物之情形時，其含量較佳為聚烯烴系樹脂整體之40質量%以上，更佳為50質量%以上，進而較佳為60質量%以上，進而更佳為100質量%。
又，於使用直鏈狀低密度聚乙烯之情形時，可單獨使用直鏈狀低密度聚乙烯作為聚烯烴系樹脂，亦可與直鏈狀低密度聚乙烯以外之聚烯烴系樹脂併用。作為併用之聚烯烴系樹脂，可列舉乙烯-乙酸乙烯酯共聚物。又，於使用直鏈狀低密度聚乙烯之情形時，直鏈狀低密度聚乙烯之含量較佳為聚烯烴系樹脂整體之20~100質量%以上，較佳為30~100質量%。另一方面，與直鏈狀低密度聚乙烯併用之乙烯-乙酸乙烯酯共聚物之含量較佳為80質量%以下，更佳為70質量%以下。
<茂金屬化合物>
作為較佳之茂金屬化合物，可列舉具有於π電子系之不飽和化合物之間夾有過渡金屬之結構之雙(環戊二烯基)金屬錯合物等化合物。更具體而言，可列舉於鈦、鋯、鎳、鈀、鉿、及鉑等四價過渡金屬存在1個或2個以上之作為配位子(配位基)之環戊二烯基環或其類似物的化合物。
此種茂金屬化合物之活性部位之性質均一且各活性部位具備相同之活性度。使用茂金屬化合物合成之聚合物由於分子量、分子量分佈、組成、組成分佈等之均勻性較高，故而於使包含使用茂金屬化合物所合成之聚合物之片材進行交聯之情形時，交聯均勻地進行。經均勻地交聯之片材由於容易均勻地延伸，故而容易使交聯聚烯烴系樹脂發泡片之厚度均勻。
作為配位子，例如可列舉：環戊二烯基環、茚基環等。該等環式化合物亦可經烴基、取代烴基或烴-取代類金屬基取代。作為烴基，例如可列舉：甲基、乙基、各種丙基、各種丁基、各種戊基、各種己基、2-乙基己基、各種庚基、各種辛基、各種壬基、各種癸基、各種鯨蠟基、苯基等。再者，所謂「各種」，意指包含正-、第二-、第三-、異-之各種異構物。
又，亦可使用將環式化合物作為低聚物進行聚合而成者作為配位子。
進而，除π電子系之不飽和化合物以外，亦可使用氯或溴等一價陰離子配位子或二價陰離子螯合物配位子、烴、烷氧化物、芳基醯胺、芳基氧化物、醯胺、芳基醯胺、磷化物、芳基磷化物等。
作為包含四價過渡金屬或配位子之茂金屬化合物，例如可列舉：環戊二烯基鈦三(二甲基醯胺)、甲基環戊二烯基鈦三(二甲基醯胺)、二 氯化雙(環戊二烯基)鈦、二甲基矽基四甲基環戊二烯基第三丁基醯胺二氯化鋯等。
茂金屬化合物係藉由與特定之共觸媒(輔觸媒)組合而於各種烯烴之聚合時發揮作為觸媒之作用。作為具體之共觸媒，可列舉甲基鋁氧烷(MAO)、硼系化合物等。再者，共觸媒相對於茂金屬化合物之使用比率較佳為10~100萬莫耳倍，更佳為50~5,000莫耳倍。
<齊格勒-納他化合物>
齊格勒-納他化合物係三乙基鋁-四氯化鈦固體複合物，並且較佳為藉由將利用有機鋁化合物將四氯化鈦還原並進而以各種電子供體及電子受體進行處理而得之三氯化鈦組成物、有機鋁化合物、及芳香族羧酸酯組合之方法(參照日本特開昭56-100806號、日本特開昭56-120712號、日本特開昭58-104907號之各公報)、及使四氯化鈦及各種電子供體與鹵化鎂接觸之擔載型觸媒之方法(參照日本特開昭57-63310號、日本特開昭63-43915號、日本特開昭63-83116號之各公報)等製造而成者。
<聚烯烴系樹脂可含有之其他成分>
作為聚烯烴系樹脂，亦可併用上述聚烯烴系樹脂以外之樹脂。
進而，亦可於聚烯烴系樹脂中混合下述各種添加劑、其他任意成分，發泡片亦可為其混合物經交聯、發泡而成者。
作為發泡片中所含有之任意成分，可列舉聚烯烴系樹脂以外之樹脂、橡膠，該等之合計含量少於聚烯烴系樹脂，相對於聚烯烴系樹脂100質量份，通常為50質量份以下、較佳為30質量份以下之程度。
[發泡片之製造方法]
本發明之發泡片可藉由利用通常之方法將聚烯烴系樹脂發泡而製造，其製造方法並無限制，亦可藉由視需要使聚烯烴系樹脂組成物交聯後進行發泡而製造。
具體而言，本發明之發泡片例如可藉由具有以下之步驟(1)~(3)之方法而製造。
步驟(1)：藉由將聚烯烴系樹脂、熱分解型發泡劑、及其他添加劑供給至擠出機中進行熔融混練，並自擠出機以片狀擠出而獲得製成片狀之聚烯烴系樹脂組成物之步驟
步驟(2)：使製成片狀之聚烯烴系樹脂組成物交聯之步驟
步驟(3)：對經交聯之片狀聚烯烴系樹脂組成物進行加熱而使熱分解型發泡劑發泡，使發泡片沿較佳為MD方向或TD方向之任一方向或兩方向延伸之步驟
再者，作為交聯聚烯烴系樹脂發泡片之製造方法，除該方法以外，亦可藉由國際公開第2005/007731號所記載之方法進行製造。
作為熱分解型發泡劑，並無特別限制，例如可列舉：偶氮二甲醯胺、N,N'-二亞硝基五亞甲基四胺、對甲苯磺醯胺基脲等。該等之中，較佳為偶氮二甲醯胺。再者，熱分解型發泡劑可單獨使用，亦可將2種以上組合使用。
關於聚烯烴系樹脂組成物中之熱分解型發泡劑之含量，相對於聚烯烴系樹脂100質量份，較佳為1~15質量份，更佳為1~12質量份，進而較佳為1~8質量份。若熱分解型發泡劑之含量為上述範圍內，則聚烯烴系樹脂組成物之發泡性提高，容易獲得具有所欲發泡倍率之聚烯烴系樹脂發泡 片，並且抗拉力及壓縮恢復性提高。
作為上述步驟(1)中使用之其他添加劑，例如可列舉分解溫度調整劑、交聯助劑、抗氧化劑等。
分解溫度調整劑係摻合作為調節降低熱分解型發泡劑之分解溫度或提高分解速度等，作為具體之化合物，可列舉氧化鋅、硬脂酸鋅、脲等。為了調整發泡片之表面狀態等，分解溫度調整劑例如相對於聚烯烴系樹脂100質量份，調配0.01~5質量份。
作為交聯助劑，可使用多官能單體。藉由向聚烯烴系樹脂中添加交聯助劑而減少下述步驟(2)中照射之游離放射線量，防止游離放射線之照射所伴隨之樹脂分子之切斷、劣化。
作為交聯助劑，具體而言，可列舉：三羥甲基丙烷三甲基丙烯酸酯、三羥甲基丙烷三丙烯酸酯、偏苯三甲酸三烯丙酯、1,2,4-苯三羧酸三烯丙酯、異氰尿酸三烯丙酯等1分子中具有3個官能基之化合物、或1,6-己二醇二甲基丙烯酸酯、1,9-壬二醇二甲基丙烯酸酯、1,10-癸二醇二甲基丙烯酸酯、二乙烯苯等1分子中具有2個官能基之化合物、鄰苯二甲酸二烯丙酯、對苯二甲酸二烯丙酯、間苯二甲酸二烯丙酯、乙基乙烯基苯、新戊二醇二甲基丙烯酸酯、甲基丙烯酸月桂酯、甲基丙烯酸硬脂酯等。
該等交聯助劑可單獨使用，或將2種以上組合使用。
關於交聯助劑之添加量，相對於樹脂成分100質量份，較佳為0.2~10質量份，更佳為0.3~5質量份，進而較佳為0.5~5質量份。若該添加量為0.2質量份以上，則可穩定地獲得發泡片所欲之交聯度，若為10質量份以下，則控制發泡片之交聯度變得容易。
又，作為抗氧化劑，可列舉2,6-二第三丁基對甲酚等酚系抗氧化劑等。
作為使聚烯烴系樹脂組成物發泡之方法，並無特別限制，例如可列舉藉由熱風對聚烯烴系樹脂組成物進行加熱之方法、藉由紅外線進行加熱之方法、藉由鹽浴進行加熱之方法、藉由油浴進行加熱之方法等，亦可將該等併用。
再者，聚烯烴系樹脂組成物之發泡並不限定於使用熱分解型發泡劑之例，亦可使用利用丁烷氣體等之物理發泡。
作為使聚烯烴系樹脂組成物交聯之方法，例如可列舉於聚烯烴系樹脂組成物中預先摻合有機過氧化物，並對聚烯烴系樹脂組成物進行加熱而使有機過氧化物分解之方法。
作為交聯所使用之有機過氧化物，例如可列舉：1,1-雙(過氧化第三丁基)3,3,5-三甲基環己烷、1,1-雙(過氧化第三丁基)環己烷等。該等可單獨使用1種，亦可將2種以上併用。關於有機過氧化物之添加量，相對於聚烯烴系樹脂100質量份，較佳為0.01~5質量份，更佳為0.1~3質量份。若有機過氧化物之添加量為上述範圍內，則容易進行聚烯烴系樹脂組成物之交聯，又，可於所獲得之交聯聚烯烴系樹脂發泡片中抑制有機過氧化物之分解殘渣之量。
又，作為使聚烯烴系樹脂組成物交聯之方法，亦可列舉對聚烯烴系樹脂組成物照射電子束、α射線、β射線、γ射線等游離放射線之方法。
關於游離放射線之照射量，較佳為0.5~20Mrad、更佳為3~12Mrad以使凝膠分率成為5~60質量%。
上述使聚烯烴系樹脂組成物交聯之方法亦可併用，就均質地進行交聯之觀點而言，較佳為照射游離放射線之方法。
本發明之聚烯烴系樹脂發泡片較佳為如上所述般沿MD方向或TD方向之任一方向或兩方向延伸。
上述延伸可於使聚烯烴系樹脂組成物發泡而獲得發泡片後進行，亦可一面使聚烯烴系樹脂組成物發泡一面進行。再者，於使聚烯烴系樹脂組成物發泡而獲得發泡片後使發泡片延伸之情形時，較佳為不對發泡片進行冷卻而直接維持發泡時之熔融狀態並繼續延伸發泡片，亦可於對發泡片進行冷卻後，再次對發泡片進行加熱而製成熔融或軟化狀態，然後延伸發泡片。
又，發泡片之MD方向上之延伸倍率較佳為1.1~3.2倍，更佳為1.3~3.0倍。若將發泡片之MD方向上之延伸倍率設為上述下限值以上，則發泡片之隔熱性、柔軟性及抗拉力容易變得良好。另一方面，若為上限值以下，則可防止發泡片於延伸過程中斷裂、發泡氣體自發泡中之發泡片逸出導致發泡倍率降低，發泡片之柔軟性及抗拉力變得良好，亦容易使品質均勻。又，發泡片於TD方向上亦較佳為以上述範圍之延伸倍率進行延伸。
[黏著帶]
本發明之黏著帶係將本發明之發泡片用作基材，並於發泡片之一面或兩面設置有黏著劑層者。黏著帶之厚度通常為0.03~2.0mm，較佳為0.05~1.0mm。
構成黏著帶之黏著劑層之厚度較佳為5~200μm，更佳為7~150μm，進而較佳為10~100μm。若構成黏著帶之黏著劑層之厚度為5~200 μm，則可使黏著帶之厚度變薄，並且可有助於使用黏著帶之電子機器本身之小型化、及薄型化。
作為構成設置於發泡片之一面或兩面之黏著劑層之黏著劑，並無特別限制，例如使用丙烯酸系黏著劑、胺酯系黏著劑、橡膠系黏著劑等。
作為將黏著劑塗佈於發泡片而於發泡片上積層黏著劑層之方法，例如可列舉使用塗佈機等塗敷機將黏著劑塗佈於發泡片之至少一面之方法、使用噴霧器將黏著劑噴霧、塗佈於發泡片之至少一面之方法、使用毛刷將黏著劑塗佈於發泡片之一面之方法等。
使用本發明之發泡片之黏著帶可作為防止內裝於行動電話或攝錄影機等電子機器本體內之電子零件受到衝擊之衝擊吸收材、或防止灰塵或水分等滲入至電子機器本體內之密封材料來使用。
實施例
藉由實施例對本發明進而更詳細地進行說明，但本發明並不受該等例之任何限定。
[測定方法]
本說明書中之各物性之測定方法如下所述。
<密度及發泡倍率>
依據JIS K7222測定實施例及比較例中所獲得之發泡片之密度，並將其倒數設為發泡倍率。
<獨立氣泡率>
依據ASTM D2856(1998)，使用島津製作所股份有限公司製造之 ACCUPYC 1330進行測定。
<凝膠分率(交聯度)>
自實施例及比較例中所獲得之發泡片取約50mg之試片，準確稱量試片之重量A(mg)。繼而，將該試片浸漬於105℃之二甲苯30ml中並放置24小時後，利用200目之金屬線網進行過濾並採集金屬線網上之不溶解成分，進行真空乾燥，準確稱量不溶解成分之重量B(mg)。根據所獲得之值，藉由下述式算出凝膠分率(質量%)。
凝膠分率(質量%)=(B/A)×100
<平均氣泡直徑>
將實施例及比較例中所獲得之發泡片切斷成50mm見方並於液態氮中浸漬1分鐘後，利用剃刀將其沿與MD方向及ZD方向平行之面切斷。使用數位顯微鏡(基恩士股份有限公司製造之「VHX-900」)對切斷面拍攝200倍之放大照片，針對MD方向上之長度2mm左右之切斷面所存在之所有氣泡測定MD方向之氣泡直徑。將該操作重複進行5次，將所有MD方向氣泡直徑之平均值設為MD方向之平均氣泡直徑。
除沿與發泡片TD方向及ZD方向平行之面切斷以外，以與上述相同之方式拍攝200倍之放大照片，針對TD方向上之長度2mm左右之切斷面所存在之所有氣泡測定TD方向之氣泡直徑。將該操作重複進行5次，將所有TD方向氣泡直徑之平均值設為TD方向之平均氣泡直徑。
<23℃之抗拉力、及90℃之抗拉力>
於23℃或90℃之條件下使用拉伸試驗機並依據JIS K6767(A法)測定實施例及比較例中所獲得之發泡片之抗拉力。就提高片材之剪切強度之觀 點而言，抗拉力之值較佳為較大。
<25%壓縮強度>
25%壓縮強度係指依據JIS K6767對聚烯烴系樹脂發泡片進行測定而得者。就提高柔軟性及階差追隨性之觀點而言，25%壓縮強度之值較佳為較小。
<90℃之剪切強度>
於發泡片之30mm見方之範圍內塗佈接著劑。其後，立刻以與上述接著劑塗佈部分重合之方式放置短邊30mm、長邊100mm之木製治具A，使發泡片與治具A壓接，其後，沿著治具A之大小將發泡片切斷。
繼而，將接著劑塗佈於切斷之發泡片之未接著治具A之面，其後立刻將木製治具B重疊，並使發泡片與治具B壓接。
將其於室溫下放置24小時，藉此使接著劑熟化而製成剪切強度測定用樣品。
繼而，以使發泡片之片材面相對於拉伸方向成為平行之方式將剪切強度測定用樣品安裝於設置有1kN之負載單元之試驗機(A&D股份有限公司製造之「Tensilon萬能材料試驗機」)。將治具之一側以速度100mm/min垂直向上拉伸而使發泡片層間剝離。測定此時之負載，並將其最大值設為剪切強度，藉此進行測定。
實施例1
將作為聚烯烴系樹脂之直鏈狀低密度聚乙烯(LLDPE)(埃克森化學公司製造之「Exact 3027」，密度：0.900g/cm3)100質量份、作為熱分解型發泡劑之偶氮二甲醯胺2.0質量份、作為分解溫度調整劑之氧化鋅1質量份、及作為抗氧化劑之2,6-二第三丁基對甲酚0.5質量份供給至擠出機，並於 130℃進行熔融混練，擠出厚度約0.3mm之長條片狀之聚烯烴系樹脂組成物。
繼而，於對上述長條片狀之聚烯烴系樹脂組成物之兩面照射4.5Mrad之加速電壓500kV之電子束而使之交聯後，連續地送入藉由熱風及紅外線加熱器而保持為250℃之發泡爐內進行加熱，從而使之發泡，並且一面使之發泡，一面將MD之延伸倍率設為1.5倍、將TD之延伸倍率設為1.7倍來進行延伸，藉此獲得厚度0.06mm之發泡片。將所獲得之發泡片之評價結果示於表1。
實施例2~9、比較例1~8
使聚烯烴系樹脂組成物之組成如表1及2所示般變更，並且將交聯時之劑量以成為表1及2之凝膠分率(交聯度)之方式進行調整，將TD之延伸倍率調整為1.2倍~3.5倍，除該等方面以外，與實施例1同樣地實施。
再者，於實施例8、9、比較例8中，如表1、2所記載般，作為聚烯烴樹脂，除實施例1中使用之直鏈狀低密度聚乙烯以外，亦使用乙烯-乙酸乙烯酯共聚物(EVA)(乙酸乙烯酯量19質量%，Tosoh股份有限公司製造，商品名「Ultrathene 636」)。
根據上述結果明確得知，根據本發明，可提供一種即便厚度較薄亦具有優異之剪切強度之聚烯烴系樹脂發泡片。更具體而言，例如於使用相同之樹脂且具有相同程度之壓縮強度之發泡片中，即便厚度較薄，亦可發揮優異之剪切強度。

Claims (8)

  1. 一種聚烯烴系樹脂發泡片，其係將聚烯烴系樹脂發泡而成者，上述發泡片之發泡倍率為1.5~20cm3/g，上述發泡片之MD方向及TD方向之平均氣泡直徑為130μm以下，且滿足下述式(1)及式(2)：TM/D≧6 (1) TT/D≧5 (2)TM：90℃之MD方向之抗拉力TT：90℃之TD方向之抗拉力D：上述發泡片之密度(g/cm3)。
  2. 如申請專利範圍第1項之聚烯烴系樹脂發泡片，其90℃之剪切強度為0.3~10MPa。
  3. 如申請專利範圍第1或2項之聚烯烴系樹脂發泡片，其25%壓縮強度為10~1,000kPa。
  4. 如申請專利範圍第1至3項中任一項之聚烯烴系樹脂發泡片，其23℃之MD方向之抗拉力為0.5~35MPa。
  5. 如申請專利範圍第1至4項中任一項之聚烯烴系樹脂發泡片，其23℃之TD方向之抗拉力為0.5~30MPa。
  6. 如申請專利範圍第1至5項中任一項之聚烯烴系樹脂發泡片，其厚度為0.02~0.8mm。
  7. 如申請專利範圍第1至6項中任一項之聚烯烴系樹脂發泡片，其凝膠分率為5~60質量%。
  8. 一種黏著帶，其係於申請專利範圍第1至7項中任一項之聚烯烴系樹 脂發泡片之至少一面設置有黏著劑層。
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