TWI624498B - 聚四氟乙烯多孔質膜及其製造方法、以及使用其之通氣膜及通氣構件 - Google Patents
聚四氟乙烯多孔質膜及其製造方法、以及使用其之通氣膜及通氣構件 Download PDFInfo
- Publication number
- TWI624498B TWI624498B TW102127248A TW102127248A TWI624498B TW I624498 B TWI624498 B TW I624498B TW 102127248 A TW102127248 A TW 102127248A TW 102127248 A TW102127248 A TW 102127248A TW I624498 B TWI624498 B TW I624498B
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- Prior art keywords
- liquid
- membrane
- ptfe
- repellent
- porous membrane
- Prior art date
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 174
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 174
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Medicinal Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Laminated Bodies (AREA)
Abstract
本發明係一種聚四氟乙烯多孔質膜,其具有被撥液劑披覆之表面,且上述撥液劑為實質上僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物。該聚四氟乙烯多孔質膜適於阻擋液體及/或粉塵並同時使氣體透過之通氣膜、具體為例如防水通音膜、防水通氣膜、防塵通氣膜。
Description
本發明係關於一種經賦予撥液性之聚四氟乙烯多孔質膜及其製造方法。又,本發明係關於一種使用該多孔質膜之通氣膜及通氣構件。
近年來,行動電話、筆記型電腦、電子記事本、數位相機、遊戲機等電子機器一般具備音頻功能。該等機器雖期待能製成防水構造,但於具備音頻功能之電子機器之殼體中,通常必須在對應於揚聲器、麥克風、蜂鳴器等發音部及受音部之位置設有開口,通過該開口來傳達音頻,因此同時確保音頻功能與防水構造之目標不易實現。迄今為止,藉由利用防水通音膜堵塞設於殼體之開口而兼顧該開口處之通音性與防水性之防水通音膜,係由不易阻礙聲音透過之材料構成之薄膜,藉由對開口處配置該膜,可獲得良好之通音性並且可抑制水滲入殼體內部。對於防水通音膜,較佳為能同時阻擋水並使氣體透過之通氣膜,更具體而言,較佳為具有聚四氟乙烯(PTFE)多孔質膜之通氣膜(參照專利文獻1)。
具有PTFE多孔質膜之通氣膜除作為防水通音膜使用以外,亦可作為阻擋水及/或粉塵並同時使氣體透過之防水通氣膜或防塵通氣膜使用。然而,根據使用環境不同,通氣膜亦會與皮脂、界面活性劑、油等接觸。即便對通氣膜使用撥水性優異之PTFE多孔質膜,亦無法充分地防止表面張力低之液體滲入。因此,對於通氣膜,會根據其用途進行撥液處理,該撥液處理使用含有可賦予撥油性之含氟聚合物的處理劑。
眾所周知,具有碳數為8以上之直鏈狀全氟烷基(以下,有時將「直鏈狀全氟烷基」記為「Rf基」)之含氟聚合物適於賦予撥液性。碳數為8以上之Rf基之結晶性與碳數較少之(例如6以下)Rf基相比明顯較高,認為該結晶性之高低有助於優異之撥液性之表現。亦已知根據結晶性之高低,可自具有碳數為8以上之Rf基之處理劑獲得高後退接觸角(與前進接觸角均為動態接觸角)。該後退接觸角係隨著結晶性之提高,於碳數6至8之範圍內急遽增加。根據此種情況,為了對通氣膜賦予撥液性,使用含有具有碳數為8以上之Rf基之含氟聚合物的處理劑已成為慣例。
專利文獻1:日本專利特開2004-83811號公報
專利文獻2:日本專利特開平4-506982號公報
然而,上述以往之經賦予撥液性之通氣膜具有如下問題:於藉由模具進行之衝孔加工及組入於殼體(典型而言,對行動電話之殼體嵌入式麥克風或揚聲器部分之安裝)時,容易因變形而產生膜皺及膜鬆弛。於以往之經賦予撥液性之通氣膜中,因該膜皺及膜鬆弛而會導致通音性降低。
因此,本發明之目的在於提供一種確保能夠應實用上之要求之程度之撥液性,且抑制因加工時及對殼體組入時變形導致產生膜皺及膜鬆弛的PTFE多孔質膜。
本發明提供一種PTFE多孔質膜,其具有被撥液劑披覆之表面,上述撥液劑為實質上僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物。
本發明提供一種PTFE多孔質膜之製造方法,其係製造上述本發明之PTFE多孔質膜之方法,該方法包含:成形步驟,其係自含有PTFE之混合物成形片成形體;第1延伸步驟,其係將上述片成形體於第1方向上延伸而形成多孔質膜;撥液步驟,其係對在上述第1方向上延伸後之上述片成形體,使用含有實質上僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物作為撥液劑之撥液處理液,進行撥液處理;及第2延伸步驟,其係於與上述第1方向不同之第2方向上延伸,形成經賦予撥液性之多孔質膜。
本發明提供一種通氣膜,其係可阻擋液體及/或粉塵並同時使氣體透過者,且具有上述本發明之PTFE多孔質膜與通氣性支持材之積層構造,於至少一主面露出有上述PTFE多孔質膜。
本發明提供一種通氣構件,其具備:上述本發明之PTFE多孔質膜或上述本發明之通氣膜、及支持上述PTFE多孔質膜或上述通氣膜之支持構件。
根據本發明,可提供一種確保能夠應實用上之要求之程度之撥液性,且抑制因加工時及對殼體組入時變形導致產生膜皺及膜鬆弛的PTFE多孔質膜。
1、2、3、4‧‧‧通氣膜
5‧‧‧通氣構件
11‧‧‧PTFE黑色多孔質膜
12‧‧‧通氣性支持材
13‧‧‧PTFE多孔質膜
14‧‧‧支持構件
圖1係示意性表示本發明之通氣膜一例之剖面圖。
圖2係示意性表示本發明之通氣膜另一例之剖面圖。
圖3係示意性表示本發明之通氣膜再另一例之剖面圖。
圖4係示意性表示本發明之通氣膜再進而另一例之剖面圖。
圖5係示意性表示本發明之通氣構件一例之立體圖。
圖6A及圖6B係用以說明斷裂伸長率之評估方法之剖面圖。
以下,一面參照圖式,一面說明本發明之經賦予撥液性的PTFE多孔質膜(以下,有時記為「PTFE撥液多孔質膜」)、通氣膜及通氣構件之實施形態。再者,以下之記載並非限定本發明。
(PTFE撥液多孔質膜)
本實施形態之PTFE多孔質膜為經撥液處理之PTFE多孔質膜,具有被撥液劑披覆之表面。該撥液劑為實質上僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物。再者,所謂「實質上僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物」係指作為構成撥液劑之聚合物之單體,除不可避免之情形以外,不積極添加CH2=CHCOOCH2CH2C6F13以外之化合物。例如,構成撥液劑之聚合物之單體之至少98.0莫耳%以上、較理想為99.0莫耳%以上為CH2=CHCOOCH2CH2C6F13。構成撥液劑之聚合物之單體亦可僅由CH2=CHCOOCH2CH2C6F13構成。
為了對PTFE多孔質膜賦予超過實施撥液處理前之PTFE多孔質膜的撥液性能,構成撥液劑之化合物必須為側鏈具有由氟飽和之烴基(全氟烷基:Rf基)之構造。如上所述,於本實施形態中,使用Rf基為C6F13之丙烯酸酯作為撥液劑。
由上述撥液劑形成之被膜具有PTFE多孔質膜之加工時及對殼體之組入時不會產生膜皺及膜鬆弛之程度之柔軟性(追隨性)。因此,本實施形態之PTFE多孔質膜可將斷裂伸長率設為例如200~600%之範圍內。
此處所謂之斷裂伸長率係由針貫通試驗測定之拉伸最大荷重伸長率,詳情如下述實施例所記載般。
進而,根據上述撥液劑,可對PTFE多孔質膜賦予能夠應實用上之要求之程度之撥液性。
又,本實施形態之PTFE多孔質膜亦具備能夠應實用上之要求之程度之聲音特性。例如,可將500Hz下之聲壓損失(sound pressure loss)設為2.0dB以下、例如0.5~2.0dB之範圍內。求出此處所謂之聲壓損失之方法如下述實施例所記載般。
賦予撥液性之PTFE多孔質膜可藉由公知之方法獲得。例如,可藉由擠出成形及軋壓將PTFE細粉(fine powder)與成形助劑之混合物製成片狀,其後去除成形助劑而製成成形體之片材後,進一步將所獲得之片材延伸而形成。
對PTFE多孔質膜進行之撥液處理係使用上述撥液劑進行,但並不特別限定於撥液處理之方法。於本實施形態中,亦可採用與對PTFE多孔質膜進行之公知之撥液處理法相同之方法。如上所述,由上述撥液劑形成之被膜與由以往之撥液劑形成之被膜相比,具有較高之柔軟性。因此,藉由上述撥液劑,亦可於撥液處理之後將片材延伸。即,藉由上述撥液劑,撥液處理可於片材之延伸前實施,亦可於片材之延伸後實施。撥液處理係藉由於片材塗佈將撥液劑溶解於溶劑而成之溶液(撥液處理液)而實施。作為具體之方法,例如可列舉吻合塗佈法、凹版塗佈法及噴霧塗佈法等。再者,由於PTFE多孔質膜為化學穩定,故撥液處理液之溶劑之種類並無特別限定。
例如,撥液處理於延伸前實施之情形時之PTFE撥液多孔質膜之製造方法成為包含如下步驟之製造方法:成形步驟,其係自含有PTFE之混合物成形片成形體;
第1延伸步驟,其係將上述片成形體於第1方向(例如片成形體之長度方向)上延伸而形成多孔質膜;撥液步驟,其係對於在上述第1方向上延伸後之上述片成形體,使用含有實質上僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物作為撥液劑之撥液處理液,進行撥液處理;及第2延伸步驟,其係於與上述第1方向不同之第2方向(例如片成形體之寬度方向)上延伸,形成經賦予撥液性之多孔質膜。
以此方式製作而成之PTFE撥液多孔質膜具有以無數個形成之PTFE之微細纖維(fibril)間之空隙作為細孔的多孔質構造。該多孔質構造中之平均孔徑及孔隙率可藉由變更片材之延伸條件而調整,其具體值根據本實施形態之PTFE撥液多孔質膜之用途進行選擇即可。
本實施形態之PTFE撥液多孔質膜亦可進行染色處理。PTFE多孔質膜本來之顏色為白色。因此,於該PTFE多孔質膜以堵塞殼體之開口之方式配置時,有膜易引人注目之問題。因此,藉由根據所要配置之殼體對PTFE多孔質膜實施染色處理,可實現配置於殼體時不易引人注目之PTFE撥液多孔質膜。
染色處理例如可藉由如下操作實施,即,將PTFE多孔質膜浸漬於含有染料之染色液,或將含有染料之染色液塗佈於PTFE多孔質膜後,藉由乾燥等去除染色液中所含之染料之溶劑。浸漬及塗佈之方法並無特別限定。染料為可將未進行任何著色處理之白色之PTFE多孔質膜染色為其主面之白色度為30以下之染料,可使用偶氮系染料、苯胺黑系染料、蒽醌系染料、波絢(Procion)染料、雷馬素(Remazol)染料、油溶性染料等。染色液通常包含染料、及稀釋該染料使染色之作業性提高之溶劑。由於PTFE多孔質膜為化學穩定,故溶劑之種類並無特別限定,可根據染料之種類及染色之作業性等適當選擇。染色液中之染料之濃度必須為可將未進行任何
著色處理之白色之PTFE多孔質膜染色為其主面之白色度為30以下之濃度,通常為5重量%以上。
(通氣膜)
本實施形態之通氣膜之構成只要具有本實施形態之PTFE撥液多孔質膜,則無特別限定。
圖1係本實施形態之通氣膜之一例。圖1之通氣膜1係由本實施形態之PTFE撥液多孔質膜11構成。基於PTFE撥液多孔質膜11所具有之上述多孔質構造,通氣膜1具有阻擋液體及/或粉塵並同時使氣體透過之特性。又,由於通氣膜1為PTFE撥液多孔質膜11之單層構造,故可將面密度抑制為較低。通氣膜1之面密度越低,該膜中之聲音透過損失越小,藉此通音性提高。因此,通氣膜1尤其適於作為配置於具有發音部及/或受音部之電子機器2殼體之開口,用以確保該開口處之通音性與防水性之防水通音膜之用途。
當然,通氣膜1亦適於防水通音膜以外之用途,例如作為利用有阻擋液體及/或粉塵並同時使氣體透過之特性的防水通氣膜或防塵通氣膜用途。例如將防水通氣膜(防塵通氣膜)配置於燈、馬達、感測器、ECU等車輛用電氣零件之殼體,用於確保殼體內外之通氣,並且緩和因溫度變化所致之殼體內之壓力變化。
通氣膜1中之PTFE撥液多孔質膜11之平均孔徑一般為0.01~20μm,較佳為0.05~5μm。於將通氣膜1作為防水通音膜使用之情形時,自謀求防水性與通音性之併存之觀點而言,PTFE撥液多孔質膜11之平均孔徑較佳為1μm以下,更佳為0.7μm以下,進而較佳為0.5μm以下。平均孔徑之下限並無特別限定,例如為0.1μm。PTFE多孔質膜之平均孔徑可依據ASTM F316-86之規定而測定,例如可將依據該規定之能夠自動測定之市售之測定裝置(可自美國Porous Material Inc.獲取之Perm-Porometer)利
用於PTFE多孔質膜之平均孔徑之測定。
於將通氣膜1作為防水通音膜使用之情形時,自謀求作為膜之物理性強度與通音性之併存之觀點而言,通氣膜1之面密度較佳為1~10g/m2,更佳為2~8g/m2,進而較佳為3~6g/m2。於將通氣膜作為並不要求良好之通音性之防水通氣膜或防塵通氣膜使用之情形時,通氣膜1之面密度無特別限定。
PTFE撥液多孔質膜11例如亦可被染為黑色。於PTFE撥液多孔質膜11如此般被進行染色之情形時,即便將通氣膜1配置於例如電子機器之殼體之開口處,與白色之PTFE多孔質膜相比亦不會引人注目。關於使用經染色處理之PTFE撥液多孔質膜11之效果,以後之圖2、3所示之通氣膜2、3、4亦相同。
圖2係本實施形態之通氣膜之另一例。圖2之通氣膜2具有本實施形態之PTFE撥液多孔質膜11與支持該多孔質膜11之通氣性支持材12之積層構造。通氣膜2基於PTFE撥液多孔質膜11所具有之上述多孔質構造而具有阻擋液體及/或粉塵並同時使氣體透過之特性。通氣膜2中PTFE撥液多孔質膜11露出,例如即便將通氣膜2配置於電子機器之殼體之開口處,只要PTFE撥液多孔質膜11面向殼體之外部,則與白色之PTFE多孔質膜相比亦不會引人注目。通氣膜2之用途無特別限定,可較佳地使用於防水通音膜、防水通氣膜、防塵通氣膜等。
通氣性支持材12之材料或構造並無特別限定,但較佳為通氣性優於PTFE撥液多孔質膜11。通氣性支持材12例如為由金屬或樹脂或該等之複合材料構成之織布、不織布、篩網、網狀物、海綿、泡沫、多孔體。樹脂例如為聚烯烴、聚酯、聚醯胺、聚醯亞胺、聚芳醯胺(aramid)、氟樹脂、超高分子量聚乙烯。於將PTFE撥液多孔質膜11與通氣性支持材12積層時,可使用熱層壓、加熱熔接、超音波熔接等各種接合方法將兩者
接合。
通氣膜2亦可具有2層以上之PTFE撥液多孔質膜11及/或2層以上之通氣性支持材12,於此情形時,其積層順序無特別限定。然而,為了在配置於電子機器之殼體之開口處時進而確實地阻擋液體及/或粉塵,較佳為如圖2所示,於至少一主面露出有PTFE撥液多孔質膜11。換言之,本實施形態之通氣膜可具有本實施形態之PTFE撥液多孔質膜與通氣性支持材之積層構造,於此情形時,較佳為於至少一主面露出有PTFE撥液多孔質膜。
通氣膜2中之PTFE撥液多孔質膜11之平均孔徑如圖1所示之通氣膜1之說明中所例示般。將通氣膜2作為防水通音膜使用之情形時PTFE撥液多孔質膜11之平均孔徑亦如圖1所示之通氣膜1之說明中所例示般。於通氣膜2具有2層以上之PTFE撥液多孔質膜11之情形時,至少1層之PTFE撥液多孔質膜11具有所例示之平均孔徑即可。
於將通氣膜2作為防水通音膜使用之情形時,自謀求作為膜之物理性強度與通音性之併存之觀點而言,通氣膜2之面密度(包含PTFE撥液多孔質膜11及通氣性支持材12之複數層之合計)較佳為1~10g/m2,更佳為2~8g/m2,進而較佳為3~6g/m2。
圖3係本實施形態之通氣膜之又一例。圖3之通氣膜3具有本實施形態之PTFE撥液多孔質膜11和與其不同之另一PTFE多孔質膜13之積層構造。PTFE多孔質膜13可不實施撥液處理,亦可藉由公知之撥液劑實施撥液處理。又,亦可實施與PTFE撥液多孔質膜11相同之撥液處理。又,PTFE多孔質膜13可為無著色(即白色)亦可被著色為任意顏色(例如黑色)。PTFE多孔質膜13與PTFE撥液多孔質膜11同樣地具有將無數個形成之PTFE之微細之纖維(fibril)間之空隙設為細孔之多孔質構造。通氣膜3係基於選自PTFE撥液多孔質膜11及PTFE多孔質膜13之至少一個PTFE
多孔質膜所具有之上述多孔質構造,而具有阻擋液體及/或粉塵並同時使氣體透過之特性。
通氣膜3中被實施撥液處理之多孔質膜11露出,例如即便於將通氣膜3配置於電子機器之殼體之開口處時,只要PTFE撥液多孔質膜11面向殼體之外部,則亦可進而確實地阻擋液體及/或粉塵。即,本實施形態之通氣膜可具有本實施形態之PTFE撥液多孔質膜11和與其不同之另一PTFE多孔質膜13之積層構造,於此情形時,較佳為於至少一主面露出有PTFE撥液多孔質膜11。
通氣膜3亦可具有2層以上之PTFE撥液多孔質膜11及/或2層以上之PTFE多孔質膜13,於此情形時,其積層順序無特別限定。
通氣膜3之用途並無特別限定,可較佳地使用於防水通音膜、防水通氣膜、防塵通氣膜。
通氣膜3中,選自PTFE撥液多孔質膜11及PTFE多孔質膜13之至少一個PTFE多孔質膜之平均孔徑如圖1所示之通氣膜1之說明中所例示般。將通氣膜3作為防水通音膜使用之情形亦同樣地,選自PTFE撥液多孔質膜11及PTFE多孔質膜13之至少一個PTFE多孔質膜之平均孔徑如圖1所示之通氣膜1之說明中所例示般。於通氣膜3具有2層以上之PTFE撥液多孔質膜11及/或PTFE多孔質膜13之情形時,至少1層之PTFE撥液多孔質膜11或PTFE多孔質膜13具有所例示之平均孔徑即可。PTFE撥液多孔質膜11之平均孔徑與PTFE多孔質膜13之平均孔徑可相同亦可不同。
於將通氣膜3作為防水通音膜使用之情形時,自謀求作為膜之物理性強度與通音性之併存之觀點而言,通氣膜3之面密度(包含PTFE撥液多孔質膜11及PTFE多孔質膜13之複數層之合計)較佳為1~10g/m2,更佳為2~8g/m2,進而較佳為3~6g/m2。
圖4係本實施形態之通氣膜之又一例。圖4之通氣膜4係於
圖3所示之通氣膜3進而具有通氣性支持材12。通氣膜4中被實施撥液處理之多孔質膜11露出。通氣性支持材12如圖2所示之通氣膜2之說明中所示般。
本實施形態之通氣膜亦可具有除PTFE撥液多孔質膜11、通氣性支持材12、PTFE多孔質膜13以外之任意構件。此時,PTFE撥液多孔質膜11較佳為於本實施形態之通氣膜中之至少一主面露出。
(通氣構件)
將本實施形態之通氣構件之一例示於圖5。圖5所示之通氣構件5具備本實施形態之通氣膜1。通氣膜1為圓板狀,於通氣膜1之周緣部安裝有環狀之支持構件14。根據設置有環狀之支持構件14之形態,可加強通氣膜1,並且其操作變得容易。又,由於支持構件14成為安裝於電氣製品之殼體之物件,故通氣膜1對殼體之安裝作業性提高。關於該通氣構件,可代替通氣膜1,而使用通氣膜2~4之任一者,亦可使用PTFE撥液多孔質膜11。
支持構件之形狀只要可支持本實施形態之通氣膜,則無特別限定。支持構件之材質亦無特別限定,典型而言由樹脂或金屬或該等之複合材料構成。
通氣膜1與支持構件14之接著方法無特別限定,例如可應用加熱熔接、超音波熔接、利用接著劑之接著、利用雙面膠帶之接著等方法。
實施例
最初,示出本實施例中製作而成之PTFE撥液多孔質膜之評估方法。
[斷裂伸長率]
斷裂伸長率係由圖6A及圖6B所示之針貫通試驗(針之直徑:2mm)測定之拉伸最大荷重伸長率,由下式予以定義。針貫通試驗中,首先,如
圖6A所示,利用試樣架63以達到繃緊狀態之方式載持試驗片61(此處為PTFE撥液多孔質膜)。將針62之前端垂直碰觸於試驗片61之膜面,使針62向抵壓於試驗片61之方向移動,而對試驗片61施加荷重。將如圖6B所示般針62貫通試驗片61時(最大荷重時)之試驗片61之伸長率設為斷裂伸長率。
I={(A-X)/X}×100(式)
I:斷裂伸長率(拉伸最大荷重伸長率)(%)
Y:最大荷重時之針62之移動距離(mm)
X:針62與試樣架63之間的距離(mm)
A:(X2+Y2)1/2
[聲音特性(聲壓損失)]
PTFE撥液多孔質膜之聲音特性係以如下方式進行評估。
最初,準備假定為行動電話之殼體之模擬殼體(聚苯乙烯製造、外形67mm×37mm×12mm)。於該模擬殼體中設置有各1處揚聲器安裝孔(=13mm)及揚聲器纜線之導通孔。再者,該模擬殼體中,除該揚聲器安裝孔及揚聲器纜線之導通孔以外,無開口。繼而,將雙面膠帶(日東電工製造、No.5620A、厚度0.2mm)衝孔為外徑16mm、內徑13mm之環狀,使用該環狀之雙面膠帶,於模擬殼體中之揚聲器安裝孔之內側貼附揚聲器(斯大精密製造、SCG-16A)。揚聲器纜線通過上述導通孔導出至模擬殼體之外部。再者,導出揚聲器纜線後,利用油灰(putty)堵塞導通孔。
繼而,使用湯姆森(Thomson)模將各實施例及比較例之PTFE撥液多孔質膜衝孔成直徑16mm之圓形。使用上述環狀之雙面膠帶將經衝孔之PTFE撥液多孔質膜貼附於模擬殼體中之揚聲器安裝孔之外側。於將PTFE撥液多孔質膜貼附於模擬殼體時,使PTFE撥液多孔質膜覆蓋揚聲器安裝孔之整體,且於雙面膠帶與模擬殼體之間、以及PTFE撥液多孔質膜與
雙面膠帶之間不出現間隙。
繼而,將揚聲器纜線與麥克風(B & K製造、型號2669)連接於聲音評估裝置(B & K製造、Multi-analyzer System 3560-B-030)。麥克風配置於與模擬殼體之揚聲器安裝孔相距50mm之位置。
繼而,作為評估方式,選擇、執行SSR分析(試驗信號20Hz~20kHz、sweep(掃描)),評估PTFE撥液多孔質膜之聲音特性(聲壓損失)。再者,未貼附PTFE撥液多孔質膜而另外測定之空白樣品之聲壓為84dB(頻率500Hz)。
聲壓損失係由自聲音評估裝置輸入至揚聲器之試驗信號、及麥克風接收到之信號自動求出,係藉由上述空白樣品之聲壓減去貼附有PTFE撥液多孔質膜之狀態下測定出之聲壓而獲得之值。可判斷聲壓損失越小,越能夠維持自揚聲器輸出之音量。
[通氣度]
PTFE撥液多孔質膜之通氣度係依據JIS P8117(哥雷(Gurley)法)而評估。
[耐水壓]
PTFE撥液多孔質膜之耐水壓係使用JIS L1092中記載之耐水度試驗機(高水壓法)而求出。但若為JIS L1092中所規定之面積則膜顯著變形,故將不鏽鋼篩網(開口徑2mm)設置於膜之加壓面之相反側,以抑制了變形之狀態進行測定。
[撥液性]
將複製用紙與PTFE撥液多孔質膜以複製用紙成為下方之方式積層,使用點滴器對PTFE撥液多孔質膜滴1滴煤油後,放置1分鐘。其後,除去多孔質膜確認複製用紙之狀態,將複製用紙被煤油潤濕之情形設為無PTFE多孔質膜之撥液性,將未被潤濕之情形設為有撥液性。
[加工及組入時之膜皺及膜鬆弛產生之有無]
於各實施例及比較例中獲得之PTFE撥液多孔質膜之一面,使用雙面膠帶(日東電工製造、No.5603)貼合厚度0.1mm之聚對苯二甲酸乙二酯(PET)膜,進而亦於PTFE撥液多孔質膜之另一面貼附雙面膠帶(日東電工製造、No.5620A),而製作積層體。對該積層體,以外徑6.0mm、內徑2.5mm實施衝孔加工,製作50個(樣品數N=50)試驗樣品。再者,內徑2.5mm之孔於構成積層體之層中僅形成於PET膜與雙面膠帶,於PTFE撥水多孔質膜中未形成。其後,將該樣品以堵塞麥克風安裝孔之方式組入設置有麥克風安裝孔(1.0mm)之模擬殼體(聚苯乙烯製造、外形60mm×50mm×25mm),安裝麥克風(Knowles Acoustics公司製造、SPM0405HD4H),以成為相當於安裝前之厚度之70%的方式進行鉚接固定。其後,卸除所組入之樣品。於衝孔加工後、組入中、卸除後分別以目視確認樣品之膜皺及膜鬆弛之有無,求出50個樣品中產生膜皺及膜鬆弛之樣品之數量。
(實施例1)
將PTFE細粉(大金工業製造、F104)100重量份、與作為成形助劑之正十二烷(Japan Energy製造)20重量份均勻地混合,使用氣缸將所獲得之混合物壓縮後進行柱塞擠出而製成片狀之混合物。繼而,將所獲得之片狀混合物通過一對金屬輥而軋壓為厚度0.2mm,進而藉由150℃之加熱乾燥去除成形助劑,而獲得PTFE之片成形體。繼而,將所獲得之片成形體於其長度方向(軋壓方向)上以延伸溫度260℃、延伸倍率10倍進行延伸。
繼而,將以上述方式製作而成之PTFE多孔質膜於混合黑色染料(Orient Chemical Industries製造、SP BLACK 91-L、乙醇稀釋溶液25wt%)20重量份與作為染料之溶劑之乙醇(純度95%)80重量份所得之染色液中浸漬數秒鐘後,將整體加熱至100℃而乾燥去除溶劑,獲得染為黑色之PTFE多孔質膜。
繼而,將所獲得之PTFE多孔質膜於以實質上僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物為撥液成分之撥液處理液中浸漬數秒鐘。撥液處理液係以如下方式製備而成。首先,將CH2=CHCOOCH2CH2C6F13100g、作為聚合起始劑之偶氮雙異丁腈0.1g、作為溶劑之信越化學工業公司製造之「FS稀釋劑」300g投入至裝設有氮氣導入管、溫度計、攪拌機之燒瓶中,一面導入氮氣以70℃進行攪拌一面進行16小時加成聚合,獲得含氟聚合物80g。該聚合物之數平均分子量為100000。將該含氟聚合物以成為3.0重量%之方式利用稀釋劑(信越化學工業公司製造之「FS稀釋劑」)進行稀釋,而製備撥液處理液。將浸漬於撥液處理液後之PTFE多孔質之整體加熱至100℃,乾燥去除溶劑,獲得經撥液處理之PTFE多孔質膜(PTFE撥液多孔質膜)。
繼而,於寬度方向上以延伸溫度150℃、延伸倍率10倍延伸,進而將整體以超過PTFE之熔點之溫度即360℃煅燒,獲得PTFE撥液多孔質膜。所獲得之PTFE撥液多孔質膜之平均孔徑為0.5μm,面密度為6g/m2。所獲得之PTFE撥液多孔質膜之斷裂伸長率、聲壓損失、通氣度、耐水性及撥液性如表1所示。又,加工及組入時之膜皺及膜鬆弛產生之有無如表2所示。
(實施例2)
除將寬度方向之延伸倍率設為15倍以外,以與實施例1相同之方式獲得經撥液處理之PTFE撥液多孔質膜(實施例2)。實施例2之PTFE撥液多孔質膜之面密度為4g/m2。斷裂伸長率、聲壓損失、通氣度、耐水性及撥液性如表1所示。又,加工、組入及卸除時之膜皺及膜鬆弛產生之有無如表2所示。
(實施例3)
除將寬度方向之延伸倍率設為7倍以外,以與實施例1相同之方式獲
得經撥液處理之PTFE撥液多孔質膜(實施例3)。實施例3之PTFE撥液多孔質膜之面密度為8.6g/m2。斷裂伸長率、聲壓損失、通氣度、耐水性及撥液性如表1所示。又,加工、組入及卸除時之膜皺及膜鬆弛產生之有無如表2所示。
(比較例1)
將CH2=C(CH3)COOCH2CH2C8F17100g、作為聚合起始劑之偶氮雙異丁腈0.1g、作為溶劑之信越化學工業公司製造之「FS稀釋劑」300g投入至裝設有氮氣導入管、溫度計、攪拌機之燒瓶中,一面導入氮氣以70℃進行攪拌一面進行16小時加成聚合,獲得含氟聚合物80g。該聚合物之數平均分子量為100000。將該含氟聚合物以濃度達到3.0重量%之方式利用稀釋劑(信越化學工業公司製造之「FS稀釋劑」)進行稀釋而製備撥液處理液。除使用該撥液處理液以外,以與實施例1相同之方式獲得經撥液處理之PTFE撥液多孔質膜(比較例1)。再者,比較例1之PTFE撥液多孔質膜藉由撥液處理寬度方向之伸長率明顯降低,而無法延伸。因此,斷裂伸長率、聲壓損失、通氣度、耐水性及撥液性無法評估。又,加工、組入及卸除時之膜皺及膜鬆弛產生之有無亦無法評估。
(比較例2)
使用與比較例1相同之撥液處理液,且將撥液處理及染色處理於延伸及煅燒後進行而非於寬度方向之延伸前進行,除此以外,以與實施例1相同之方式獲得經撥液處理之PTFE撥液多孔質膜(比較例2)。比較例2之PTFE撥液多孔質膜之面密度為6g/m2。斷裂伸長率、聲壓損失、通氣度、耐水性及撥液性如表1所示。又,加工及組入時之膜皺及膜鬆弛產生之有無如表2所示。
將僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物用作撥液劑之實施例1~3之PTFE撥液多孔質膜儘管係於寬度方向之延伸前進行撥液處理,寬度方向之伸長率仍不會降低而可延伸。相對於此,將以CH2=C(CH3)COOCH2CH2C8F17為單體聚合而成之聚合物用作撥液劑之情形時,若於延伸前進行撥液處理,則其後無法延伸(比較例1),必須於延伸後進行撥液處理(比較例2)。實施例1~3之PTFE撥液多孔質膜較比較例2之PTFE撥液多孔質膜而言,斷裂伸長率及通氣度之特性優異。
如表2所示,將僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物用作撥液劑的實施例1~3其PTFE撥液多孔質膜於衝孔加工後、組入中及卸除後之任一情形時均未確認到膜皺及膜鬆弛之產生。相對於此,確認到比較例2之PTFE撥液多孔質膜於衝孔中有1個樣品出現皺折。可確認到,組入中有7個樣品、卸除後有2個樣品皺折消除,但仍有5個樣品殘留有皺折。
認為產生膜皺或膜鬆弛之原因在於:第1,由於在衝孔加工或鉚接之步驟中對厚度方向施加荷重,故衝孔內徑收縮0.2~0.5%之幅度;
第2,無法追隨內徑收縮之膜(膜未收縮之情形)產生皺折或鬆弛。一般而言,若對延伸後之PTFE多孔質膜實施染色處理或撥液處理,則延伸時之殘留應力產生影響,寬度方向或長度方向會收縮。認為若產生該收縮,則衝孔加工或鉚接之步驟中無法收縮,而成為皺折或鬆弛產生之原因之一。然而,認為藉由如本發明之PTFE撥液多孔質膜般,使用柔軟性較高之撥液劑CH2=CHCOOCH2CH2C6F13,可改善塗佈被膜之物性,進而實現撥液處理後之向寬度方向之延伸,亦可防止上述機制所致之皺折或鬆弛之產生。
[產業上之可利用性]
本發明之PTFE多孔質膜可使用於與以往之PTFE多孔質膜相同之用途、例如防水通音膜、防水通氣膜、防塵通氣膜。
Claims (8)
- 一種聚四氟乙烯多孔質膜,其具有被撥液劑披覆之表面,該撥液劑為實質上僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物。
- 如申請專利範圍第1項之聚四氟乙烯多孔質膜,其被染為黑色。
- 如申請專利範圍第1項之聚四氟乙烯多孔質膜,其中,斷裂伸長量為200~600%。
- 如申請專利範圍第1項之聚四氟乙烯多孔質膜,其於500Hz之聲壓損失為0.5~2.0dB。
- 一種聚四氟乙烯多孔質膜之製造方法,其係製造申請專利範圍第1項之聚四氟乙烯多孔質膜之方法,該方法包含:成形步驟,其係自含有聚四氟乙烯之混合物成形片成形體;第1延伸步驟,其係將該片成形體於第1方向上延伸而形成多孔質膜;撥液步驟,其係對在該第1方向上延伸後之該片成形體,使用含有實質上僅以CH2=CHCOOCH2CH2C6F13為單體聚合而成之聚合物作為撥液劑的撥液處理液,進行撥液處理;及第2延伸步驟,其係於與該第1方向不同之第2方向上延伸,形成經賦予撥液性之多孔質膜。
- 一種通氣膜,其係阻擋液體及/或粉塵並同時使氣體透過者,具有申請專利範圍第1項之聚四氟乙烯多孔質膜與通氣性支持材之積層構造,於至少一主面露出有該聚四氟乙烯多孔質膜。
- 一種通氣構件,其具備申請專利範圍第1項之聚四氟乙烯多孔質膜、及支持該聚四氟乙烯多孔質膜之支持構件。
- 一種通氣構件,其具備申請專利範圍第6項之通氣膜、及支持該通氣膜之支持構件。
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