TW201351444A - 電子絕緣材料 - Google Patents

電子絕緣材料 Download PDF

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Publication number
TW201351444A
TW201351444A TW102109750A TW102109750A TW201351444A TW 201351444 A TW201351444 A TW 201351444A TW 102109750 A TW102109750 A TW 102109750A TW 102109750 A TW102109750 A TW 102109750A TW 201351444 A TW201351444 A TW 201351444A
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TW
Taiwan
Prior art keywords
article
woven
layers
nonwoven
woven paper
Prior art date
Application number
TW102109750A
Other languages
English (en)
Inventor
Robert Hamilton Turpin
David Stanley Stankes
Martin Harold Fox
Mitchell Tseng-Teh Huang
Original Assignee
3M Innovative Properties Co
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Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of TW201351444A publication Critical patent/TW201351444A/zh

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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/659—Including an additional nonwoven fabric
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/693—Including a paper layer

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Abstract

本發明提供一種物件，其含有介於兩個非纖維素性非編織紙層之間的非纖維素性不織布層，其中該非編織紙及該不織布中之一或兩者為電子絕緣的。至少一些實施例為阻燃性的。

Description

電子絕緣材料
本發明係關於適用於電子絕緣應用之材料。
電子裝備(諸如電動馬達、發電機及變壓器)常常需要某種形式之介電絕緣以將處於一種電壓下之導體與處於不同電壓下之導體隔開及/或向電子組件提供機械保護。工業中常常使用電子絕緣材料之層合物來達成此目的。該等材料之實例描述於WO 2012/082180、JP 2000/008299、CA 2003221及JP 9158092中。
某些電子絕緣應用中需要可達到高耐火性等級(例如UL 94V-0)同時仍提供優良機械強度且在熱老化後保留可撓性之材料。
本發明之材料適用於使變壓器、馬達、發電機及其他需要電子組件絕緣之裝置中之電子組件(尤其具有阻燃性要求之電子組件)絕緣。至少一些本發明實施例提供具有極佳機械強度、可撓性及耐火性之獨特可撓性電子絕緣物件。儘管至少一些本發明實施例含有一些可燃材料，但其仍能夠達到高耐火性等級。至少一些本發明實施例提供一種具有理想的性質(包括阻燃性、介電強度、拉伸強度及撕裂強度)平衡之電子絕緣材料。至少一些本發明實施例另外提供理想的導熱性質。
至少一個本發明實施例提供一種包含非纖維素性不織布層之物 件，該非纖維素性不織布層具有對置的第一主表面及第二主表面且具有附著至不織布層之各主表面之非纖維素性非編織紙層，其中非編織紙及不織布中之一或兩者為電子絕緣的。
如本說明書中所使用：「非纖維素性」意謂含有小於10重量%之纖維素材料，較佳含有小於5重量%之纖維素材料，更佳僅含有微量之纖維素材料且最佳不含纖維素材料。
「直接融合」意謂不存在介入層，諸如黏著層；「非編織紙」意謂主要包含短纖維之薄片材料；「不織布」意謂主要包含長纖維之薄片材料；「短纖維」意謂長度小於1吋之纖維；「長纖維」意謂長度大於或等於1吋之纖維；「MD」或「縱向」係指平行於連續材料薄片之收捲方向之方向；及「CD」或「橫向」係指垂直於連續材料薄片之收捲方向之方向。
至少一個本發明實施例之優點在於儘管其含有可燃纖維材料，但其仍在UL 94耐火性測試中達到V-0等級，同時亦為可撓性的且具有良好機械強度。
本發明之上述【發明內容】不欲描述本發明之各揭示實施例或每個實施。以下【實施方式】更具體地說明本發明之實施例。
在以下描述中，應瞭解，涵蓋其他實施例且其可在不脫離本發明之範疇或精神的情況下產生。因此，以下【實施方式】並不視為限 制性含義。
除非另有指示，否則說明書及申請專利範圍中所用之所有表示特徵尺寸、量及物理性質之數值應理解為在所有情況下均由術語「約」修飾。因此，除非有相反指示，否則本說明書及隨附申請專利範圍中所闡述之數值參數為近似值，其可視熟習此項技術者利用本文所揭示之教示內容設法獲得之所需性質而變化。由端點表示之數值範圍的使用包括彼範圍內之所有數值及任何值(例如1至5包括1、1.5、2、2.75、3、3.80、4及5)。
至少一個本發明實施例提供介於兩個非編織紙層之間的不織布層。其他實施例提供交替之非編織紙層及不織布層。一些實施例提供彼此相鄰且介於非編織紙層之間的多個不織布層。一些實施例另外包括介於兩個相鄰層之間的黏著劑。
提供耐火性之物件之至少一些實施例包括可燃材料。舉例而言，一些實施例包括可燃性PET非編織物。在至少一些實施例中，發現將可燃性不織布層置於至少兩個外部非編織紙層之間可向物件提供極佳耐火性質。
至少一些本發明實施例之非編織紙層包含由短纖維(亦即長度小於1吋(2.54 cm)之纖維)製成之薄片材料。在至少一個本發明實施例中，非編織紙中之大部分纖維為有機的。然而，許多實施例可包括具有無機纖維或填料之非編織紙。
適用於本發明之市售非編織紙之實例包括可按商標名CeQUIN自3M Company,USA獲得之非編織紙，包括(但不限於)CeQUIN I(約90%無機內含物)、CeQUIN II(CeQUIN I之雙層(單布層)複合物)、CeQUIN X(濕強度增強以供B級應用)及CeQUIN 3000(約74%無機內含物加上有機纖維強化物)；FLAME BARRIER FRB，包括(但不限於)FLAME BARRIER-FRB-NT壓延型絕緣紙及FLAME BARRIER FRB- NC非壓延型絕緣紙；可按商標名NOMEX自DuPont(www2.dupont.com)獲得之非編織紙，包括(但不限於)NOMEX紙410型、411型(較低密度型式)、414型、418型(包括雲母)、419型(418型之較低密度型式)及E56型；可按商標名X-FIPER自SRO Group(China)Limited獲得之非編織紙；及可按商標名METASTAR自Yantai Metastar Special Paper Co.,Ltd.,China獲得之非編織紙。
適合之非編織紙可包括有機及無機纖維，諸如(但不限於)芳族聚醯胺(包括間芳族聚醯胺及對芳族聚醯胺)、聚苯硫醚(PPS)、聚酯、聚醯胺、丙烯酸類、三聚氰胺、玻璃、聚烯烴及聚醯亞胺。在至少一個本發明實施例中，非編織紙亦包含聚合黏合劑。適合之聚合黏合劑包括(但不限於)丙烯酸類、腈、苯乙烯丙烯酸系乳膠、瓜爾膠(guar gum)、澱粉及天然橡膠乳膠。
在至少一個本發明實施例中，非編織紙亦包含一或多種無機填料。適合之無機填料包括(但不限於)高嶺黏土、滑石、雲母、碳酸鈣、三水合氧化鋁、蒙脫石(montmorillonite)、膨潤石(smectite)、膨潤土(bentonite)、伊利石(illite)、綠泥石(chlorite)、海泡石(sepiolite)、鎂鋁海泡石(attapulgite)、埃洛石(halloysite)、蛭石(vermiculite)、合成鋰皂石(laponite)、累托石(rectorite)、珍珠岩(perlite)、氮化鋁、碳化矽、氮化硼及其組合。適合類型之高嶺黏土包括(但不限於)水洗滌之高嶺黏土；分層高嶺黏土；經煅燒之高嶺黏土；及經表面處理之高嶺黏土。
含有無機纖維及無機粒子中之一或兩者之本發明非編織紙可稱為基於無機物之紙。與例如完全基於有機物之間芳族聚醯胺紙相比，基於無機物之紙在存在電暈/部分放電之情況下提供改良之長期耐壓特性，此係因為已知無機材料對電暈之抗性比有機材料大得多(參見例如The Electrical Insulation Conference(EIC)/Electrical Manufacturing and Coil Winding(EMCW)Expo 2001,Cincinnati,Ohio 10/15-10/18/2001,High Temperature Electrical Insulation Short Course，第21頁)。此等基於無機物之紙與例如完全基於有機物之間芳族聚醯胺紙相比，亦可提供較大尺寸穩定性以及較高導熱性，用於改良熱消散。
至少一些本發明實施例之不織布層包含由長纖維(亦即長度大於或等於1吋(2.54 cm)之纖維)製成之薄片材料。
不織布層通常主要由有機纖維製成，但亦可含有無機纖維。適用於製造不織布之有機纖維之實例包括(但不限於)芳族聚醯胺纖維，包括間芳族聚醯胺纖維及對芳族聚醯胺纖維。適用於本發明之不織布之至少一些實施例可包括間芳族聚醯胺纖維及對芳族聚醯胺纖維中之一或兩者。在至少一個本發明實施例中，芳族聚醯胺纖維為不織布層之較佳組分。本發明之不織布之至少一些實施例可包括一或多種類型之芳族聚醯胺纖維。芳族聚醯胺纖維之類型包括(但不限於)間芳族聚醯胺、對芳族聚醯胺、經改質之間芳族聚醯胺或對芳族聚醯胺，或其他類型之芳族聚醯胺。不織布可包含0(零)至100重量%之量的芳族聚醯胺纖維。在至少一個實施例中，不織布包含約20重量%至約70重量%芳族聚醯胺纖維。
適合之非芳族聚醯胺有機纖維包括(但不限於)聚苯硫醚(PPS)、聚酯(包括聚對苯二甲酸伸乙酯(PET)及聚(對苯二甲酸環己烷二甲醇酯)(PCT))、經乙二醇改質之聚酯、聚苯碸、聚醯胺(耐綸(nylon))及聚丙烯纖維。不織布可包含約0(零)至100重量%之量的非芳族聚醯胺纖維。在至少一個實施例中，不織布包含約30重量%至約80重量%非芳族聚醯胺纖維。適用於本發明之不織布可包含切段(亦即非黏合)纖維及黏合纖維。切段纖維可包括例如間芳族聚醯胺及對芳族聚醯胺、聚苯硫醚(PPS)、聚酯(包括聚對苯二甲酸伸乙酯(PET))、經乙二醇改質 之聚酯、聚苯碸、耐綸及聚丙烯纖維。黏合纖維可包括例如間芳族聚醯胺、聚苯硫醚(PPS)、聚酯(包括聚對苯二甲酸酯(PET)及聚(對苯二甲酸環己烷二甲醇酯)(PCT))、經乙二醇改質之聚酯、聚苯碸及聚丙烯纖維。通常，黏合纖維將在施加熱及/或壓力時軟化及/或流動，從而使其與切段纖維黏結。黏合纖維可包含單一聚合物及/或具有兩種具不同化學及/或物理性質之聚合物之雙組分組態。
對於由切段纖維及黏合纖維製成之適用於本發明之不織布，切段纖維可通常包含約30重量%至約80重量%織品且黏合纖維可通常包含約20重量%至約70重量%織品。
在一些本發明實施例中，替代使用黏合纖維或除使用黏合纖維以外，不織布可含有黏結劑以促進不織布內材料之黏結。其他黏結或強化不織布之方法包括水刺、點黏結或壓延。
通常將纖維摻合在一起以形成不織布。與先前技術之方法(諸如使非編織紙層合於連續聚酯膜以增加紙強度)相比，摻合不同纖維之能力可實現滿足產品效能(諸如改良撕裂強度)之較大設計靈活性。
不織布通常包含形成可撓性薄片材料之纖維網狀物，其可在非編織或非針織情況下產生且由以下方式保持在一起：(i)以機械方式連鎖至少一些纖維，(ii)使一些纖維之至少一些部分融合，或(iii)藉由使用黏結材料使至少一些纖維黏結。在黏結或融合一些纖維之前，不織布可類似於棉絮，一種柔軟的龐大纖維束。
不織布可呈任何適合形式，諸如(但不限於)經梳理之非編織網、紡黏網、熔噴網、稀洋紗、布、單向網、氈、射流噴網、水刺網及其類似物。
在至少一個實施例中，經梳理之非編織網可包括約20重量%至約70重量%芳族聚醯胺纖維摻合物及約30重量%至約80重量%其他非芳族聚醯胺纖維。
本發明之不織布可由此項技術中已知之任何適合方法製造。典型方法包括用於長度通常等於或大於1吋之纖維的乾式成形(乾式成網)製程。乾式成形製程中所用之較長纖維通常產生具有開放、多孔結構之不織布，其具有良好機械強度。乾式成形製程之實例包括梳理及紡黏。在典型乾式成形梳理製程中，將切段纖維塊機械分離成個別纖維且成形為黏著網。梳理機使用具有間隔較小之針的對置移動床來抽拉及分離纖維塊。為被針抓住，梳理中所用之輸入纖維通常為捲曲的，亦即製成波浪狀。
適用於本發明之市售不織布包括可按商標名THERMAL SHIELD (非編織PPS材料)自3M Company獲得之不織布及可按商標名NOMEX LT自DuPont(www2.dupont.com)獲得之不織布，包括(但不限於)180型。
非編織紙層及不織布層可包含一或多個薄片，亦即單布層或子層，其組合形成層。單布層或子層可為相同或不同材料。薄片可由任何適合方式組合，諸如使用化學黏著劑或藉由諸如熱壓延之製程。
在至少一個其他實施例中，不織布層置於兩個非編織紙層之間且與兩個非編織紙層直接融合。在至少一個實施例中，藉助於熱壓延堆疊經熱及壓力而以機械及熱黏結使不織布層與至少一個非編織紙層融合在一起。
在製造一些本發明實施例之物件時，不施用黏著劑(亦即除了可能已用於形成非編織紙或不織布層之黏著劑外)將各種層或子層接合在一起。替代地，藉由僅在熱及壓力下壓延使不織布層及非編織紙層黏結。
在製造一些其他本發明實施例之物件時，使用某種類型之層黏著。黏著可藉由例如構造中存在熱塑性層、在層之間添加黏著劑或黏著增強表面處理(諸如電漿處理)來實現。可使用任何適合黏著劑。舉 例而言，黏著劑可基於水或基於溶劑。黏著劑可具有任何適合組成。適合組成之實例包括丙烯酸類、苯乙烯及聚酯。可視情況且較佳向黏著劑中添加阻燃劑。阻燃劑可為任何適合材料。適合阻燃劑材料之實例包括金屬氫氧化物(例如ATH及MgOH)及有機磷酸酯。阻燃劑可佔黏著劑之至多約50重量%，較佳至多30重量%。添加過多阻燃劑將降低黏著劑之黏著性質。
黏著劑可最適用於具有相對較厚非編織紙層之實施例。在此等類型之較厚產品構造中，熱轉移至層中所需之時間較長(線速度較慢)。因此，在一些情形中，宜施用黏著劑使某些層黏結在一起，從而可利用較快的線速度。
不織布之配方亦可經設計而與非編織紙黏結或促進與非編織紙整合，從而無需施用黏著劑。舉例而言，於不織布層中存在黏合纖維、黏結劑或紡黏(熱塑性)纖維可使得非編織紙層與不織布層在施加熱及/或壓力時黏結在一起。
可在連續過程(線內整合)或不連續步驟(離線整合)中形成及組合或整合非編織紙層及不織布層。
如先前所述，本發明物件適用於使變壓器、馬達、發電機及其他需要電子組件絕緣之裝置中之電子組件絕緣。至少一些本發明實施例適用於具有耐火性要求之變壓器中，諸如礦業、海運業及鐵道業中使用之變壓器。不同產品應用需求可由本發明之非編織紙與不織布之不同組合來解決。舉例而言，可調整非編織紙與不織布之重量比。對於至少一些本發明物件，不織布層佔約3重量%至約50重量%且非編織紙層佔約50重量%至約97重量%。較佳結構將視層厚度及其他因素而變化。
絕緣物件之各層可促成最終構造之獨特性質。舉例而言，在一些實施例中，非編織紙可提供耐火性、長期耐熱性及理想電學性質； 不織布可提供極佳抗撕裂性，同時亦增強拉伸強度及熱老化後之整體可撓性。兩種類型之層的組合提供具有耐火性、物理強度及理想電學性質，同時在約464℉(240℃)下高溫熱老化後保持極佳可撓性的物件。
在至少一些本發明實施例中，當根據ASTM D149-09量測時，絕緣物件之介質擊穿強度大於100伏/密耳(3.9千伏/毫米)，較佳大於或等於150伏/密耳(5.9千伏/毫米)。
在至少一些本發明實施例中，當根據ASTM E1530-11量測時，絕緣物件之熱導率為0.18 W/m．K或大於0.18 W/m．K。
實例
提供以下實例及比較實例以幫助理解本發明且不應將其視為限制本發明之範疇。除非另有指示，否則所有份數及百分比均以重量計。採用以下測試方法及方案評估以下說明性及比較實例：
材料清單
測試方法
比較實例CE1及CE2
僅使用非編織紙層(亦即不使用不織布層)製得比較實例CE1及CE2。CE1及CE2使用來源於上述材料清單中記錄之來源的市售非編織紙。結構、製程條件及測試結果提供於表1中。CE2之「5-5-5」複合結構指示三個FLAME BARRIER FRB-NC非壓延型非編織紙層(在壓延後各自厚度為5 mil)堆疊在一起且在所指示之條件下壓延形成CE2。
不織布層：
使用6種不同不織布摻合物製備實例1-27及比較實例CE3-CE7。不織布摻合物NW1-NW6由表2中所提供之量的對芳族聚醯胺纖維、聚酯(PET)切段纖維、未延伸PET纖維、雙組分聚酯黏合纖維、聚苯硫醚(PPS)黏合纖維及/或雙組分PET/PPS纖維組成。纖維混合物通過梳理機以產生基本重量介於22至24 gsy(公克/平方碼)之間的非編織棉絮。接著經鋼質軋棉機(steel cotton nip)壓延非編織棉絮，其中鋼輥加熱至介於230℉至240℉(110℃至116℃)之間的溫度且軋點壓力介於590 lb/in(106 kg/cm)至800 lb/in(143 kg/cm)之間。
用於厚複合紙之層合之黏著劑：
為製備如稍後所述之實例27中使用之黏著劑，向ROBOND L-330黏著劑分散液中添加CR-9-101催化劑且在室溫下混合15分鐘。將TI-Rite #HA水性分散液添加至混合物中且混合直至充分分散。以下提供黏著劑配方之最終組成。
複合絕緣紙
為製備比較實例CE3-CE7及實例1-27之複合絕緣紙，排列不織布層及非編織紙層且藉助於熱壓延機堆疊經熱及壓力而以機械及熱黏結使其融合在一起。比較實例CE3-CE7及實例1-27之不織布摻合物、非編織紙厚度及複合構造提供於表3-7中。所有實例均使用FLAME BARRIER FRB-NC非壓延型非編織紙。表2-7中所列之非編織紙厚度值係指各FLAME BARRIER FRB-NC層在壓延後將具有之厚度。下表提供壓延前及壓延後非編織紙之等效厚度。
在表3-7中之標題「複合結構」下，「NW」係指不織布層且數值係指非編織紙之厚度。舉例而言，「7-NW-7」複合結構指示一個不織布層置於兩個非編織紙層(壓延後各自厚度為7 mil)之間。對於實例1-26，對任何層之表面未施用黏著劑。最終複合物壓延係在375℉至385℉(191℃至196℃)之溫度及1000 lb/in(179 kg/cm)之軋點壓力下在鋼輥之間進行。實例CE3-CE4、1-6及23-27通過鋼-鋼軋點兩次。
實例1、4、5及6由呈交替層形式之三個非編織紙層及兩個不織布層構成，其結構為非編織紙-不織布-非編織紙-不織布-非編織紙。實例2、7、8及12-26由置於兩個非編織紙層之間的兩個不織布層構成。實例3、9、10及11由置於兩個非編織紙層之間的一個不織布層構成。藉由將兩個不織布層置於兩個非編織紙層之間，壓延產生複合紙，在此複合紙之兩個層之間施用先前所述之阻燃性黏著劑且壓延整個堆疊產生厚複合紙來製備實例27。藉由將1、2或3個非編織紙層置於兩個不織布層之間來形成比較實例CE3-CE7。
實例1-26及比較實例CE3-CE7之標準性質及UL 94垂直燃燒測試結果展示於表3-7中。實例1-6及23-26以及比較實例CE3及CE4之最終複合物厚度為約15 mil(0.38 mm)。實例7、8、11、12及15-18之厚度 為約7 mil(0.18 mm)。實例9、10、13及14以及比較實例CE5-CE7之厚度為約5 mil(0.13 mm)。實例19-22之最終複合物厚度為約10 mil(0.25 mm)。實例27之厚度為24.6 mil(0.62 mm)。
儘管標準FLAME BARRIER FRB-NT非編織紙本身具有極佳阻燃性質，但如表1中之實例CE1及CE2所見，將其與不織布層組合會改良機械(拉伸及撕裂)強度及殘留熱老化可撓性。
儘管本文中出於描述較佳實施例之目的而說明及描述特定實施例，但一般技術者應瞭解，可在不脫離本發明範疇之情況下用多種替 代性及/或等效實施來替代所展示及描述之特定實施例。本申請案欲涵蓋本文所論述之較佳實施例之任何修改或變化。因此，顯然本發明欲僅受申請專利範圍及其等效物限制。

Claims (20)

  1. 一種物件，其包含：非纖維素性不織布層，其具有對置的第一主表面及第二主表面且具有附著至該不織布層之各主表面之非纖維素性非編織紙層，其中該非編織紙及該不織布中之一或兩者為電子絕緣的。
  2. 如請求項1之物件，其中該等非編織紙層中之至少一者與該不織布層直接融合。
  3. 如請求項1之物件，其中該等非編織紙層中之至少一者係藉由黏著劑附著至該不織布層。
  4. 如請求項3之物件，其中該黏著劑包含阻燃劑。
  5. 如請求項4之物件，其中該黏著劑包含至多30重量%之阻燃劑。
  6. 如請求項4之物件，其中該黏著劑包含至多50重量%之阻燃劑。
  7. 如請求項1之物件，其包含多個交替之非編織紙層及不織布層，其中兩個外部層均為非編織紙。
  8. 如請求項7之物件，其包含5個交替層。
  9. 如請求項1或7之物件，其中該等非編織紙層中之至少一者包含多於一個非編織紙之薄片。
  10. 如請求項9之物件，其中構成該等非編織紙層中之至少一者的該等薄片具有不同性質。
  11. 如請求項10之物件，其中該等不同性質係選自由厚度、組成、密度、可撓性、撕裂強度、拉伸強度、介電強度及耐火性組成之群。
  12. 如請求項1之物件，其中該不織布層包含多於一個不織布之薄片。
  13. 如請求項7之物件，其中至少一個不織布層包含多於一個不織布 之薄片。
  14. 如請求項12之物件，其中構成該等不織布層中之至少一者的該等薄片具有不同性質。
  15. 如請求項14之物件，其中該等不同性質係選自由厚度、組成、密度、可撓性、撕裂強度、拉伸強度、介電強度及耐火性組成之群。
  16. 如請求項1之物件，根據ASTM D149-09，其複合部分之介質擊穿強度大於或等於150伏/密耳。
  17. 如請求項1之物件，其中該物件之UL 94耐火性測試等級達到V-0。
  18. 如請求項12之物件，其中該不織布層包含可燃材料。
  19. 如請求項1之物件，其中該不織布包含芳族聚醯胺纖維。
  20. 如請求項1之物件，其中該不織布層之重量%為約3至約50且該一或多個非編織紙層之重量%為約50至約97。
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EP2861418B1 (en) 2021-02-17
RU2014149281A (ru) 2016-08-10
CA2875304A1 (en) 2013-12-19
JP2018006353A (ja) 2018-01-11
CN104364078A (zh) 2015-02-18
MX2014014667A (es) 2015-03-04
RU2602117C2 (ru) 2016-11-10
US20150118464A1 (en) 2015-04-30
EP2861418A1 (en) 2015-04-22
WO2013187956A1 (en) 2013-12-19
SG11201408346YA (en) 2015-01-29
JP6257608B2 (ja) 2018-01-10

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