TWI535560B - 熱壓機用緩衝材 - Google Patents
熱壓機用緩衝材 Download PDFInfo
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- TWI535560B TWI535560B TW102127737A TW102127737A TWI535560B TW I535560 B TWI535560 B TW I535560B TW 102127737 A TW102127737 A TW 102127737A TW 102127737 A TW102127737 A TW 102127737A TW I535560 B TWI535560 B TW I535560B
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- 239000000463 material Substances 0.000 title claims description 72
- 238000007731 hot pressing Methods 0.000 title description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 75
- 239000000835 fiber Substances 0.000 claims description 65
- 239000000470 constituent Substances 0.000 claims description 12
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000009940 knitting Methods 0.000 claims description 5
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 claims description 5
- HERSWHWQXZRIDA-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-amine Chemical compound CC(C)=CCCC(C)(N)C=C HERSWHWQXZRIDA-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyparaphenylene Polymers 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 239000001888 Peptone Substances 0.000 claims 1
- 108010080698 Peptones Proteins 0.000 claims 1
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 235000019319 peptone Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- 230000008859 change Effects 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 5
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 229920006277 melamine fiber Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- VSSAADCISISCOY-UHFFFAOYSA-N 1-(4-furo[3,4-c]pyridin-1-ylphenyl)furo[3,4-c]pyridine Chemical compound C1=CN=CC2=COC(C=3C=CC(=CC=3)C3=C4C=CN=CC4=CO3)=C21 VSSAADCISISCOY-UHFFFAOYSA-N 0.000 description 2
- 229920001494 Technora Polymers 0.000 description 2
- 229920000561 Twaron Polymers 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004950 technora Substances 0.000 description 2
- 239000004762 twaron Substances 0.000 description 2
- 229920000945 Amylopectin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 239000012790 adhesive layer Substances 0.000 description 1
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- 230000020169 heat generation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
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Description
本發明係關於可使用於熱壓之熱壓機用緩衝材,尤其關於在製造銅箔積層板、可撓性印刷基板、多層板等之印刷基板或IC卡、液晶顯示板、陶瓷積層板等精密機器零件(以下在本發明中稱為「積層板」)的步驟中,加壓成形或熱壓接對象製品時所使用之熱壓機用緩衝材。
在積層板之製造步驟中,首先要重疊材料之積層板素材而製作被壓縮體。接著將其投入熱盤間之後熱壓,亦即藉由熱壓機進行加熱加壓,將積層板素材所含之樹脂經過流動狀態而硬化並一體化。進行該加熱加壓之步驟中,在熱盤或投入構件之被壓縮體中若有厚度不均、熱所產生之變形、溫度不均等,則無法對之後成為製品之被壓縮體施以均一的溫度、壓力。其結果於製品產生板厚不良、龜裂、翹曲等之缺陷。因此,為了解決製品之板厚不良等,而使用在熱壓成形時會跟隨被壓縮體的形狀而用以施加均一的溫度、壓力之具備緩衝性的熱壓用緩衝材(以下,僅稱為緩衝材)。
關於如此之在熱壓機所使用的熱壓機用緩
衝材的技術,係已揭示於日本特開平6-91780號公報(專利文獻1)及日本特開平6-166935號公報(專利文獻2)。若根據專利文獻1及專利文獻2,係已揭示一種耐熱緩衝材,其係形成包含未延伸之間位系芳香族聚醯胺纖維之織物或含有間位系芳香族聚醯胺纖維之織物經針織成之覆蓋層,並以在間位系芳香族聚醯胺纖維之玻璃轉移點以上之溫度進行熱處理。
專利文獻1:日本特開平6-91780號公報
專利文獻2:日本特開平6-166935號公報
近來係對於積層板要求更高之板厚精度或薄形化等。因此,呼應對於如此之積層板的高度要求,即使對於製造積層板時所使用之熱壓機用緩衝材也要求特性進一步提昇。亦即,有關熱壓機用緩衝材,係尋求可承受在高溫條件下使用之耐熱性、在高溫條件下之長時間使用亦可維持緩衝性之高緩衝性、及可降低因熱所造成之緩衝材本身之劣化等。
對應如此之要求,專利文獻1或專利文獻2所揭示之熱壓機用緩衝材中係有無法應付之虞。例如若在高溫條件下重複使用已利用如聚間伸苯基異酞醯胺之間位型芳香族聚醯胺纖維的熱壓機緩衝材,會因熱所造成之劣
化致產生纖維的粉末,有黏著於被壓縮體等之虞。在如此之狀態下,係很難使用來作為至少經過長時間的高溫條件下之緩衝材。
此時,對於所謂纖維粉末之發生或黏著的問題,亦可考量在構成上述緩衝材之纖維表層貼上所謂的接著劑,使纖維之表層形成表面平滑之接著層。但是在近來所要求之高溫的使用環境下,係有接著劑不堪在高溫下使用,而發生接著層從纖維剝離的問題之虞。亦即,如此之對策係不妥當。
本發明之目的係提供一種即使在高溫條件下使用亦具有高的緩衝性,且可經長時間使用之熱壓機用緩衝材。
本案發明人等充分考量近來對於緩衝材之高度要求,精心研究在使用於熱壓之熱壓機用緩衝材中構成緩衝材之纖維。終達到使用兼具緩衝材所要求之特性的複數纖維,並以該等作為積層構造而構成緩衝材之想法。
亦即,本發明之熱壓機用緩衝材係使用於熱加壓之熱壓機用緩衝材,其係具備:構成內部層之第一不織布、與配置在第一不織布兩面側且構成外部層之第二不織布。第二不織布係之構成材料係使用基重為80至400g/m2之共聚系對位型芳醯胺纖維。第一不織布之構成材料係使用纖維之剛性高於共聚系對位型芳醯胺纖維的纖維。第一不織布及第二不織布之耐熱溫度分別為270℃以
上。
如此之熱壓機用緩衝材係由構成內部層之第一不織布、與構成配置在第一不織布的兩面側之外部層的第二不織布所形成之積層構造,分別具有緩衝材所要求之功能,而可達成近來所要求之作為緩衝材的特性。
亦即,使用第二不織布作為構成表層之外部層,第二不織布之構成材料係使用基重為80至400g/m2之共聚系對位型芳醯胺纖維,故即使在高溫之使用環境下也不會產生纖維粉末或黏著。具體上,使用共聚系對位型芳醯胺纖維作為構成材料之第二不織布,係在初期之加壓中容易產生纖維之塑性變形,而形成纖維一體化之膜狀的層,所謂薄膜狀的層。接著,第二不織布之耐熱溫度為270℃以上,故即使在經過高溫條件下長時間使用,也可消除源自由薄膜狀的層產生纖維粉末或黏著。此時,第二不織布之基重亦高於80g/m5,故可達成所謂抑制毛邊發生或撕裂之緩衝材所要求的特性。又,使第二不織布之基重的上限為400g/m2的理由,係因即使大於此基重亦無法期待抑制毛邊發生或撕裂之效果進一步的提昇。
接著,使用第一不織布作為內部層,第一不織布之構成材料係使用纖維的剛性高於共聚系對位型芳醯胺纖維的纖維,故不易產生纖維之塑性變形,可形成容易在纖維體內部維持空隙之構成。因此可維持內部層之高緩衝性。繼而,對於第一不織布,因耐熱溫度為270℃以上,故可承受在高溫下之使用。亦即,即使在高溫條件下
經過長時間的使用也不會引起纖維之熱分解而可使用。此處,所謂耐熱溫度係表示構成材料之纖維的熔點或熱分解溫度。
其結果,如此之緩衝材係即使在高溫條件下使用亦具有高緩衝性,且可長時間使用。
在此,第一不織布與第二不織布亦可形成藉針織法一體化之構成。藉由如此作法,可更適當地使第一不織布與第二不織布形成為積層構造體。
又,共聚系對位型芳醯胺纖維係可形成如包含共聚對伸苯基‧3,4-氧二伸苯基‧對酞醯胺纖維之構成。此外,纖維之剛直性高的纖維係可形成如含有聚對伸苯基對酞醯胺纖維之構成。
如此之熱壓機用緩衝材係即使在高溫條件下使用亦具有高緩衝性,並可長期使用。
11‧‧‧熱壓機裝置
12a、12b‧‧‧熱盤
13‧‧‧被壓縮體
14a、14b‧‧‧熱壓機用緩衝材
15‧‧‧第一不織布
16a、16b‧‧‧第二不織布
17a、17b、18a、18b、19a、19b、20a、20b‧‧‧面
第1圖係表示製造積層板時所使用之熱壓機裝置的概略剖面圖。
第2圖係本發明一實施型態之熱壓機用緩衝材在厚度方向剖切時之概略剖面圖。
以下參照圖面而說明本發明之實施型態。第1圖係表示製造積層板時所使用之熱壓機裝置的概略剖
面圖。參照第1圖,熱壓機裝置11係具有配置在上下方向並互相面對之2個熱盤12a、12b。接著說明有關積層板之製造方法。首先準備重疊複數片成為材料之積層板素材之被壓縮體13。接著,將被壓縮體13夾於具有同樣構成之2片熱壓機用緩衝材14a、14b之間。將其配置在配置於上下方向之熱盤12a、12b之間。亦即形成為在被壓縮體13與熱盤12a、12b之間分別配置有熱壓機用緩衝材14a、14b的狀態。接著藉熱盤12a、12b加熱加壓被壓縮體13並進行加壓成形。以如此做法而可製造作為製品之積層板。在此,藉由配置在熱盤12a、12b與被壓縮體13之間的熱壓機用緩衝材14a、14b,可對被壓縮體13施加均一的溫度、壓力。
接著說明有關本發明之一實施型態之熱壓機用緩衝材14a的構成。又,熱壓機用緩衝材14b的構成係與以下所說明之熱壓機用緩衝材14a的構成相同,故省略說明。第2圖係本發明之一實施型態之熱壓機用緩衝材在厚度方向剖切時之概略剖面圖。
參照第2圖,本發明之一實施型態之熱壓機用緩衝材14a係使用於熱壓之熱壓機用緩衝材,其係具備構成內部層之第一不織布15、與配置在第一不織布15兩面側且構成外部層之第二不織布16a、16b。
第二不織布16a、16b係設有2片。具體上,係以使第一不織布15在第2圖中的紙面上側之面17a,與被配置於第2圖的紙面上側之一側的第二不織布16a在第
2圖中的紙面下側的面18a相接觸之方式構成。此外,以使第一不織布15在第2圖中的紙面下側之面17b,與被配置於第2圖的紙面下側之另一側的第二不織布16b在第2圖中的紙面上側之面19a相接觸之方式構成。亦即,熱壓機用緩衝材14a係在2片第二不織布16a、16b之間介有1片第一不織布15之構成,熱壓機用緩衝材14a係由合計3片之不織布所構成。另外,在一側之第二不織布16a在第2圖中的紙面上側之面18b,係在進行熱壓時與熱盤12a之紙面下側的面20a抵接,另一側之第二不織布16b在第2圖中的紙面下側之面19b,係在進行熱壓時與被壓縮體13之上側面20b抵接。
第一不織布15及第二不織布16a、16b之耐熱溫度係分別為270℃以上。亦即,第一不織布15及第二不織布16a、16b係同時地以耐熱溫度成為270℃以上之方式構成。此外,第一不織布15與第二不織布16a、16b係以針織法一體化。
在此,第二不織布16a、16b之構成材料係使用基重為80至400g/m2之共聚系對位型芳醯胺纖維。此外,第一不織布15之構成材料係使用纖維之剛性高於共聚系對位型芳醯胺纖維的纖維。
具體而言,構成第二不織布16a、16b之共聚系對位型芳醯胺纖維係可舉出共聚對伸苯基‧3,4-氧二伸苯基‧對酞醯胺纖維。共聚對伸苯基‧3,4-氧二伸苯基‧對酞醯胺纖維係以如下之化1的構造式表示。
此外,纖維之剛性高於共聚系對位型芳醯胺纖維的纖維係可舉出聚對伸苯基對酞醯胺(PPTA(poly-p-phenylene-terephthalamide))纖維。以如下之構造式表示。PPTA纖維係以如下之化2的構造式表示。
如此之熱壓機用緩衝材14a、14b係由構成內部層之第一不織布15、與構成配置在第一不織布15兩面側之外部層的第二不織布16a、16b所形成的積層構造,分別具有作為緩衝材所要求之功能,而可達成近來所要求之作為緩衝材的特性。
亦即,使用第二不織布16a、16b作為構成表層之外部層,第二不織布16a、16b之構成材料係使用基重為80至400g/m2之共聚系對位型芳醯胺纖維,故即使在高溫之使用環境下也不會產生纖維之粉末或黏著。具體來說,使用共聚系對位型芳醯胺纖維作為構成材料之第二不織布16a、16b,係在初期之加壓易產生纖維之塑性變形,而成為纖維一體化之膜狀的層,所謂薄膜狀的層。接著,第二不織布16a、16b之耐熱溫度為270℃以上,故即使在高溫條件下經過長時間使用,亦可消除薄膜狀的層之纖維
的粉末發生或黏著。此時,因第二不織布16a、16b之基重高於80g/m5,故可達成所謂抑制毛邊發生或撕裂之緩衝材所要求的特性。又,即使第二不織布16a、16b之基重大於400g/m2也無法期待抑制毛邊之發生或撕裂之效果會更提昇。
接著,使用第一不織布15作為內部層,第
一不織布15之構成材料係使用纖維之剛性高於共聚系對位型芳醯胺纖維的纖維,故不易產生纖維之塑性變形,可形成為在纖維體內部容易維持空隙之構成。因此可維持內部層之高緩衝性。繼而,有關第一不織布15,因耐熱溫度為270℃以上,故可承受高溫下之使用。亦即,即使在高溫條件下長時間使用也不會引起熱分解而可使用。
據上,如此之熱壓機用緩衝材14a、14b係即使在高溫條件下使用亦具有高緩衝性,並可長期使用。
另外,此時在兩側配置有具有相同構成之第二不織布16a、16b,故作為緩衝材時不須考量方向性。亦即成為作業性亦良好者。
在此,若根據上述實施型態,第一不織布15與第二不織布16a、16b係藉由針織法一體化,但並不限定於此,亦可以其他之方法使第一不織布15與第二不織布16a、16b一體化。
另外,上述實施型態中,共聚系對位型芳醯胺纖維係採用共聚對伸苯基‧3,4-氧二伸苯基‧對酞醯胺纖維,但並不限定於此,亦可使用其他之共聚系對位型
芳醯胺纖維。此外,就纖維之剛性高於共聚系對位型芳醯胺纖維的纖維而言,係採用PPTA纖維,但並不限定於此,亦可使用其他之纖維。
以如下方式構成實施例1。第二不織布係使用2片共聚對伸苯基‧3,4-氧二伸苯基‧對酞醯胺纖維(商品名「TECHNORA」:Teijin Techno Products股份公司製)。使用基重為100g/m2者。此外,第一不織布係使用PPTA纖維(商品名「TWARON」:Teijin Techno Products股份公司製)。使用基重為800g/m2者。在第一不織布兩面側分別配置第二不織布,並以針織法一體化,而得到整體之基重成為1000g/m2之實施例1之熱壓機用緩衝材。
就比較例1而言,使用PPTA纖維(商品名「TWARON」:Teijin Techno Products股份公司製)、基重1000g/m2之1片不織布,而得到熱壓機用緩衝材。
就比較例2而言,使用聚對伸苯基苯并二噁唑(PBO(p-phenylene-2,6-benzobisoxazole))纖維(商品名「Zylon」:東洋紡績股份公司製)、基重1000g/m2之1片不織布,而得到熱壓機用緩衝材。
就比較例3而言,使用共聚對伸苯基‧3,4-氧二伸苯基‧對酞醯胺纖維(商品名「TECHNORA」:Teijin Techno Products股份公司製)、基重1000g/m2之1片不織布,而得到熱壓機用緩衝材。
對於該實施例1及比較例1至3之熱壓機用
緩衝材進行熱壓之耐久試驗。表1中表示進行耐久試驗時之實施例1及比較例1至3的表面狀態之結果。表2中表示進行耐久試驗時之實施例1及比較例1至3的緩衝性之結果。
表1、表2中之實施例1及比較例1至3的加壓條件係在溫度300℃中施加壓力10MPa之負載。加壓循環為加熱110分鐘、冷卻15分鐘。另外,加壓10次是以進行加壓10次後之狀態所測定者。
表1中之「○」符號係表示表面狀態為良好,亦即沒有毛邊之脫落或撕裂。此外,表1中之「×」符號表示表面狀態不佳,亦即產生毛邊之脫落或撕裂、或是產生兩者。
參照表1,在實施例1及比較例3中,從初期經過加壓1次、10次、50次後,也沒有發生毛邊之脫落或撕裂,可知表面狀態良好。然而,對於比較例1係在加壓1次後即產生毛邊之脫落,在其後的加壓也產生毛邊。
此外,對於比較例2係在加壓10次後產生毛邊之脫落,在50次後也產生毛邊之脫落。再者,在比較例2中在50次後易產生撕裂。毛邊之脫落或撕裂的產生會污染積層板之生產線,因脫落物之捲入會對加壓對象物之積層板製品造成不良影響。亦即在表面狀態中,與實施例1相比,可確認比較例1、2之表面狀態較不佳。
表2係表示相對於初期及進行特定次數之加壓後之熱壓機用緩衝材,在施加10MPa之負載時,緩衝材的厚度較加壓前會有何種程度之變化。以該厚度變化量作為緩衝性之評定指標。另外,厚度係以測微計測定。此外,表2中表示各自之初期厚度。
參照表2,實施例1中,對於初期之厚度變化量2824μm,在加壓1次後,厚度變化量為628μm。再者,隨著加壓次數增加,厚度變化量漸變少,但在加壓10次後,厚度變化量為336μm,即使加壓50次後,厚度變化量為276μm,在各別之狀況中皆顯示較高的值。另外,有關厚度變化量係表示越高值緩衝性越良好。亦即,即使進行加壓,也是厚度變化量高者較佳。
然而,在比較例3中,相對於初期之厚度變化量2282μm,在加壓1次後,厚度變化量為206μm,可知緩衝性非常地降低。再者,隨著壓機次數增加,厚度變化量漸變少,在加壓10次後,厚度變化量為132μm,再者在加壓50次後為114μm,緩衝性變得非常差。亦即,可知在緩衝性上相對於實施例1,比較例3較差。
另外,有關比較例1,係對於初期之厚度變化量2225μm,在加壓1次後,厚度變化量為657μm。再者,在加壓10次後,厚度變化量為317μm,即使在加壓50次後,厚度變化量亦為259μm,在各別之狀況中皆顯示較高的值。此外,有關比較例2,係對於初期之厚度變化量2461μm,在加壓1次後,厚度變化量為875μm。再者,在加壓10次後,厚度變化量為311μm,即使在加壓50次後,厚度變化量亦為278μm,在各別之狀況中皆顯示較高的值。但如上所述,有關比較例1及比較例2,雖然緩衝性良好,但由表面狀態之觀點來看為使用變困難者。
由以上可知,從緩衝性及表面狀態兩者之觀點來看,相對於比較例1至3,實施例1較良好。
以上參照圖面而說明本發明之實施型態,但本發明係不限於圖示之實施型態者。對於圖示之實施型態,在與本發明相同之範圍內、或是均等之範圍內,可加以各種修正或變形。
本發明之熱壓機用緩衝材係可有效利用在要求積層板良好生產性等的情形。
14a‧‧‧熱壓機用緩衝材
15‧‧‧第一不織布
16a、16b‧‧‧第二不織布
17a、17b、18a、18b、19a、19b‧‧‧面
Claims (4)
- 一種熱壓機用緩衝材,係使用於熱加壓之熱壓機用緩衝材,其係具備:構成內部層之第一不織布、與配置在前述第一不織布之兩側且構成外部層之第二不織布;前述第二不織布之構成材料係使用基重為80至400g/m2之共聚系對位型芳醯胺纖維;前述第一不織布之構成材料係使用纖維之剛直性高於前述共聚系對位型芳醯胺纖維的纖維;前述第一不織布及前述第二不織布之耐熱溫度係分別為270℃以上。
- 如申請專利範圍第1項所述之熱壓機用緩衝材,其中,前述第一不織布及前述第二不織布係以針織法一體化。
- 如申請專利範圍第1項所述之熱壓機用緩衝材,其中,前述共聚系對位型芳醯胺纖維係包含共聚對伸苯基‧3,4-氧二伸苯基‧對酞醯胺纖維。
- 如申請專利範圍第1項所述之熱壓機用緩衝材,其中,前述纖維之剛直性高的纖維係包含聚對伸苯基對酞醯胺纖維。
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CN110001164A (zh) * | 2019-04-14 | 2019-07-12 | 广州恒荣电子科技有限公司 | 一种耐高温热压缓冲材料 |
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JPS62156100A (ja) * | 1985-12-27 | 1987-07-11 | Hiroshima Kasei Kk | プレス用クツシヨン材 |
JP3121175B2 (ja) * | 1992-07-29 | 2000-12-25 | 市川毛織株式会社 | 耐熱クッション材 |
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US5614280A (en) * | 1993-12-02 | 1997-03-25 | James W. Post, III | Shielding blanket for racing engines |
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CN104284765A (zh) | 2015-01-14 |
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US20150140298A1 (en) | 2015-05-21 |
WO2014027525A1 (ja) | 2014-02-20 |
JP5726141B2 (ja) | 2015-05-27 |
KR20140144308A (ko) | 2014-12-18 |
EP2886284A1 (en) | 2015-06-24 |
WO2014027525A9 (ja) | 2014-04-10 |
EP2886284A4 (en) | 2016-03-23 |
JP2014037654A (ja) | 2014-02-27 |
TW201412524A (zh) | 2014-04-01 |
EP2886284B1 (en) | 2017-05-31 |
CN104284765B (zh) | 2016-01-13 |
US11077642B2 (en) | 2021-08-03 |
US20180015690A1 (en) | 2018-01-18 |
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