TW201438815A - 方法 - Google Patents
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- TW201438815A TW201438815A TW102137017A TW102137017A TW201438815A TW 201438815 A TW201438815 A TW 201438815A TW 102137017 A TW102137017 A TW 102137017A TW 102137017 A TW102137017 A TW 102137017A TW 201438815 A TW201438815 A TW 201438815A
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000002775 capsule Substances 0.000 claims abstract description 33
- 238000007906 compression Methods 0.000 claims abstract description 13
- 230000006835 compression Effects 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 239000012736 aqueous medium Substances 0.000 claims abstract description 3
- -1 poly(methacrylic acid) Polymers 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
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- 229920002125 Sokalan® Polymers 0.000 claims description 6
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- 150000001412 amines Chemical class 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
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- 229920002396 Polyurea Polymers 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
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Classifications
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- A—HUMAN NECESSITIES
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- Manufacturing Of Micro-Capsules (AREA)
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Abstract
本發明係關於一種囊封活性物質之方法,該方法包括:(a)將活性物質分散於具有小於6之pH之水性介質中;(b)於此經分散之活性物質上形成聚合物殼,該形成包括連續沉積一系列聚合物層,各層能夠與前一層氫鍵鍵結;以形成含活性物質膠囊之水性漿液;其特徵在於,頭兩層中之一層為多羧酸及該等頭兩至四層一起展現大於10 mN/m之界面壓縮膨脹模數。該方法容許精確定製聚合物殼,容許膠囊壁遠遠較薄而不會損失強度。該技術尤其適用於囊封香味劑及調味劑。
Description
本發明係關於活性物質(及特別是香味劑)之囊封。
已知核-殼微膠囊(即,其中所需活性物質之核完全藉由聚合物殼包覆之微膠囊)且已使用一段時間。用於囊封之典型活性物質包括醫藥及藥用物質、香味劑及調味劑,囊封係用於其之保存及以後之釋放。用途之典型實例包括在香味劑領域中,微細香味劑、消費產品,諸如洗衣應用,包括柔軟劑、液體洗滌劑、及粉末洗滌劑;個人護理及頭髮保養應用,包括洗髮精、調理劑、促進梳理之霜劑、可停留型調理劑、造型乳霜、肥皂、體霜;除臭劑及止汗劑;口腔護理應用、家庭應用,諸如清潔組合物;及在調味劑領域中,所有類型之可消耗組合物(包括食品、飲料及醫藥組合物)。
囊封通常係藉由在殼形成材料之溶液中乳化活性物質及環繞經乳化之活性物質顆粒或液滴外部形成聚合物殼來實現。已知且已使用多種殼材料,例如動物膠、胺基塑膠(脲-及三聚氰胺-甲醛)樹脂、聚脲、聚胺基甲酸酯及丙烯酸系物。其等通常會涉及在形成殼期間,或在其後來固結期間例如藉由交聯進行化學反應。
現已發現另一技術可成功地用於提供經囊封活性物質。因此提供一種囊封活性物質之方法,該方法包括:(a)使活性物質分散於具有小於6之pH之水性介質中;(b)於此經分散之活性物質上形成聚合物殼,該形成包括連續沉積一系列聚合物層,各層能夠與前一層氫鍵鍵結;
以形成含活性物質膠囊之水性漿液;其特徵在於,頭兩層中之一層為多羧酸及該等頭兩至四層一起展現大於10mN/m之界面壓縮膨脹模數。
另外提供一種經囊封活性物質,其包括完全被聚合物殼環繞之活性物質之核,該殼包括至少兩層聚合物,各聚合物層係與相鄰層氫鍵鍵結,及頭兩層中之一層為多羧酸,該等頭兩至四層一起展現大於10mN/m之界面壓縮膨脹模數。
本文所採用之技術為所謂的逐層(LbL)囊封。較佳地,涉及將兩種聚電解質交錯施覆至犧牲性模板核(通常係二氧化矽)以堆積一系列藉由靜電吸引及/或氫鍵鍵結固持在一起之層。當在已獲得所需層時,接著將該核溶解可提供中空膠囊,該中空膠囊可接著負載所需的活性物質。該技術提供前所未有的控制釋放性能之可能性,及已受到醫藥工業的極大關注(參見(例如)Kozlovskaya等人,Chem.Mater. 2006年,18,328-336)。
於此特定應用中已發現可無需任何類型模板地製得含活性物質之LbL膠囊。為作成這點,該等頭兩至四層必須滿足特定物理參數。此點將在下文作進一步的論述。
該方法具有許多優點:
1.其不採用可能會留下殘餘物之任何化學反應。殘餘物在某些可能用途(例如,化妝品及個人護理應用)中可能係難題。此外,所使用的聚合物可選自穩定及不解聚提供不想要的物質之聚合物。
2.其容許精確定製膠囊殼之性能,及因此精確定製其堅固性及易碎性,以致可確保在正確的時間破碎。
3.其容許堅固膠囊製成具有明顯薄於彼等由其他技術製得者之殼。由常規方法製成之典型膠囊殼具有約100至150nm之厚度。可製得厚度低為5nm之堅固殼。典型尺寸範圍自5至100、特定言之自5至
70、更特定言之自5至50nm。
4.於香味劑囊封之具體情況中,其容許製備具有對香味最小影響之膠囊。熟知一些香味劑組分(尤其係醛)具有與某些囊封材料反應之傾向。此點導致香料所製成香味劑不展現其全部愉悅性能力(full hedonic capacity)。
最初兩層殼中一者必須為多羧酸。所謂「多羧酸」意指具有複數個羧酸側基之任何聚合材料(該術語包括在該方法之條件下成為酸之酸酐)。
這兩層係藉由氫鍵鍵結組合。相關技藝中熟知氫鍵鍵結之現象及欲滿足之使得一種材料係與另一者氫鍵鍵結之標準。於此特定情況中,另外必須順從於另一參數,如下文中所述。典型的組合包括聚(甲基丙烯酸)/聚(乙烯吡咯啶酮)、聚(丙烯酸)/聚(乙烯吡咯啶酮)、聚(乙酸乙烯酯)/乙烯-馬來酸酐共聚物及聚(乙烯醇)/乙烯-馬來酸酐共聚物。
一旦施覆最初兩層,後續的層不需要係選自與最初的這兩層相同的材料。僅要求各層與前一層氫鍵鍵結。此容許在定製殼之性能達成所期望性能上之顯著多樣性。
該殼必須為使得頭兩至四層展現大於10mN/m、較佳大於15mN/m、更佳大於20mN/m之界面壓縮膨脹模數之殼。任何特定聚合物之選擇成滿足此點,係透過例行非發明試驗。
由以下公式給定界面壓縮膨脹模數E:
其中A0為液滴之最初表面積,A為液滴表面積及γ為界面張力。
相關技藝中熟知用於測定界面壓縮膨脹模數之設備。適宜裝置之一典型實例為由Cao等人在Journal of Colloid and Interface Science
(2004年)270:295-298中所描述類型之上升/懸掛液滴張力計。
適宜設備及測量方法之實例進一步詳細述於後文實例中。
製造膠囊之該方法係由將連續的聚合物溶液施覆至分散於水溶液中之活性物質所組成。於各個層化階段中,使用過量的聚合物及在施覆下一層之前洗去殘餘物。此舉之優點在於不需要使用特定比例之聚合物,故不需遵守精確的組成限制。
該方法之另一優點為由聚合物締合所產生之高界面模數容許藉由多種方法(諸如乳化、微流或造粒)來形成微膠囊。
該方法可簡便及穩健地容許具有活性物質之膠囊獲得迄今為止尚無法獲得薄度之非交聯壁。三聚氰胺-甲醛膠囊之一典型壁厚度為150nm;此處該厚度可低至5nm。此外,該方法容許精確定製膠囊特性,以提供孔隙度、堅固性(以耐受嚴格之製造、混練、輸送及貯藏)及易碎性(以容許膠囊在適宜時間破碎及釋放其活性物質)之間之最佳折衷。此外,該等薄壁非交聯微膠囊在塗覆於皮膚之情況下不會留下任何毒性及敏感性殘餘物。
該聚合物殼可視需要經交聯或固定。此可藉由任何簡便方式達成。例如,具有胺基或羥基之聚合物可藉由添加諸如胺、戊二醛、異氰酸酯、環氧化物之物質或具有此種反應性官能之矽酸酯偶聯劑來交聯。或者,可提供最終的矽酸酯層。該矽酸酯層係藉由水解(R)nSi(ROH)4-n(其中R為C1-C3烷基且n=1至4),及添加水解產物至LbL膠囊之漿液來提供。
該聚合物殼可視需要用作用於其他化學品之基質以便可藉由使該等材料沉積於該殼上獲得胺基塑膠、聚脲、聚胺基甲酸酯、聚丙烯酸或無機微膠囊。
如上文所述製得的膠囊可用於許多不同應用中。市售組合物(即,銷售針對特定消費者或工業最終用途之組合物)之典型實例包括
下列:(i)在香味劑工業中,微細香味劑、消費產品,諸如洗衣應用,包括柔軟劑、液體洗滌劑、及粉末洗滌劑;個人護理及頭髮保養應用,包括洗髮精、調理劑、促進梳理之霜劑、可停留型調理劑、造型乳霜、肥皂、體霜;除臭劑及止汗劑;口腔護理應用,諸如牙膏及漱口水;家庭應用,諸如清潔組合物、醫藥產品;(ii)在調味劑工業中,所有類型之可消耗性組合物,諸如罐頭及速食湯、預包裝的膳食、冷凍食品、冷凍甜點、焙烤食品、飲料、乳製品;(iii)在醫藥領域中,所有形式之醫藥及藥用物質。
其自然可包括超過一種的活性物質。
因此亦提供一種包含市售組合物基質及經囊封活性物質之市售組合物,該活性物質裝納於如上文所述製得之膠囊中。所謂「市售產品基質」意指通常用於特定組合物中之所有為相關技藝認可之組分。其等之性質及比例將根據組合物之性質改變,但所有該等配方係於相關技藝之習知技術範圍內。
膠囊之添加量將完全取決於最終用途及組合物之性質。假設該等最終用途及組合物之種類寬廣,所涉及之可能比例亦寬廣,但始終可以非發明例行試驗來確定適宜比例。
參照描述特定實施例之以下非限制性實例來進一步論述本發明。
實例1:
界面壓縮膨脹模數之測定方法。
利用由Cao等人在Journal of Colloid and Interface Science(2004年)270:295-298中所描述類型之上升/懸掛液滴張力計來測量界面壓縮膨脹模數。
1.製備聚合物溶液(1重量%含於水中)
a.以2重量%將聚合物溶解於Milli-Q水中。使用具有18.2MΩ電阻之Millipore(Milli-Q系統)過濾水
b.攪拌該溶液至少12h
c.利用1M NaOH或1M HCl將該聚合物溶液之pH調整至3
d.添加水直到獲得1重量%聚合物溶液。
2.製備沖洗溶液:利用1M HCl將Millipore水調整至pH 3
3.於油/水界面處之層建構
a.將5mL之第一聚合物(聚合物A)溶液引入單元
b.於該單元中在針末端處形成一滴香味劑(液滴體積隨系統改變)
c.1h至12h的等待時間可使聚合物吸附於油-水界面處
d.利用沖洗溶液沖洗該單元中之水相以移除過量的聚合物。該沖洗係經整體相交換作成。進行15min的10mL/min之流動。
e.等待15min
f.接著利用第二聚合物溶液(聚合物B)沖洗該單元中之水相。該沖洗係經整體相交換作成。進行5min的10mL/min之流動。
g.25min至1h的等待時間可使第二聚合物吸附於該油-水界面處
h.重複該方法直到在該油-水界面處獲得所需數量的層。
4.測定界面膨脹壓縮模數
a.一旦吸附獲得該等層,即進行測定
b.運作0.1Hz頻率之面積震盪,面積改變量為0.1至10%
c.依上文給定的公式計算得界面壓縮膨脹模數之值。
實例2
製造含香味劑膠囊
用於此製造中之聚合物為聚(甲基丙烯酸)及聚(乙烯吡咯啶酮)。當依上文所述方法測量時,2層展現150mN/m之界面壓縮膨脹模數。
將5mL 1%(重量)PMAA水溶液調整至pH 3。取5mL專用香味劑添加至該溶液。維持兩種溶液接觸24小時,接著使用Ultra-turraxTM混合器於24000rpm下乳化2分鐘。將該乳液添加至分液漏斗及利用pH 3之水(10-3M HCl)洗滌得到10%香味劑溶液。
緩慢混合該溶液且接著使其沉降24小時。
移除下層水相及洗滌四次以萃取過量的聚合物。在輕輕攪拌之下將該經洗滌之相添加至1(重量)% PVP水溶液(pH3)。使該相沉降24h及其接著利用如在前一步驟中所述的pH 3之水洗滌。重複該等沉降、下層移除及洗滌步驟。
利用PMAA溶液重複前一步驟,且接著再次利用PVP溶液重複該前一步驟。持續這種交替直到沉積5層。在沉積2層之後,可在顯微鏡下觀察到微膠囊,及其堅固到足以保持其完整性。
最終的含香味劑膠囊具有31μm之平均直徑及14nm之壁厚度。
實例3
製造含香味劑膠囊
用於本實例中之聚合物為50PAA1C12及聚(乙烯吡咯啶酮)。50PAA1C12為含有某些疏水組分之聚丙烯酸:其主鏈為約50 000g/莫耳。接枝部分具有12個碳及其以1(莫耳)%(100個單位有1個疏水部分)接枝。
當在沉積到4層時,界面壓縮膨脹模數為40mN/m。
將5mL 1%(重量)50PAA1C12水溶液調整至pH 3。取5mL專用香味劑添加至該溶液。維持這兩種溶液接觸24小時,接著使用Ultra-turraxTM混合器於24000rpm下乳化2分鐘。將該乳液添加至分液漏斗
及利用pH 3(10-3M HCl)之水洗滌可提供10%香味劑溶液。
該溶液經過溫和混合且接著讓其沉降24小時。
移除下層水相及洗滌四次以萃取過量的聚合物。在輕輕攪拌之下將該經洗滌之相添加至1(重量)% PVP水溶液(pH3)。讓該相沉降24h及其接著利用如在前一步驟中所述的pH 3之水洗滌。重複該等沉降、下層之移除及洗滌步驟。
利用PAA溶液重複前一步驟,且接著再次利用PVP溶液重複該前一步驟。持續這種交替直到獲得所需數量的層,於此情況中,直到獲得5層。在沉積2層之後,可在顯微鏡下觀察到微膠囊及進行相關操縱。
最終的含香味劑膠囊具有31μm之平均直徑及18nm之壁厚度。
實例4
微膠囊之測試
將實例2中所述類型但具有10層之PMAA/PVP微膠囊沉積於吸墨紙上。將該等膠囊中該類型專用香味劑添加至另一吸墨紙,以致香味劑的添加量相等。
令該等吸墨紙在25℃及標準大氣壓下靜置24小時,及由一隊8位經過培訓之香味劑研究組員對其作評估。
組員們發現在這兩種情況中氣味微弱及強度亦同。然而,摩擦該具有膠囊之吸墨紙可明顯增強香味。
實例5:
製造包含在實例2中所述類型之10層PMAA/PVP微膠囊之體霜。
體霜調配物係藉由將下表所列組分混合製得。
體霜係藉由將以相對於表中所顯示體霜調配物總重量計2重量%之微膠囊混入該體霜而製得。將該等膠囊中該類型專用香味劑添加至同一體霜,以致香味劑的添加量相等。
利用微量吸移管以0.5g的量將體霜塗覆於人前臂皮膚上,及在以指部擦摩整個表面的10秒期間輕輕地按摩該前臂。
在4小時後由8位經過培訓之研究組員組成之專家小組基於盲測基礎來評估香味強度。組員們發現在這兩種情況中氣味微弱及具有相同的強度。然而,摩擦具有該等膠囊之該前臂可明顯增強香味。
實例6:
製造包含實例2之10層PMAA/PVP微膠囊之口味轉變型冰淇淋(flavour-shifting ice cream)。
冰淇淋係藉由在pH 5下含香草口味之冰淇淋調配物中混合含櫻桃口味之微膠囊製得。
最初的味覺係香草,接著在膠囊於嘴中pH 7下融解後很快變為櫻桃口味。
實例7:
製造包含實例2之10層PMAA/PVP微膠囊之可停留型髮霜調配物可停留型調配物係藉由混合下表所列組分製得。
1 DC 200流體(來自Univar)
2 DC 345流體(來自Univar)
3 ABILTM OSW 5(來自Goldschmidt)
4 DC 556流體(來自Univar)
該可停留型調配物係將以相對髮乳髮霜總重量計2重量%之微膠囊混入以上所製得調配物中而製得。將該等膠囊中該類型專用香味劑添加至沐浴露(body wash)之另一樣本,以致香味劑的添加量相等。
利用微量移液管以0.5g的量將這兩種調配物塗覆至頭髮樣版,及在整個表面上用指部按摩頭髮10秒。
在4小時後由8位經過培訓之研究組員組成之專家小組基於盲測基礎來評估香味強度。組員們發現在這兩種情況中氣味微弱及具有相同的強度。然而,摩擦具有該等膠囊之該頭髮樣版可明顯增強香味。
實例8
製造包含實例2之10層PMAA/PVP微膠囊之馬桶清潔圓型塊(rim block)。
馬桶清潔圓型塊凝膠調配物係藉由混合以下所列組分製得。
馬桶清潔圓型塊凝膠係藉由將以相對馬桶清潔圓型塊總重量計2重量%之包含專用香味劑2(不同於上述調配物中之香味劑1)的微膠囊混入以上所製得馬桶清潔圓型塊調配物中而製得。將該等膠囊中該類型專用香味劑2(其不同於自由香味劑)添加至具有相同調配物之另一馬桶清潔圓型塊(亦含有香味劑1),以致香味劑的添加量相等。
將該等馬桶清潔圓型塊凝膠施用於個別馬桶。
在使馬桶清潔圓型塊與水(pH 7)接觸之前及之後由8位經過培訓之研究組員組成之專家小組基於盲測基礎來評估香味。
於不含膠囊之馬桶清潔圓型塊之情況中,組員們發現就不存在微膠囊之情況而言在使該馬桶清潔圓型塊與水接觸之前及之後香味相同。
於包含微膠囊之馬桶清潔圓型塊之情況中,在使該馬桶清潔圓型塊與水接觸之前及之後香味明顯不同,此乃因膠囊由於因馬桶水(pH 7)引起之pH的增加而破碎。
Claims (13)
- 一種囊封活性物質之方法,該方法包括:(a)將活性物質分散於具有小於6之pH之水性介質中;(b)於此經分散之活性物質上形成聚合物殼,該形成包括連續沉積一系列聚合物層,各層能夠與前一層氫鍵鍵結;以形成含活性物質膠囊之水性漿液;其特徵在於,頭兩層中之一層為多羧酸及該等頭兩至四層一起展現大於10mN/m、較佳大於20mN/m之界面壓縮膨脹模數。
- 如請求項1之方法,其中該頭兩層包括選自聚(甲基丙烯酸)/聚(乙烯吡咯啶酮)、聚(丙烯酸)/聚(乙烯吡咯啶酮)、聚(乙酸乙烯酯)/乙烯-馬來酸酐共聚物及聚(乙烯醇)/乙烯-馬來酸酐共聚物之聚合物之組合。
- 如請求項1之方法,其中該方法包括一系列個別層化階段,其中過量施覆連續之聚合物水溶液及在施覆下一層之前洗去剩餘物。
- 如請求項1之方法,其中該聚合物殼係經交聯。
- 如請求項5之方法,其中該等聚合物包含胺基或羥基,及交聯係藉由添加交聯材料(較佳係胺、戊二醛、異氰酸酯、環氧化物或矽酸酯偶聯劑)來實現。
- 如請求項1之方法,其中該聚合物殼具有最終矽酸酯層。
- 如請求項6之方法,其中矽酸酯層係藉由水解(R)nSi(ROH)4-n(其中R為C1-C3烷基且n=1至4)及添加水解產物至膠囊之水性漿液來提供。
- 如請求項1之方法,其中可於該聚合物殼上沉積其他材料。
- 如請求項8之方法,其中該等其他材料係選自胺基塑膠 (aminoplast)、聚脲、聚胺基甲酸酯、聚丙烯酸及無機材料。
- 一種經囊封活性物質,其包括完全被聚合物殼環繞之活性物質之核,該殼包括至少兩層聚合物,各聚合物層係與相鄰層氫鍵鍵結,及頭兩層中之一層為多羧酸,該等頭兩至四層一起展現大於10mN/m、較佳大於20mN/m之界面壓縮膨脹模數。
- 如請求項10之經囊封活性物質,其中該聚合物殼具有5nm之最小厚度。
- 如請求項10之經囊封活性物質,其中該聚合物殼具有自5至100、特定言之自5至70、更特定言之自5至50nm之厚度。
- 一種市售組合物,其包含市售組合物基質及如請求項10之經囊封活性物質。
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CN108473917A (zh) | 2015-12-22 | 2018-08-31 | 荷兰联合利华有限公司 | 微囊 |
JP7231611B2 (ja) | 2017-07-31 | 2023-03-01 | ダウ グローバル テクノロジーズ エルエルシー | 洗剤添加剤 |
EP3498253B1 (en) * | 2017-12-14 | 2021-02-17 | Clariant International Ltd | Vesicles for delayed delivery of fragrance their preparation and use thereof |
GB202118166D0 (en) | 2021-12-15 | 2022-01-26 | Givaudan Sa | Improvements in or relating to organic compounds |
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JPS61125432A (ja) * | 1984-11-22 | 1986-06-13 | Lion Corp | マイクロカプセルの製造方法 |
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ES2621203T3 (es) | 2002-08-14 | 2017-07-03 | Givaudan S.A. | Composiciones que comprenden un material encapsulado |
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JP2007514518A (ja) * | 2003-10-02 | 2007-06-07 | トラスティーズ オブ スティーヴンス インスティチュート オブ テクノロジー | 水素結合によって結合した多層中性ポリマーフィルムのカプセル |
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KR102182371B1 (ko) | 2020-11-25 |
BR112015008313A2 (pt) | 2014-05-01 |
EP2911779B1 (en) | 2018-12-12 |
JP6423350B2 (ja) | 2018-11-14 |
CN105188906A (zh) | 2015-12-23 |
AU2013336577A1 (en) | 2015-04-09 |
EP2911779A2 (en) | 2015-09-02 |
AR093133A1 (es) | 2015-05-20 |
CA2886338C (en) | 2021-01-12 |
WO2014064252A2 (en) | 2014-05-01 |
US10940336B2 (en) | 2021-03-09 |
CA2886338A1 (en) | 2014-05-01 |
TWI605870B (zh) | 2017-11-21 |
BR112015008313A8 (pt) | 2019-07-16 |
MX366824B (es) | 2019-07-25 |
AU2013336577B2 (en) | 2016-10-06 |
ZA201502344B (en) | 2016-10-26 |
BR112015008313B1 (pt) | 2020-12-01 |
JP2016501707A (ja) | 2016-01-21 |
US20150223502A1 (en) | 2015-08-13 |
WO2014064252A3 (en) | 2014-07-10 |
KR20150092123A (ko) | 2015-08-12 |
CN105188906B (zh) | 2018-09-04 |
MX2015004367A (es) | 2015-12-15 |
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