CN103154226B - 经涂覆的颗粒洗涤剂的制造 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
- C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
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Abstract
制造具有正交尺寸x、y和z的大的涂覆洗涤剂颗粒的方法,其中x为0.2-2mm,y为2.5-8mm,而z为2.5-8mm,颗粒彼此基本上是相同形状和大小的,并且未涂覆的核颗粒包含至少50重量%可溶性表面活性剂,该方法包括以下步骤:将未涂覆的核颗粒悬浮于流化床中,并且向核颗粒上喷雾与0.6-3重量%羧甲基纤维素钠混合的碳酸钠水性浆料,和干燥以形成涂覆颗粒。
Description
技术领域
本发明涉及直径大、厚度较小和颗粒大小分布窄的涂覆颗粒洗涤剂的制造。
背景
理论上,通过从组合物中除去那些仅有有限清洁作用或无清洁作用的所有成分,可以设计出具有提高的环境特性的颗粒洗涤剂组合物。这样的压缩产品还将降低包装需求。然而,在实践中实现这个目的是困难的,因为颗粒洗涤剂组合物的制造通常需要使用没有显著提供清洁作用,但仍需包含以将液体成分结构化成固体的成分,以帮助加工和提高颗粒洗涤剂组合物的操作和稳定性。
在我们未决的申请PCT/EP2010/055256和PCT/EP2010/055257中,我们提出了通过制造新的颗粒洗涤剂组合物来解决这些问题。一般而言,使用包括以下步骤的方法来制造:将表面活性剂混合物干燥、将其挤出并切割挤出物,以形成直径大于2mm和厚度大于0.2mm的硬核颗粒。然后将这些大的核颗粒优选进行涂覆,尤其是使用无机涂层。
包含至少70重量%的这些具有挤出表面活性剂核的涂覆大颗粒的组合物不同于现有技术的挤出洗涤剂组合物,因为它们有很少的或没有固体结构材料来硬化或结构化表面活性剂核。相反,它们使用低水分表面活性剂的混合物来获得硬度。表面活性剂的选择使得颗粒产生良好的去污力,甚至不需要任何常规的洗涤剂增效剂,因此消除了颗粒中对这种增效剂的需求。尽管挤出颗粒足够硬,使得能够切割成所需的形状而没有变形,但它们是吸湿的并且如果没有涂覆的话将粘在一起。因此,通过在流化床中将无机材料(如碳酸钠)喷雾至核颗粒上来对其涂覆将是有利的。涂层和大的颗粒大小(直径5mm)的组合基本上消除了任何变形或结块的趋势,并且可以生产大于常规洗涤剂颗粒的具有极好的光滑和均一外观的新的自由流动的组合物。令人惊讶地,尽管它们的体积大并且密度高,但颗粒快速溶解,残留低,并且形成清澈的清洗液体,具有极好的初始去污力。
在PCT/EP2010/055257中,通过在流化床中将碳酸钠溶液喷雾在核上,将无机盐(碳酸钠)的涂层施加于大的洗涤剂核上。因为碳酸钠溶解度不高,因此该过程需要排出大量的水,以在水溶性洗涤剂核上形成20至30重量%涂层。需要小心不能溶解核。因此所述的碳酸钠涂覆过程是费时且耗能的。
尽管我们已经从碳酸钠溶液生产了非常成功的涂层,但由于对碳酸盐溶液强度的限制和随后必需除去大量水以在洗涤剂颗粒上获得显著水平(例如,>20重量%)的涂层,因此它们的生产较慢。此外,流化过程必须非常严密且小心地控制,以避免床的骤冷。
US6596683B(P&G)还描述了一种方法,其中用无机水溶液喷雾涂覆包含洗涤剂的核颗粒。该核还包括无机增效剂材料。可能由于这个原因,实施例中从碳酸钠溶液仅获得了2重量%的涂层水平。这与第10栏中无机溶液以6%的最大水平施用的教导相一致。由于核中增效剂的存在,没有动机将涂层水平提高至高于最大值6%。
US2004235704A(P&G)描述了流化床中的洗涤剂颗粒的涂层。在至少3.5的流量数(flux number)下运行该流化床。干燥后,据称所得到的洗涤剂颗粒具有提高的外观和流动特性。优选的涂层是非水合无机盐,特别是碳酸钠矾(Burkeite)。与大部分现有技术的教导一样,其在第68段教导了涂覆的基础颗粒包括增效剂。实施例使用了25%的碳酸钠矾溶液,以获得4%的涂层。
US6858572B(P&G)公开了用于制备洗涤剂颗粒的方法,所述颗粒包含洗涤剂活性材料的颗粒核。然后该颗粒核至少部分被水溶性无机材料的颗粒涂层覆盖。特别优选的是不可水合的无机涂层材料,包括碱金属碳酸盐和硫酸盐的双盐组合(碳酸钠矾)。该方法包括使颗粒核通过涂层混合机(如,低速混合机或流化床混合机)并用水溶性无机材料的涂层溶液或浆料涂覆颗粒核的步骤。在优选的实施方式中,涂层混合机是流化床。为了获得最佳效果,将喷嘴放置在流化床中的颗粒流化高度处或之上。其目的似乎是为了形成相同大小并且尽可能是球形的颗粒。流化床的涂层区之后是干燥区,再然后是冷却区。实施例1喷雾了28.5重量%碳酸钠矾,或等效溶液,以形成5%的涂层。实施例2喷雾了67%柠檬酸钾溶液,以制得5%的涂层。实施例2中较高的溶液浓度意味着比实施例1中更少的水需要蒸发。然而,涂覆颗粒会是粘的,除非另外增加附加的干燥涂层。该专利没有以可实施的方式充分公开喷雾浆料。
US3989635A(Lion)公开了一种改进颗粒洗涤剂的方法。在实施例9中,颗粒涂覆有与碳酸钠粉一起加入流化床的15%碳酸钠溶液。所得到的1重量%涂层一半来自溶液,一半来自单独添加的固体。单独的固体添加的缺陷在于它们不利地影响了涂层的外观,并且与其他现有技术中进行的在溶液中添加全部固体负荷物相比,它们不具有预期的降低干燥时间的益处。
US2004198629A(Henkel)公开了用不溶性材料包覆的洗涤剂颗粒。包覆层由具有至少12个碳原子的羟基化脂肪酸的多价金属盐(例如,蓖麻醇酸锌)形成。包覆材料优选在流化床中以水性分散体的形式来施加。示例性涂层悬浮液由16重量%二氧化钛、16重量%PEG 12000、1.5重量%的混合物(50重量份蓖麻醇酸锌、35重量%三乙氧基化月桂醇和15重量%四(2-羟丙基)乙二胺(Tegosorb conc 50))、0.5重量%羧甲基纤维素钠以及剩余的水组成。尽管SCMC因此存在于实施例1中,但不存在于实施例2中的相似悬浮液中,因此不能认为是悬浮体系的必要部分。这与本领域技术人员的理解相一致:在浆料中存在大量表面活性剂时,通常不需要悬浮聚合物。因此,本领域技术人员将理解加入SCMC可能是用于悬浮二氧化钛颜料。其不是必需的(如从实施例2可以清楚看出),因为非离子型表面活性剂可以起到相同作用。即使存在表面活性剂,相同的本领域技术人员通常将选择聚合物,如丙烯酸马来酸共聚物。
发明概述
根据本发明,提供了制造具有核和涂层的涂覆洗涤剂颗粒的方法,该涂覆洗涤剂颗粒具有正交尺寸x、y和z,其中x为0.2-2mm,y为2.5-8mm(优选3-8mm),且z为2.5-8mm(优选3-8mm),并且未涂覆的核颗粒包含至少50重量%的可溶性表面活性剂,该方法包括以下步骤:将未涂覆核颗粒悬浮于流化床中,并且将水性浆料喷雾在核上,并且干燥以形成该经涂覆的颗粒,其中所述浆料在至少35℃的温度下进行喷雾,该水性浆料包含:碳酸钠与0.6-3重量%的羧甲基纤维素钠的混合物。
优选地,该浆料包含45-60重量%的碳酸钠。
理想地,该浆料的最大颗粒大小为50微米。可以通过研磨方便地将颗粒大小控制在该最大值。更大的颗粒难以喷雾并且不会有效地形成薄膜。
优选通过至少一个喷雾头进行该喷雾。该至少一个喷雾头优选浸没在流化的表面活性剂颗粒中,以避免喷入流化床的自由空间中。
优选地,该浆料在至少45℃的温度下进行喷雾,更优选至少55℃。浆料必需保持在升高的温度下,以保持其是单水合物。如果其回复成溶解性较低的形式,可能形成大的碳酸钠晶体,这对于随后的喷雾将引起问题。
流化空气的温度优选在30-80℃的范围内。最优选,流化空气温度优选在35-150℃的范围内。
浆料添加速率与空气流动速率的比率有利地为30-350m3空气/kg浆料喷雾。
此外,根据本发明,提供了涂覆挤出的可溶性表面活性剂颗粒的方法,其包括如下步骤:通过空气流将该挤出的可溶性表面活性剂颗粒流化,之后在该挤出的可溶性表面活性剂颗粒处于流化态时,在至少35℃的温度下将该水性浆料喷雾到该挤出的可溶性表面活性剂的颗粒上,该水性浆料包含至少33重量%的碳酸钠和0.6-3重量%的羧甲基纤维素钠,悬浮液中的碳酸钠颗粒的大小小于或等于50微米。
用于喷雾到颗粒上的水性浆料中夹带的颗粒的大小优选为小于50微米;特别地,这适用于碳酸钠,但优选还适用于水性浆料中所有的夹带材料。
浆料可以包含最高60重量%的碳酸钠,任选与其他可溶性或不溶性无机材料混合。
浆料可以包含至多5重量%的表面活性剂,优选低于1重量%的表面活性剂,和最优选其不包含表面活性剂。
对于待涂覆的含表面活性剂的核颗粒,与LAS/SLES/PAS相比LAS/非离子型一般粘性较小,硬度较高,并且更易于涂覆浆料。然而,LAS/SLES/PAS对于高泡应用是感兴趣的。
可以将硅酸盐加入涂层浆料中。
使用不含任何表面活性剂的浆料喷雾涂层不是容易的。当使用浆料时,遇到了问题。浆料沉淀,因此其没有如预期那样浓缩。进料管和喷嘴随着浆料沉淀或干燥而阻塞。此外,在流体床中涂覆颗粒前,浆料易于喷雾干燥。通过使用SCMC来帮助悬浮,解决了所有这些问题。通过碾磨浆料获得了更多改进,并且通过将喷头浸没在流化床中甚至获得进一步改进。优选地,涂覆的洗涤剂颗粒中核与涂层比率为3-1∶1,最优选2.5-1.5∶1,例如2∶1。
发明详述
羧甲基纤维素钠(SCMC)是聚合物的理想选择,因为其是为了其他目的已用于洗涤剂制剂中的材料。因此,这不是简单地添加不具有其他目的的加工助剂。这种添加不具有清洁作用的聚合物与发明人工作所针对的高度浓缩的组合物的制剂原则相背。令人惊讶地,我们发现了满足高度浓缩颗粒洗涤剂的一般制剂原则的其他聚合物,如CP5(常用于帮助洗涤剂浆料在其喷雾干燥之前悬浮的聚合物),在基本上不存在表面活性剂的浆料中没有提供相同的浆料悬浮特性,而基本上不存在表面活性剂的浆料是本发明的方法优选的情况。
可以加入浆料中的其他材料是硅酸盐、荧光剂、染料、沸石和颜料。
我们发现了碳酸盐的浆料只在35.4℃以上是稳定的,否则形成固体水合物。需要微量加热来保持升高的温度在35℃以上。保持升高的温度以避免形成大的晶体是高度有利的。大的晶体从悬浮液中沉落,引起管线和喷头阻塞。
甚至发现了碳酸钠未再结晶的浆料阻塞了喷嘴。通过使浆料悬浮液通过在线的Silverson碾磨机以使颗粒大小减小至小于或等于50微米来解决这个问题,使得成功雾化。
高于床进行喷雾可能使浆料在到达颗粒之前喷雾干燥,这种倾向部分可通过接近床进行喷雾(<250mm)来解决,或更优选,通过在床内进行喷雾,例如,经由底部喷雾。
现在将参照以下非限制性实施例进一步描述本发明。
实施例1
按照PCT/EP2010/055256中的方法,制造了涂覆的大洗涤剂颗粒。
将表面活性剂原料混合在一起,以获得包含85份LAS(直链烷基苯磺酸盐)和15份非离子型表面活性剂的67重量%活性糊状物。所用的原料为:
LAS:Unger Ufasan 65
非离子型:BASF Lutensol AO30
将糊状物预热至进料温度并且加入刮膜式蒸发器的顶部以降低含水量并且产生固体紧密的表面活性剂混合物。表1中给出了用于产生这种LAS/NI混合物的条件。
表1
*通过Karl Fischer方法分析
从刮膜式蒸发器的底部出来时,干燥的表面活性剂混合物落在冷却辊上,在那冷却至低于30℃。
离开冷却辊后,使用锤式碾磨机碾磨冷却的干燥表面活性剂混合物颗粒,还将2%Alusil作为碾磨助剂加入锤式碾磨机中。所得到的碾碎材料是吸湿的并且储存在密封容器中。
将冷却的碾碎组合物进料到配置有成型孔板和切割刀片的双螺杆共旋转(corotating)挤出机中。还将如表2中所示的多种其他成分定量进料到挤出机中:
表2
实施例1 | |
挤出机 | 份(最终颗粒=100) |
LAS/NI混合物 | 64.3 |
SCMC | 1.0 |
香料 | 0.75 |
发现挤出的核颗粒样品的平均颗粒直径(y和z)和厚度(x)分别是4.46mm和1.13mm。标准偏差低,是可接受的。
实施例2和比较实施例A
然后将实施例1中产生的洗涤剂颗粒核转移至Agglomaster流化床并且在60℃下用浆料进行喷雾,所述浆料由49.5重量%碳酸钠、49.5重量%水和1重量%SCMC组成。涂覆的核具有施加到实施例1中制得的LAS/NI核上的碳酸盐涂层。为了比较,使用碳酸钠溶液涂覆相同的核颗粒,这是比较实施例A。
浆料涂覆工艺条件-实施例2
所用的空气进口温度范围:35-70℃
该方法过程中的产品温度:38-42℃
空气流动速率(冷空气):850-926m3/hr
浆料添加速率:70g/min至496g/min
所用的外部雾化喷嘴:喷雾系统60100喷液孔(fluid cap)和120喷气孔(air cap)
在线Silverson研磨机设定在2500rpm
管线上的伴随加热:60℃
容器上的伴随加热:45℃
涂覆速率=对于每获得1%涂层水平为5.291kg核/min
流量数高于3.5
比较实施例A
LAS/NI晶体,30%碳酸钠溶液
最终产品:LAS/NI核上的碳酸盐涂层
溶液涂覆工艺条件-实施例A
所用的空气进口温度范围:45-90℃
该方法过程中的产品温度:35-47℃
空气流动速率(冷空气):850m3/hr
浆料添加速率:82g/min至427g/min
所用的内部雾化喷嘴:喷雾系统40100喷液孔和1401110喷气孔
管线上的伴随加热:45℃
容器上的伴随加热:45℃
涂层速率=对于每获得1%涂层水平为2.703kg核/min
实施例2和比较实施例A二者都产生了碳酸盐涂覆的核,然而在实施例2的情况中,涂覆速率接近两倍。
实施例3以及比较实施例B和C
NaLAS/NI核优于NaLAS/PAS/SLES或LAS/NI铵盐
用悬浮有SCMC的浆料涂覆时,我们发现了NaLAS/NI(实施例3)优于NaLAS/PAS/SLES(B)和LAS/NI铵盐(C),尤其是在较大规模的涂覆下(10kg规模)。不希望受到理论的束缚,我们认为这是因为基于NaLAS/NI的核较硬——尤其是如在流化床涂层设备中发现的温热潮湿的条件下。已经发现了如果将涂层速率设定为对现实的商用方法可接受的高,核柔软性和相关的粘性在核得到适当涂覆前将引起床崩解。本领域技术人员将能够使用常规实验室涂层设备来测试核是否足够硬以可被涂覆。
实施例4以及具有CP5的比较实施例D和E
我们制得了悬浮有SCMC(实施例4)和两种水平的替换聚合物CP5(来自BASF的用于悬浮常规洗涤剂浆料的丙烯酸马来酸聚合物)(比较实施例D和E)的50重量%碳酸钠浆料。将60mm深度的每种浆料加入试管中并且在40℃下储存14小时。然后从储存中取出并且测量沉淀量。表3中给出了详细内容和结果。
表3
除了静态沉降行为的差异,我们发现了SCMC样品更易于重新悬浮。CP5比较样品都更压实并且因此更难以重新悬浮。这在任何实践过程中都将是问题,因为尽管存储罐可以通过连续搅拌保持悬浮,但防止进料管线中的沉淀不是那么容易,因此使浆料材料重新悬浮的能力是有利的。
Claims (13)
1.制造具有核和涂层的涂覆洗涤剂颗粒的方法,所述涂覆洗涤剂颗粒具有正交尺寸x、y和z,其中x为0.2-2mm,y为2.5-8mm,且z为2.5-8mm,并且所述未涂覆的核颗粒包含至少50重量%的可溶性表面活性剂,所述方法包括以下步骤:将未涂覆核颗粒悬浮于流化床中,并将水性浆料喷雾在核上,和干燥以形成所述涂覆颗粒,其中所述水性浆料在至少35℃的温度下进行喷雾,所述水性浆料包含:碳酸钠与0.6-3重量%羧甲基纤维素钠的混合物,所述浆料的最大颗粒尺寸为50微米。
2.根据权利要求1的方法,其中所述水性浆料包含45-60重量%的碳酸钠。
3.根据权利要求1或2的方法,其中在喷雾之前将所述浆料进行碾磨。
4.根据权利要求1或2的方法,其中通过至少一个喷头进行所述喷雾。
5.根据权利要求4的方法,其中将所述至少一个喷头浸没在流化的表面活性剂颗粒中。
6.根据权利要求1或2的方法,其中所述浆料在至少45℃的温度下进行喷雾。
7.根据权利要求1或2的方法,其中流化空气温度在35-150℃的范围内。
8.根据权利要求1或2的方法,其中浆料添加速率与空气流动速率的比率为30-350m3空气/kg浆料喷雾。
9.涂覆挤出的可溶性表面活性剂颗粒的方法,所述方法包括如下步骤:通过空气流将所述挤出的可溶性表面活性剂颗粒流化,然后在所述挤出的可溶性表面活性剂颗粒处于流化态时,在至少35℃的温度下将水性浆料喷雾到挤出的可溶性表面活性剂的颗粒上,所述水性浆料包含至少33重量%的碳酸钠和0.6-3重量%羧甲基纤维素钠,悬浮液中的碳酸钠颗粒的尺寸小于或等于50微米。
10.根据权利要求9的方法,其中所述浆料包含最高60重量%碳酸钠,任选与其他可溶性或不溶性无机材料混合。
11.根据权利要求1、2、9或10的方法,其中所述浆料包含至多5重量%的表面活性剂。
12.根据权利要求1、2、9或10的方法,其中所述可溶性表面活性剂包含直链烷基苯磺酸盐(LAS)和乙氧基化醇类非离子型表面活性剂的混合物。
13.根据权利要求1、2、9或10的方法,其中所述浆料进一步包含硅酸盐。
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- 2011-08-10 US US13/878,440 patent/US9365811B2/en active Active
- 2011-08-10 PL PL11741237T patent/PL2627750T3/pl unknown
- 2011-08-10 EP EP11741237.9A patent/EP2627750B1/en active Active
- 2011-08-10 WO PCT/EP2011/063748 patent/WO2012048926A1/en active Application Filing
- 2011-08-10 ES ES11741237.9T patent/ES2542240T3/es active Active
- 2011-08-10 BR BR112013008992-0A patent/BR112013008992B1/pt active IP Right Grant
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2013
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ZA201302300B (en) | 2014-06-25 |
ES2542240T3 (es) | 2015-08-03 |
BR112013008992A2 (pt) | 2016-07-05 |
US20130287940A1 (en) | 2013-10-31 |
AU2011316094B2 (en) | 2014-01-23 |
AR083370A1 (es) | 2013-02-21 |
WO2012048926A1 (en) | 2012-04-19 |
CA2813697A1 (en) | 2012-04-19 |
MY158490A (en) | 2016-10-14 |
EP2627750A1 (en) | 2013-08-21 |
BR112013008992B1 (pt) | 2020-12-08 |
CN103154226A (zh) | 2013-06-12 |
CL2013001023A1 (es) | 2013-12-06 |
US9365811B2 (en) | 2016-06-14 |
PL2627750T3 (pl) | 2015-08-31 |
CA2813697C (en) | 2018-08-28 |
MX2013003936A (es) | 2013-06-28 |
EP2627750B1 (en) | 2015-04-08 |
AU2011316094A1 (en) | 2013-04-11 |
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