CN1925959A - 多层合成物品 - Google Patents
多层合成物品 Download PDFInfo
- Publication number
- CN1925959A CN1925959A CNA2005800067246A CN200580006724A CN1925959A CN 1925959 A CN1925959 A CN 1925959A CN A2005800067246 A CNA2005800067246 A CN A2005800067246A CN 200580006724 A CN200580006724 A CN 200580006724A CN 1925959 A CN1925959 A CN 1925959A
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- CN
- China
- Prior art keywords
- layer
- resin
- article
- functional
- layers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Images
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Abstract
一种轴对称多层物品，其形成一厚度为E的壁，所述物品由第一树脂和第二树脂构成，其中第一树脂形成物品的结构并至少占据物品体积的80％，其中第二树脂至少形成两个功能细层，所述功能层分别包裹在第一树脂中，该多层结构的特征在于：功能层分布在物品的不同部分中；功能层形成旋转体，该旋转体的中心位于物品的对称轴上；两功能层在布置上其中一层沿所述壁的垂直方向部分地布置在另一层顶上。
Description
技术领域
本发明涉及一种对一剂多层物料进行压模从而制造一种多层物品的方法。
背景技术
美国专利US4876052公开了一种多层物品(参见图1)，其特征在于第一合成树脂3完全封闭在第二合成树脂2中。这种多层物品是由一剂复合物料经压模获得的，其中第一树脂完全封闭在第二树脂中。美国专利US4876052中公开的多层结构特别适用于像容器或盖子这样的物品上。然而，这种由美国专利US4876052中描述的方法所获取的物品要求功能树脂在物品中占很高比例，因此存在两个缺点。第一就是成本高，第二就是对机械应力的阻抗下降。功能树脂和外层树脂之间缺少粘性也降低了物品的稳固性并有可能使外层脱开。美国专利US487605的另一个缺点是树脂2和3量不好调节。如本发明所述的那样，树脂2和3的量是由物品的几何结构以及该剂物料在压制过程中的流动确定的。该方法同样要求将第一树脂断续地挤到第二树脂中。美国专利US4876052公开了一种共挤设备，该设备具有一个用于第一种合成树脂的切断阀机构。
为了消除美国专利US4876052的缺点，日本专利JP2098415提出由一剂复合物料通过压模来实现多层物品，其特征在于第二合成树脂仅覆盖住第一合成树脂的侧面。沿着该剂物料的对称轴线进行压模就生产出一种具有多层结构的物品(图2)，其特征在于第一树脂2部分包裹在第二树脂3中。然而，根据日本专利JP2098415由两种树脂得到的多层物品具有两个明显的缺点：第一，曝露于物体中心表面上的阻挡树脂3超过了物体总表面的至少10％；第二，物品中所需阻挡树脂7的量至少要占到总树脂量的30％。由此生产出的物体一方面价格过高，另一方面机械特性特别是物体中心的机械特性变化很大。日本专利JP2098415的另一个缺点是树脂2和3各自的数量仅可稍微调节，它们的量均由物品的几何结构以及该剂物料压模过程中的流动来固定。
在专利JP2098415中，提出使用一剂三层物料从而部分地消除前述的缺点。该剂物料包括：第一树脂4，其形成该剂物料的中心部分，第二树脂3，其仅用来覆盖第一树脂的侧面；以及第三树脂2，其仅用来覆盖第二树脂的侧面。沿着该剂物料的对称轴线挤压该复合物料就得到一多层物品(参见图3)。三层物料的使用具有减少功能树脂3用量的优点，同时相对于内含一种树脂2的物品来说还能制造出机械特性稍有改变的物品。然而，第二树脂3并不覆盖多层物品的中心部分，其生产出的多层物品在靠近对称轴线的地方没有阻挡特性。该物品上未被阻挡树脂层3覆盖的中心区域会消弱物品的阻挡性能，并使这种解决方案缺乏有效性。
专利申请CH01619/04公开了一种由一剂多层物料经压模实现的多层物品(图4)，该专利申请中公开的物品具有一多层结构，其特征在于形成了一Z字形双折的功能层的位置。该功能层在该物品处处正确地分布，并分布在中心部分中。专利申请CH01619/04中公开的实现多层物品的方法也能对功能层的厚度进行控制。可在形成物品表面的树脂和功能树脂之间加入一粘性层。然而，该剂物料的压制需要用到一种方法以及一种特定的成型设备。相对于基本的压制工艺来说，该方法特别要求模具有额外的运动，即模具的两个部分存在相对的运动。在高速成型的时候，采用专利申请CH01619/04所公开的压制设备是不利的。
专利EP926078公开了一种通过对一剂包含层压多层结构的物料进行模压而获得的一插塞衬里(图5)。该功能树脂3形成有许多散布在树脂2中的条。该方法的操作步骤包括：用一片材生产设备挤出一剂层压物料(千层饼式)，然后压制该剂物料从而形成衬里。在衬里的厚度上(图5)是一种千层饼式的多层结构。该方法包括压模一层压合金，该剂物料中片材的数量非常大。该方法的缺点是需要很高百分比(20％量级)的阻挡树脂从而会显著降低物品的渗透性，因为这些片条不会形成一个连续的层。专利EP926078的另一个缺点是不能控制片条在物品中的位置。结果是用来形成多层物品面层的树脂就是一个由剂物料形成的不同层而构成的混合体。当被包装产品与层压多层物品接触时，出于卫生的考虑，这就限制了专利EP926078所述物品的使用。专利EP926078的另一个缺点是树脂的选择有限，这种树脂所具有的粘性和融化温度必须能使片条在该剂物料被压制时保持不变。
发明内容
本发明旨在对一剂多层物料进行压模来实现多层物品，同时其能消除前述的缺点。
本发明由一种轴对称多层物品构成，其形成一厚度为E的壁，所述物品由第一树脂和第二树脂构成，其中第一树脂形成物品的结构并至少占据物品体积的80％，其中第二树脂至少形成两个功能细层，所述功能层分别包裹在第一树脂中，该多层结构的特征在于：
功能层分布在物品的不同部分中；
功能层形成旋转体，该旋转体的中心位于物品的对称轴上；
两功能层在布置上其中一层沿所述壁的垂直方向部分地布置在另一层上。
附图说明
通过下面附图所示示例的详细说明，能够更好地理解本发明。其中：
图1到5所示为现有的多层物品
图1是专利US4876052所公开的一种多层物品，该多层物品1，由压模制成，包含一功能树脂层3，其完全包裹在形成物品可见表面的树脂2中；
图2是专利JP2098415所公开的一种多层物品，该物品1包含一功能树脂层3，其部分包裹在形成物品可见表面的树脂2；
图3是专利JP2098415所公开另一种多层物品。该物品包括一层精细的功能树脂3，其包裹在形成物品的两层树脂2和4之间；
图4所示为申请CH01619/04中公开的一种多层物品。该物品的特征是功能层3的Z字形双折；
图5所示为专利EP926078中公开的一个包括一层压多层结构的物品；
图6到11对应于本发明的多层物品
图6展示了本发明的第一种多层物品。该多层结构是沿一个穿过物品对称轴的剖面观察得到的示图。其中的功能层3、5和7形成交叠；
图7所示为第二例多层物品，其中心表面面积S未被功能层覆盖；
图8和9所示为根据本发明实现并有开孔15的物品；
图10所示为根据本发明实现的一多层塞子；
图11所示为本发明实现的一多层预型件；
图12展示的是该剂物料在压制过程中的流量剖面；
图13展示的是用来获得多层物品的方法，特别是物料与物品之间的关系；
图14所示的是比值S/Sp，即物品表面积中未被功能层覆盖的表面积与该物品表面积的比，是如何随着压缩比H/E变化的；
图15展示的是专利JP20418415的物品的实现情况；
图16所示专利JP20418415所实现的物品的比值S/Sp是如何随着H/E变化的；
图17所示为本发明物品的另一例实现情况。
具体实施方式
本发明涉及一种多层物品，其至少具有两层独立的功能树脂，其分布在用来形成物品结构的第二树脂的细层中，所述层分布在物品的不同部分中并形成部分交叠。术语“功能树脂”表示一种树脂，其对气体或香气具有阻挡性能。
图6所示了本发明的一种多层物品。该物品的厚度是沿着一个垂直物品表面并穿过对称轴的断面而观察的。该图展示了功能层在部件厚度中的分布情况。该功能树脂形成细层3、5和7，这些层分布在用来形成物品结构层2、4和6的基质树脂中。功能树脂的量通常不到整个树脂体积的10％。为了获得最优的阻挡性能，功能层在布置时其中一层布置在另一层上从而形成交叠L。在一优选实施例中(图中未示出)，交叠L的值为厚度E的1到3倍，由此所获得的渗透性接近于一个有相同厚度的连续层所获得的渗透性。在图6中，物品的中间部分由功能树脂层7形成。用来形成物品中间层7的功能树脂的量至多占总树脂体积的5％，其通常小于3％。中间的功能树脂层7具有一外露的面积S，其至多占物品总表面面积的3％，优选为小于1％。功能树脂层3、5和7的端部9、10和11靠近物品的顶面和底面，其也可与物品的表面齐平，或者是完全包裹在物品中。功能层3、5和7分别形成折12、13和14。层3的折12总的来讲靠近物品的侧壁从而在物品的整个表面上形成不渗透的特性。在某些情况下，不必使物品的整个表面都具有不渗透的特性，此时仅使所述层3分布在物品必须不渗透的地方即可。功能树脂层5和7的折13和14在布置上应使其中一层在功能层3和5的端头9和10处于另一个层的顶上并形成交叠。功能层的这种交叠能在不同层不连续的情况下依然获得很好的不渗透性。
图7所示为本发明第二例多层物品，该物品与图6所示的物品不同在于其中间部分。图7中的物品展示了独立功能层3、5和7在形成物品结构的树脂层2、4、6和8中的布置。该功能树脂层3、5和7形成各自的折12、13和14。折13和14在布置上其中一个在功能树脂层3和5的端头9和10布置于另一个的顶上，并形成交叠，从而确保很好的不渗透性。功能树脂层7的端头11并不覆盖物品的中间部分，而留了一个可渗透的表面S。考虑到未被功能层覆盖的表面面积占总曝露面积的比率S/Sp，可以看到由表面S形成的渗透非常小，本发明允许比率S/Sp小于2％，由此所形成的渗透可忽略不计。
图8所示为本发明方法所实现的第三种多层物品。该物品1包括一个中间的开孔15以及两个功能树脂细层3和5，其分布在形成物品结构的树脂层2、4和6之间。功能层3和5形成折12和13，折13被功能层3的端头9所重叠。
图9所示为另一例具有开孔的多层物品。该物品与图8所示物品的不同在于功能树脂层3和5的折12和13的方向不同。
下面给出的用来实现多层物品的方法特别适用于实现像塞子、盖子、预型件或者是管肩这样的物品。该方法同样可适用于实现层板形式的预型件，然后将这些层板用在热塑成型或者是热吹塑成型中从而形成多层物品。图10所示一多层结构，其可在塞型物品的几何结构中获得。图11所示为根据本发明实现的一种多层预型件。这些物品都具有部分叠置的功能树脂层，从而确保物品的不渗透性。
图10所示的功能层3由三个平行的细层3a、3b、3c组合而成，其中层3b和3c为阻挡层3a两侧的粘性层。这种组合能使不同性质的树脂组合起来，同时还能确保不同层之间具有良好的粘接性，这一点能用来防止多层物品中的分层或者是脱开的问题。粘性层和阻挡层相互平行并且数量很小。形成功能层3的粘性层3b和3c以及阻挡层3a合起来通常会占整个物料树脂体积的不到15％，其优选为在10％之内。
实现本发明多层物品的方法特别好用，因为其几乎不需对现有设备进行什么改变。从下面的内容可以看出，该方法能以很高的生产速度制出多层物品。
该方法包括以下步骤：共挤出一剂柱形或管形的多层物料；将融化状态下的该剂多层物料送入一压制设备中；然后在一模具中压制所述该剂物料从而形成该物品，该方法的特征在于多层物料的几何结构(高度、直径)以及功能层在所述物料中的位置。
为了更好地理解本发明的构思，必须把握多层物料到多层物品的关系。图12所示为该剂物料压制过程中树脂的流动情况。这种流动主要取决于树脂在压制过程中的流变性以及物品的几何结构。图12表明，模具两壁之间中间的流速要快于靠近壁面的流速。在靠近模具壁面的地方，颗粒的移动速率接近于零，但其剪切变形很高。相反，两壁之间中路颗粒的速度最大，同时剪切变形最小。在流动的过程中，功能树脂层被夹带着以不一致的方式变形，这取决于其在流量剖面中的位置。因此，功能树脂层在物品中的最终位置由功能层在该剂物料中的初始位置以及流动过程中的变形总量来确定。
图13所示为用来实现多层物品1的多层物料16。该剂柱形的多层物料16对应于共挤多层杆的一部分，其包括两个包裹在基体树脂层2、4和6之间的功能树脂细层3和5。该剂物料16对应于沿径向叠置的管层，中间层6为柱形。功能树脂的比例通常不超过该剂物料总体积的20％，并优选小于10％。该剂物料经压制会使树脂朝外周流动，这种流动会夹带着功能层3和5并使之在该方向上变形。由此获得的多层物品1如图13所示。在该物品中可以看到功能树脂层3和5在流动的方向上形成折，功能层5的折13与功能层3的端头9形成交叠L。交叠L的大小以及折12伸展到物品端头的情况与该剂物料的初始几何结构以及该剂物料中功能层的位置有关。为了获得图13所示的多层物品，必须将树脂层3和5正确定位于该剂物料中。该剂物料的几何结构以及功能层在该剂物料中的位置可通过计算或实验来确定。通过实验可以看到，两个相邻功能层i和j的径向位置Ri和Rj的比值恒定，其小于或等于0.5，层i比层j更靠近对称轴。
图13中所示物品1的中间表面S未被功能层覆盖。比值S/Sp，即非被覆盖的表面与物品的整个表面的比值，可参见图14。从中可以看到该比值取决于该剂物料的压缩率，即取决于比值H1/E，其中H1对应于该剂物料的高度，E对应于物品的厚度。图14所示为比值S/Sp是如何随着H1/E变化的。从该实验可以看出，在压缩率为5时，物品1的比值S/Sp小于10％，当压缩率为10时，该比值S/Sp小于2％。这一结果表明：在压缩率为10时，产生渗透的表面面积S仅占物品整个表面的不到2％。
为了展示出本发明物品的优点，下面的内容都是相对于专利JP2098415中描述的方法所获得的物品进行的。
图15展示的是如专利JP2098415中提出的一剂物料的压制情况，由此来说明该方法所获得的多层物品的有限性，同时能够更好理解本发明的物品。图15所示为专利JP2098415实现的一剂三层物料16。该剂物料包括：第一树脂4，其用来形成该剂物料的中间部分；一功能树脂3，其仅覆盖第一树脂的侧面；以及一第三树脂2，其仅覆盖功能树脂的侧面。图15所示为该剂物料16经过压制得到物品1。功能层3延伸到物品的端部，同时在物品的外周仍保持包裹状态。如图15所示，该功能层没有延伸到物品1的中间部分中。
根据专利JP2098415而实现的多层物品的实验结果打印在图16中。该图表示的是未被功能层覆盖的表面面积的比率S/Sp随压制比H/H1的变化情况。从该实验可以看出，在压缩率为5时，物品1的比值S/Sp大于25％，当压缩率为10时，该比值S/Sp接近20％。这一结果表明：在压缩率为10时，渗透表面面积S约占物品整个表面的20％。
我们已对专利JP2098415所实现的物品的阻挡性能(图15)和本发明物品的阻挡性能(图13)进行比较。用一剂接近10mm高度H1同时直径基本等于12.7mm柱形多层物料做出厚度为1mm直径为40mm的盘片。所用的基体树脂为HDPE(高密度聚乙烯)，所用的功能树脂为EVOH(乙烯乙烯基乙醇)。通过对氧的渗透性测量表明：本发明物品的阻挡性能比专利JP2098415物品的要强约5到10倍。在这两种情况下，所用功能树脂均为8％。功能层的交叠L大约为1mm。
图17所示为多层物品的第二例实现形式。其中该剂物料16包括功能树脂层3、5和7，其侧面包裹在树脂层2、4和6中。功能树脂层7形成该剂物料的中间部分。该剂物料由一杆制成，该杆由共挤头挤出并在其离开共挤头时按规律截断。接着，将该剂物料送入一压模中，然后压制。沿着该剂物料的对称轴对该剂物料16垂直压制就制得图17中所示的物品1。功能树脂层7使物品的中间部分不可渗透。
用来实现本发明多层物品的方法需要制造多层物料。第一制造方法是以恒定流速共挤一多层杆或管，然后在其离开模具时按规律切断该杆或管，从而形成该剂物料。该第一方法适用于快速制造多层物品。第二种方法是借助于周期性的断续流动来形成该剂物料，在一周期内共挤出形成一剂物料所需数量的材料。该第二方法适用于获得重量非常有规律的多层物料。
该剂物料的切断可通过已知的方法来实现。这一点例如可通过旋转切刀在杆料离开挤压机时来切断杆料。这类切刀同时还能用来将该剂物料送到模具中。通过切断挤出管来切断物料的方法可用在断续挤压设备中。
该剂物料的传送可通过已知的方法来进行，如通过重力或者是借助于传输设备等。该剂物料在压模中的定位必须非常精确，特别是该剂物料的对称轴必须与模具空腔的对称轴精确对齐。然后是沿着该剂物料的对称轴压制该剂物料。该剂多层物料需要在所用树脂适合的温度下以融化状态挤出。该多层物料在传送到压模的过程中要保持融化状态。该剂物料经压模，所获得的物品在脱模前至少要在模具中被部分冷却。
在本发明范围中所用的树脂对应于当前使用的热塑性树脂，特别是那些用于包装工业中的热塑性树脂。其中用来形成功能层3、5和7的阻挡树脂可以是所述的乙烯与乙烯基乙醇的共聚物(EVOH)、聚酰胺如尼龙一MXD6(Nylon-MXD6)、丙烯腈丙烯酸甲酯的共聚物(BAREX)、氟化聚合物如PVDF。这里也可将一些树脂用于形成物品本体结构的层2和4、6和8，如：聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚酰胺(PA)、聚酯(PET)。上述物质列表是非穷尽性的。在树脂的选择中，重要的是选择具有毗邻粘性的产品。一般来讲，优选使用这种在工作温度时其粘性比小于10的树脂，其粘性比优选为小于3。
用来实现本发明物品的设备是已知的设备。该设备最少要包括：用来共挤多层物料的装置；用来将多层物料传送到压模中的装置；以及用来压制该剂物料从而形成物品的装置。
本发明的优点是能够以很高的生产速度生产出多层物品，同时不需对现有的用来制造单层物品的设备做出明显的修改。本发明需要用多层挤出设备来代替单层挤出设备。
在这里所示的示例中，物料和物品均具为简单的几何结构，但本发明显然也适用于任一几何结构的物料和物品。
本发明的物品至少包含两个功能层，其中每一个层均形成有一个折并且其中一个层被部分放置在另一个层的顶上。本发明也可使所获得的物品包含多个功能层，其中有一个功能层被放置在另一个功能层的顶上，并且每一个功能层均能形成一个以上的折。由此获得Z字形的功能层。
物料中的功能层可以有多种布置。本发明最好采用一种特定布置的功能层，所述布置的特征是功能层到对称轴的距离变化的。根据这种变化形式，至少有一个功能层形成一旋转体的壳体，该旋转体的中心处于对称轴上，并且所述层到对称轴的距离是可变化的。
本发明也可采用其它结构的物料。显然，物料的一部分表面内凹会更好一些。这种物料的几何结构有助于阻挡层更好分布于多层物品中。
食品领域中的包装或者是包装部件均要求良好的卫生条件。因此，功能层通常最好不要与被包装的产品直接接触。最好是将功能层完全包裹在物料中，这样所述功能层就完全包裹在物品中。
作为选择，阻挡层可以有一端不被包裹。
Claims (8)
1、一种轴对称多层物品，其形成一厚度为E的壁，所述物品由第一树脂和第二树脂构成，其中第一树脂形成物品的结构并至少占据物品体积的80％，其中第二树脂至少形成两个功能细层，所述功能层分别包裹在第一树脂中，该多层结构的特征在于：
功能层分布在物品的不同部分中；
功能层形成旋转体，该旋转体的中心位于物品的对称轴上；
两功能层在布置上其中一层沿所述壁的垂直方向部分地布置在另一层顶上。
2、如权利要求1的物品，其特征在于重叠距离至少等于物品的厚度E。
3、如权利要求1或2的物品，其特征在于功能层自身形成一多层结构，其包括一层包裹在两层粘性树脂之间的阻挡树脂。
4、如前述任一权利要求的物品，其特征在于第一树脂至少占物品体积的85％。
5、一种用一剂多层物料通过压模获得的多层物品，所述多层物料为径向叠置的多个层体，其至少包含两个功能细层，并且该功能细层包裹在由第一树脂构成的层体之间，由第一树脂构成的层体至少占该剂物料体积的80％，第一层体到对称轴的距离小于或等于第二层体到对称轴距离的一半。
6、一剂通过压模来制造多层物品的多层物料，其具有一对称轴，该物料的多层结构由径向叠置的多个层体构成，所述多层结构至少包含两个功能细层，并且该功能细层包裹在由第一树脂构成的层体之间，该多层结构的特征在于：
由第一树脂构成的层体至少占该剂物料体积的80％；
第一层体到对称轴的距离小于或等于第二层体到对称轴距离的一半。
7、如权利要求6所述的多层物料，其特征在于功能层自身形成一多层结构，其包括一层包裹在两层粘性树脂之间的阻挡树脂。
8、如权利要求6或7所述的多层物料，其至少包括三个功能层，其特征在于两相邻层之间径向距离的比值小于或等于0.5。
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| JP3896524B2 (ja) | 2000-12-20 | 2007-03-22 | 株式会社吉野工業所 | 合成樹脂製２軸延伸ブロー成形壜体成形用プリフォーム |
| JP4239436B2 (ja) * | 2001-05-23 | 2009-03-18 | 東洋製罐株式会社 | 多層プリフォーム及びそれを用いた多層ボトル |
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2005
- 2005-02-26 PL PL05708852T patent/PL1720770T3/pl unknown
- 2005-02-26 CA CA 2557616 patent/CA2557616A1/fr not_active Abandoned
- 2005-02-26 WO PCT/IB2005/050707 patent/WO2005084903A1/fr active Application Filing
- 2005-02-26 CA CA 2557622 patent/CA2557622A1/fr not_active Abandoned
- 2005-02-26 EP EP20050708852 patent/EP1720770B1/fr active Active
- 2005-02-26 EP EP05708856.9A patent/EP1727657B1/fr active Active
- 2005-02-26 SI SI200531158T patent/SI1720770T1/sl unknown
- 2005-02-26 CA CA 2557627 patent/CA2557627C/fr not_active Expired - Fee Related
- 2005-02-26 CN CN2005800067284A patent/CN1925962B/zh not_active Expired - Fee Related
- 2005-02-26 BR BRPI0508336A patent/BRPI0508336B1/pt not_active IP Right Cessation
- 2005-02-26 KR KR1020067019420A patent/KR101154849B1/ko active IP Right Grant
- 2005-02-26 ES ES05708853T patent/ES2451666T3/es active Active
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- 2005-02-26 BR BRPI0508338A patent/BRPI0508338B1/pt not_active IP Right Cessation
- 2005-02-26 WO PCT/IB2005/050704 patent/WO2005087601A1/fr active Application Filing
- 2005-02-26 US US10/590,201 patent/US7875330B2/en active Active
- 2005-02-26 CN CN200580006727XA patent/CN1925961B/zh not_active Expired - Fee Related
- 2005-02-26 RU RU2006133974/12A patent/RU2352459C2/ru not_active IP Right Cessation
- 2005-02-26 JP JP2007501418A patent/JP4782768B2/ja active Active
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- 2005-02-26 KR KR1020067019358A patent/KR101149790B1/ko not_active IP Right Cessation
- 2005-02-26 JP JP2007501420A patent/JP2007525348A/ja active Pending
- 2005-02-26 KR KR1020067018941A patent/KR20070003942A/ko not_active Application Discontinuation
- 2005-02-26 CA CA 2557590 patent/CA2557590C/fr not_active Expired - Fee Related
- 2005-02-26 US US10/591,126 patent/US7923085B2/en not_active Expired - Fee Related
- 2005-02-26 EP EP20050708853 patent/EP1720690B1/fr active Active
- 2005-02-26 SI SI200531832T patent/SI1720690T1/sl unknown
- 2005-02-26 ES ES05708852T patent/ES2350188T3/es active Active
- 2005-02-26 RU RU2006133975/12A patent/RU2359824C2/ru not_active IP Right Cessation
- 2005-02-26 EP EP20050708855 patent/EP1720692B1/fr not_active Not-in-force
- 2005-02-26 CN CN2005800067250A patent/CN1925960B/zh not_active Expired - Fee Related
- 2005-02-26 CN CN2005800067265A patent/CN1926027B/zh not_active Expired - Fee Related
- 2005-02-26 WO PCT/IB2005/050706 patent/WO2005084902A1/fr active Application Filing
- 2005-02-26 CA CA 2557584 patent/CA2557584C/fr active Active
- 2005-02-26 BR BRPI0508323-0A patent/BRPI0508323A/pt not_active IP Right Cessation
- 2005-02-26 JP JP2007501422A patent/JP2007525350A/ja active Pending
- 2005-02-26 RU RU2006133721/12A patent/RU2358889C2/ru not_active IP Right Cessation
- 2005-02-26 US US10/591,117 patent/US7959996B2/en active Active
- 2005-02-26 DE DE200560022983 patent/DE602005022983D1/de active Active
- 2005-02-26 US US10/591,116 patent/US20070184236A1/en not_active Abandoned
- 2005-02-26 CN CNA2005800067246A patent/CN1925959A/zh active Pending
- 2005-02-26 WO PCT/IB2005/050705 patent/WO2005087473A1/fr active Application Filing
- 2005-02-26 EP EP05708854A patent/EP1720691A1/fr not_active Withdrawn
- 2005-02-26 JP JP2007501421A patent/JP2007525349A/ja active Pending
- 2005-02-26 RU RU2006133972/12A patent/RU2354552C2/ru not_active IP Right Cessation
- 2005-02-26 US US10/591,127 patent/US7968162B2/en active Active
- 2005-02-26 AT AT05708852T patent/ATE478013T1/de active
- 2005-02-26 BR BRPI0508331A patent/BRPI0508331B1/pt not_active IP Right Cessation
- 2005-02-26 WO PCT/IB2005/050708 patent/WO2005084904A1/fr active Application Filing
- 2005-02-26 JP JP2007501419A patent/JP4865696B2/ja not_active Expired - Fee Related
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2006
- 2006-09-11 KR KR1020067018508A patent/KR101080854B1/ko active IP Right Grant
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2007
- 2007-05-02 HK HK07104654A patent/HK1096907A1/xx not_active IP Right Cessation
- 2007-05-14 HK HK07105049A patent/HK1097497A1/xx not_active IP Right Cessation
- 2007-05-14 HK HK07105051A patent/HK1097486A1/xx not_active IP Right Cessation
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