CN101743132B - 预浸渍体 - Google Patents
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- CN101743132B CN101743132B CN200880022377XA CN200880022377A CN101743132B CN 101743132 B CN101743132 B CN 101743132B CN 200880022377X A CN200880022377X A CN 200880022377XA CN 200880022377 A CN200880022377 A CN 200880022377A CN 101743132 B CN101743132 B CN 101743132B
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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
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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
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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
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Abstract
预浸渍体,其可通过用浸渍树脂溶液浸渍装饰原纸而获得,该浸渍树脂溶液含有至少一种聚合物胶乳和至少一种具有特定分子量分布的改性淀粉。
Description
本发明涉及预浸渍体和可由其获得的装饰浸渍体或装饰性涂覆材料。
装饰性涂覆材料,所谓的装饰纸或者装饰薄膜优选在家具制造和内部装修中,特别是在层压地板中用于表面涂覆。术语“装饰纸/装饰薄膜”是指经合成树脂浸渍的或者经合成树脂浸渍且经表面处理的、经印刷的或未经印刷的纸。将装饰纸/装饰薄膜与支承板胶粘或粘合。
视浸渍过程的类型而定,在具有完全浸渍的纸芯的装饰纸/装饰薄膜与所谓的预浸渍体之间做出区分,其中所述纸在造纸机中在线地或者离线地仅仅部分浸渍。没有一种目前已知的预浸渍体满足对它们提出的全部要求,如良好的可印刷性、高抗裂强度、良好的可粘附性和良好的可涂漆性,所述预浸渍体含有含甲醛的热固性塑料树脂或者低甲醛含量的丙烯酸酯类粘结剂。
为了将装饰薄膜粘贴到木材如刨花板或MDF板上,通常使用脲胶或聚乙酸乙烯酯(PVAC)胶。装饰薄膜的粘合并不总能得到确保。
层压材料(高压层合体)是这样的层合体,其通过压制数张经浸渍的、彼此堆叠的纸而产生。一般而言,这些层压材料的构造由最上面的产生表面电阻的透明覆盖片材(Overlay)、树脂浸渍的装饰纸和一层或多层酚醛树脂涂覆的牛皮纸组成。为此,作为底层使用例如硬质纤维板和刨花板或者胶合板。
在按照短周期方法(Kurztaktverfahren)制造的层合体(低压层合体)中,将用合成树脂浸渍的装饰纸直接与底层,例如刨花板一起,在应用低压的情况下挤压。
在上文提到的涂层材料中使用的装饰纸是白色的或有色的,经过或未经过另外的印刷。
在应用技术性能方面,所述用作原材料的、所谓的装饰原纸必须满足特定的要求。属于此类的有:用于更好地覆盖底层的高不透明性、用于均匀的树脂吸收的均匀的片材构成和克重、高耐光性、高纯度和用于待印刷的图案的良好的可复制性的色彩均匀性、用于顺利的浸渍过程的高湿强度、用于达到所需的树脂饱和度的相应的可吸收性、在造纸机中的卷绕过程和印刷机中的印刷方面重要的干强度。此外,抗裂强度特别有意义,因为其是可以如何良好地加工装饰原纸的度量。因此,粘上的装饰纸/装饰箔在加工步骤,如锯切或钻孔中,必须不发生边缘磨损(ausfransen)。
为了制得装饰表面而印刷装饰原纸。主要采用所谓的轮转凹版印刷工艺,其中借助于多个凹印辊将印刷图像转移到纸上。单个印刷点应该完整并且尽可能强地被转移到纸表面上。然而在装饰凹版中,只有小部分的存在于凹印辊上的像素被转移到纸表面上。出现所谓的Missing Dots,也就是缺失点。通常,印刷油墨过深地渗透到纸结构中,由此降低颜色强度。用于具有少量缺失点和高颜色强度的良好的印刷图像的先决条件是表面形态尽可能平坦且均匀,和纸表面协调的颜色吸收性能。
出于该原因,通常使用所谓的软压延机,偶尔也称为Janus压延机使原纸平整。该处理可能导致纸表面被压碎,并由此使其压缩,这对树脂吸收能力产生负面影响。
上述性能主要受装饰原纸的浸渍,即所使用的浸渍剂的类型影响。
通常用于装饰原纸浸渍的浸渍树脂溶液是基于脲、蜜胺或酚醛树脂的树脂并含有甲醛, 并且导致具有差的后续抗断强度(Weiterreiβfestigkeit)和可印刷性的脆性产品。
近年来,越来越注意用于浸渍装饰原纸的浸渍树脂溶液不含危害健康物质,特别是不含甲醛。
DE 197 28 250 A1公开了基于苯乙烯/丙烯酸酯共聚物的不含甲醛的树脂用于制造不泛黄的预浸渍体的应用。该材料的缺点在于,这导致具有差的抗裂强度的产品。
用于浸渍装饰原纸的不含甲醛的浸渍树脂溶液还描述于EP 0 648248A1和EP 0739435A1中。它们优选由苯乙烯-丙烯酸酯共聚物和聚乙烯醇组成。然而,在抗裂强度方面,用该浸渍树脂溶液浸渍的纸仍然是可改进的。
WO01/11139提出了一种由粘结剂、水性聚合物分散体和乙二醛组成的不含甲醛的组合物,其使制备具有高抗裂强度的装饰纸成为可能。然而,用该组合物浸渍的纸不能良好地层合。
因此,本发明的目的在于,提供一种不具有上述缺点并且在好的可印刷性和高抗裂强度方面突出的不含甲醛的预浸渍体。
该目的借助于这样的预浸渍体实现,该预浸渍体可以通过用浸渍树脂溶液浸渍原纸而获得,所述浸渍树脂溶液含有至少一种聚合物胶乳和至少一种改性淀粉,该改性淀粉具有由至少为6的多分散指数Mw/Mn表示的分子量分布。优选的是具有6-23的多分散指数的淀粉。
在本发明的特定实施方案中,浸渍树脂溶液含有至少一种聚合物胶乳和至少一种改性淀粉,该改性淀粉优选具有以下的淀粉分子的分子量分布:
-最高6重量%的具有0-1000g/mol分子量的分子;
-5至20重量%的具有1000-5000g/mol分子量的分子;
-20至40重量%的具有5000-25000g/mol分子量的分子;
-20至45重量%的具有25000-200000g/mol分子量的分子;
-5至22重量%的具有200000-1000000g/mol分子量的分子;
-0.5至5重量%的具有超过1000000g/mol分子量的分子。
多分散指数通常被表述为重均摩尔质量与数均摩尔质量的比例Mw/Mn。其提供了关于分子量分布曲线宽度的信息。
改性淀粉的分子量分布由淀粉生产商借助于凝胶渗透色谱法(GPC)以常规方式测定。
使用具有Shodex KS柱的色谱仪进行GPC分析。洗提剂是在1ml/min流动速率下0.05M的NaOH。采用具有已知分子量的Pullulan标准进行校正。
在本发明中使用的所有改性淀粉均可商购获得。特别地,它们是经热和氧化降解的玉米和马铃薯淀粉。
根据本发明预浸渍体是指用树脂部分浸渍的纸。浸渍树脂的量优选为10-35重量%,但特别为12-30重量%,基于装饰原纸的单位面积重量计。
已经显示,根据本发明的浸渍树脂溶液是特别好地合适的,因为其不仅导致用其浸渍的纸的抗裂强度的改进,而且还在其他性能例如可印刷性、油漆保留性(Lackstand)或者泛黄方面使得与现有技术相比可比较地良好的或者甚至更好的结果成为可能。此外,不会出现在使用亲水性粘结剂的情况下在层合(与底层粘合或胶粘)经浸渍的纸时常见的问题。这意味着,根据本发明的浸渍树脂溶液使得制备具有良好的可层合性的预浸渍体成为可能。另一个优点在于,所述预浸渍体可在高机器速度下廉价地制得。
聚合物胶乳可以优选为苯乙烯共聚物,例如苯乙烯-丙烯酸酯共聚物、苯乙烯-乙酸乙烯酯共聚物、苯乙烯-丁二烯或者苯乙烯-马来酸共聚物。然而,也可以使用这些共聚物的共混物。特别优选的是具有高的自身可交联性的聚合物。然而,非自身交联性聚合物也是适合的。
在本发明的特别的具体实施方案中,用于制造根据本发明的预浸渍体的浸渍树脂溶液含有不含乙基的苯乙烯-丙烯酸酯。
浸渍树脂溶液中淀粉/聚合物胶乳的用量比优选为80/20至20/80,但优选地该用量比为45/55至65/35,并且特别是50/50至60/40,分别基于所述浸渍树脂的重量计(atro)。
在本发明的另一个实施方案中,所述浸渍树脂溶液含有颜料和/或填料。颜料和/或填料的用量可以为1-30重量%,特别为2-20重量%。用量数据基于粘结剂质量(atro)计。术语“粘结剂”是指含有聚合物胶乳和改性淀粉的混合物。
用于制造根据本发明的预浸渍体的浸渍树脂溶液具有9-40重量%,优选20-35重量%并且特别优选26-30重量%的总固含量,基于干质量计。
在制备浸渍树脂溶液时,首先准备淀粉,将该淀粉或者冷地,即在室温至最高60℃下溶于水,或者在约120至145℃下煮沸。在该过程中,产生具有约5至6的pH值的约40至45%的悬浮液。在随后的步骤中,在考虑到所期望的固含量和淀粉/胶乳用量比的情况下,在5至10的pH值下加入约50%的胶乳分散体。在另一个步骤中,可以加入颜料或填料。
待浸渍的装饰原纸是既不经过内部上胶也不经过表面上胶的那些。它们基本上由纸浆、颜料和填料以及常用的添加剂组成。常用的添加剂可以是湿强度剂、助留剂和固着剂。装饰原纸与常用纸区别在于高得多的填料比例或颜料含量,和缺乏对于纸而言常用的内部上胶或表面上胶。
根据本发明的待浸渍的原纸可以含有高比例的颜料或填料。原纸中的填料的比例可以为至多55重量%,特别是8-45重量%,基于单位面积重量。合适的颜料和填料为,例如二氧化钛、滑石、硫化锌、高岭土、氧化铝、碳酸钙、刚玉、硅酸铝和硅酸镁盐或它们的混合物。
作为用于制造原纸的纸浆可以是软木纸浆(长纤维纸浆)和/或硬木纸浆(短纤维纸浆)。还可以使用具有上述纸浆类型的棉纤维及其混合物。特别优选例如由软木纸浆/硬木纸浆以10∶90至90∶10,特别是20∶80至80∶20的比例构成的混合物。然而,使用100重量%的硬木纸浆也证明是有利的。用量数据基于纸浆的质量计(atro)。
优选地,纸浆混合物可以含有至少5重量%的阳离子改性的纸浆纤维比例,基于纸浆混合物的重量计。已经证明特别有利的是,纸浆混合物中10-50重量%,特别是10-20重量%的阳离子改性的纸浆的比例。纸浆纤维的阳离子改性可以通过使纤维与表氯醇树脂和叔胺的反应而进行,或者通过与季铵氯化物如氯代羟丙基三甲基氯化铵或者缩水甘油基三甲基氯化铵的反应而进行。阳离子改性的纸浆和它们的制备例如从DAS PAPIER,12卷(1980),575-579页中获知。
原纸可以在Fourdrinier造纸机或Yankee造纸机上生产。为此,可以在2-5重量%物质稠度(Stoffdichte)下将纸浆混合物打浆至10-45°SR的打浆度(Mahlgrad)。可以将填料例如二氧化钛和滑石与湿强度剂一起放入混合桶中并且与纸浆混合物良好地混合。如此获得的稠物质可以被稀释至约1%的物质稠度,并且只要需要,可以混入另外的助剂,例如助留剂、消泡剂、硫酸铝和其他上文提到的助剂。将该稀物质经由造纸机的流量箱引导到筛网区域(Siebpartie)上。形成纤维网并且在脱水后得到原纸,随后将其干燥。制得的纸的单位面积重量可以为15-300g/m2。然而,特别适合的是具有40-100g/m2单位面积重量的原纸。
根据本发明的待使用的浸渍树脂溶液的施加可以在造纸机中或脱机地通过喷洒、浸渍、辊涂或抹涂(刮刀)进行。特别优选的是通过压胶机或者压膜机施加。
经浸渍的纸的干燥以常规方式借助IR干燥机或滚筒式干燥机在120-180℃的温度范围内干燥至2至6%的残余水含量(Restfeuchte)。
干燥后,可以将如此浸渍的纸(预浸渍体)进一步印刷和涂漆,并且随后按照常规方法层合到各种基材,例如刨花板或纤维板上。
以下实施例用于进一步解释本发明。作为百分比给出的数据基于纸浆的重量计,除非另有说明。用量比是指质量比或者重量比。
实施例
实施例1
以如下方式制备纸浆悬浮液:将由80重量%的桉树纸浆和20重量%的松树-硫酸盐纸浆(Kiefer-Sulfatzellstoff)组成的纸浆混合物在5%的物质稠度下打浆至33°SR(Schopper-Riegler)的打浆度。随后,加入1.8重量%表氯醇树脂作为湿强度剂。使用硫酸铝将该纸浆悬浮液的pH调节至6.5。之后向纸浆悬浮液中添加由30重量%的二氧化钛和5重量%的滑石、0.11重量%的助留剂和0.03重量%的消泡剂组成的混合物,并且制得具有约50g/m2单位面积重量和约23重量%的灰分含量的装饰原纸。重量数据基于纸浆的重量计(atro)。
在压胶机中用约25重量%固含量、以80∶20的用量比含有改性淀粉C-薄膜07324(淀粉I,表1)和丙烯酸正丁酯-苯乙烯共聚物(S305D)的水性树脂溶液浸渍该原纸的两面。为此,首先准备45%的淀粉溶液并且用水稀释至25重量%的浓度。然后,加入相应数量的50重量%的水性聚合物分散体,并且用水将得到的聚合物溶液稀释至25重量%的固含量。
随后,在约120℃的温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
实施例2
随后,在约120℃温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为7g/m2(实施例2A)、10g/m2(实施例2B)和14g/m2(实施例2C)。
实施例3
借助压胶机用固含量为27重量%、以50∶50的用量比含有改性淀粉I和丙烯酸正丁酯-苯乙烯共聚物(S 305D)的水性树脂溶液浸渍得自实施例1的原纸。
随后,在约120℃温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
实施例4
随后,在约120℃温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
实施例5
随后,在约120℃温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
实施例6
随后,在约120℃温度下将浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
实施例7
借助压胶机用以60∶40的用量比含有改性淀粉I和疏水化苯乙烯-丙烯酸丁酯共聚物(B 641)的水性树脂溶液浸渍得自实施例1的原纸。所述树脂溶液的固含量为26重量%。随后,在约120℃温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
实施例8
借助压胶机用以60∶40的用量比含有改性淀粉I和苯乙烯-丙烯酸正丁酯共聚物(S 305D)以及以15重量%的量(基于粘结剂的比例(atro))含有二氧化钛的水性树脂溶液浸渍得自实施例1的原纸。所述树脂溶液的固含量为28重量%。随后,在约120℃温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
对比实施例V1
借助压胶机用以60∶40的用量比含有环糊精(参见表1)和丙烯酸正丁酯-苯乙烯共聚物(S 305D)的水性树脂溶液浸渍得自实施例1的原纸。所述树脂溶液的固含量为约26重量%。随后,在约120℃温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
对比实施例V2
借助压胶机用以60∶40的用量比含有改性淀粉C-薄膜07380(淀粉IV,参见表1)和苯乙烯-丙烯酸正丁酯共聚物(S 305D)的水性树脂溶液浸渍得自实施例1的原纸。所述树脂溶液的固含量为约26重量%。随后,在约120℃温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
对比实施例V3
随后,在约120℃温度下将经浸渍的纸干燥至2.5%的残余水含量。干燥后的施加量为10g/m2。
下表2示出了与现有技术相比,根据本发明处理的纸的测试结果。测试以下性能:
抗拉强度(作为抗裂强度的度量)
按照用于装饰纸的常规方法,TGL 25290/11(Institut fürTechnologie der EPH,Zürich)测定垂直于纸表面的抗拉强度。为此,首先从待测试的预浸渍体上冲压出具有20mm直径的试样,并且单个放置在两个圆筒表面之间,并且与这些表面粘合并固化。将如此产生的样品在与片材平面垂直的夹持器中夹紧,并且施加不断增加的负荷直到使其断裂。如下计算抗拉强度:
σ≈1B=Fmax/A
σ≈1B-的与片材平面垂直的拉力,以MPa(N/mm2)计;
Fmax -的样品断裂时的力,以N计;
A -样品表面积,以mm2(314mm2,在d=20mm时)计。
可印刷性
按照参考目录进行视觉评价。分数:1(非常好)-6(非常差)。
油漆保留性(视觉评价)
通过与现有技术(得自Arjo Wiggins的预浸渍体,对比实施例3)比较进行评价。为此,用常规用于该目的SH-漆(SH-底漆/耐水,具有嵌入的酸固化剂的漆)以12g/m2的量涂覆预浸渍体样品。随后,在斜射光下评价涂漆的表面并且彼此比较。
泛黄(Δb值测定)
根据DIN 6167测量泛黄指数。其提供了在一定时间间隔内在温度影响下试样的黄度值(Gelbwert)变化。其是处理和未处理的试样的所谓的黄度值的差Δb。
使用比色计SF 600(Datacolor)在D6510°下测量b值。
表2表明,根据本发明的预浸渍体展现出在拉伸方向上较高的强度和较好的可印刷性。在根据本发明的预浸渍体的情况下,泛黄性能,特别是在较高温度下,也得到改善。油漆保留性比常用的预浸渍体更好或者类似。
Claims (11)
1.预浸渍体,其可通过用浸渍树脂溶液浸渍装饰原纸而获得,其特征在于,该浸渍树脂溶液含有至少一种聚合物胶乳和至少一种具有特定分子量分布的改性淀粉,其中淀粉分子的分子量如下分布:
-至多6重量%的具有0-1000g/mol分子量的分子;
-5至20重量%的具有1000-5000g/mol分子量的分子;
-20至40重量%的具有5000-25000g/mol分子量的分子;
-20至45重量%的具有25000-200000g/mol分子量的分子;
-5至22重量%的具有200000-1000000g/mol分子量的分子;
-0.5至5重量%的具有超过1000000g/mol分子量的分子。
2.根据权利要求1的预浸渍体,其特征在于,所述聚合物胶乳是苯乙烯-(甲基)丙烯酸酯共聚物。
3.根据权利要求1-2中任一项的预浸渍体,其特征在于,所述聚合物胶乳是苯乙烯-丙烯酸丁酯。
4.根据权利要求1-2中任一项的预浸渍体,其特征在于,淀粉/聚合物胶乳的比例为20/80至80/20,基于所述浸渍树脂的质量(atro)计。
5.根据权利要求4的预浸渍体,其特征在于,所述比例为45/55至65/35,基于所述浸渍树脂的质量(atro)计。
6.根据权利要求1-2中任一项的预浸渍体,其特征在于,浸渍树脂溶液含有1-30重量%的颜料和/或填料,基于粘结剂质量(atro)计。
7.根据权利要求6的预浸渍体,其特征在于,所述颜料是二氧化钛、高岭土、膨润土和/或碳酸钙。
8.根据权利要求1-2中任一项的预浸渍体,其特征在于,所述浸渍树脂溶液具有9-40重量%的固含量。
9.根据权利要求1-2中任一项的预浸渍体,其特征在于,所述浸渍树脂的量为装饰原纸的单位面积重量的10-35重量%。
10.装饰纸,其由根据权利要求1-9中任一项的预浸渍体而获得。
11.装饰性涂覆材料,其由根据权利要求1-9中任一项的预浸渍体而获得。
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DE102007030102.4 | 2007-06-28 | ||
DE102007030102.4A DE102007030102B4 (de) | 2007-06-28 | 2007-06-28 | Vorimprägnat |
PCT/EP2008/057870 WO2009000769A1 (de) | 2007-06-28 | 2008-06-20 | Vorimprägnat |
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EP (1) | EP2158096B1 (zh) |
JP (1) | JP2010531376A (zh) |
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CL (1) | CL2008001931A1 (zh) |
DE (1) | DE102007030102B4 (zh) |
ES (1) | ES2382085T3 (zh) |
PL (1) | PL2158096T3 (zh) |
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DK177321B1 (en) * | 2011-05-10 | 2013-01-02 | Skandinavisk HTP ApS | Paper for transfer pattern printing |
DE102011105676B4 (de) * | 2011-06-22 | 2018-05-09 | Schoeller Technocell Gmbh & Co. Kg | Vorimprägnat und Dekorpapier oder dekorativer Beschichtungswerkstoff daraus |
CN103946448B (zh) | 2011-11-18 | 2016-12-28 | 罗盖特公司 | 基于部分可溶的高分子量糊精的涂料 |
DE102013114420A1 (de) | 2012-12-23 | 2014-06-26 | Michael Jokiel | Imprägnierflotte zur Imprägnierung eines Rohpapieres |
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DE202014003058U1 (de) * | 2014-04-10 | 2014-05-06 | Schoeller Technocell Gmbh & Co. Kg | Verbundkörper mit einer dekorativen Oberfläche, einer elektrisch leitfähigen Struktur und einer elektronischen Schaltung |
PT2944621T (pt) | 2014-05-15 | 2017-07-05 | Omya Int Ag | Produto placa de fibra que compreende um material contendo carbonato de cálcio |
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CN107211543B (zh) | 2014-10-10 | 2020-08-18 | 得利乐公司 | 具有嵌入式导电材料的装饰性多层表面材料,由此制成的固体表面,制备这种表面材料的方法及其用途 |
CN107407057B (zh) * | 2015-02-04 | 2020-09-04 | 奥斯龙-明士克德廷根有限公司 | 生产包含生物聚合物纳米颗粒的预浸渍装饰原纸的组合物和方法 |
ES2776904T3 (es) * | 2015-07-10 | 2020-08-03 | SWISS KRONO Tec AG | Material laminado para recubrir un material derivado de la madera en forma de placa |
WO2017029238A2 (en) * | 2015-08-14 | 2017-02-23 | Basf Se | Aqueous surface treatment composition for paper and board |
CN106337317B (zh) * | 2016-08-31 | 2018-02-23 | 浙江大盛新材料股份有限公司 | 一种环保装饰原纸制造方法 |
CN106368045B (zh) * | 2016-08-31 | 2018-02-23 | 浙江大盛新材料股份有限公司 | 一种装饰原纸制造方法 |
CN106283823B (zh) * | 2016-08-31 | 2017-09-19 | 浙江大盛新材料股份有限公司 | 一种防龟裂装饰原纸的制造方法 |
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- 2008-06-20 AT AT08761274T patent/ATE544614T1/de active
- 2008-06-20 PL PL08761274T patent/PL2158096T3/pl unknown
- 2008-06-20 ES ES08761274T patent/ES2382085T3/es active Active
- 2008-06-20 RU RU2010102771A patent/RU2431572C1/ru active
- 2008-06-20 JP JP2010513866A patent/JP2010531376A/ja active Pending
- 2008-06-20 CN CN200880022377XA patent/CN101743132B/zh active Active
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- 2008-06-20 BR BRPI0813753 patent/BRPI0813753A2/pt not_active Application Discontinuation
- 2008-06-20 WO PCT/EP2008/057870 patent/WO2009000769A1/de active Application Filing
- 2008-06-20 US US12/666,575 patent/US8349464B2/en active Active
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ES2382085T3 (es) | 2012-06-05 |
WO2009000769A1 (de) | 2008-12-31 |
CA2692288C (en) | 2013-09-24 |
PL2158096T3 (pl) | 2013-01-31 |
EP2158096B1 (de) | 2012-02-08 |
AR067037A1 (es) | 2009-09-30 |
DE102007030102B4 (de) | 2019-10-31 |
PT2158096E (pt) | 2012-05-17 |
CL2008001931A1 (es) | 2010-01-22 |
BRPI0813753A2 (pt) | 2014-12-30 |
RU2431572C1 (ru) | 2011-10-20 |
US20100183890A1 (en) | 2010-07-22 |
CA2692288A1 (en) | 2008-12-31 |
JP2010531376A (ja) | 2010-09-24 |
EP2158096A1 (de) | 2010-03-03 |
US8349464B2 (en) | 2013-01-08 |
ATE544614T1 (de) | 2012-02-15 |
DE102007030102A1 (de) | 2009-01-02 |
CN101743132A (zh) | 2010-06-16 |
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