CN1646313A - 高吸收性水敏感多层构造物 - Google Patents
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Abstract
包括第一层和布置在第一层上的第二层的多层构造物,第一层包括水敏感热塑性聚合物,第二层包括高吸收性聚合物。
Description
背景
本发明涉及高吸收性多层构造物。
高吸收性聚合物,它可以作为粉末、颗粒、和含水组合物得到,吸收大量的水和通常用于吸收制品以增加制品的吸收能力。一次性尿布和女性卫生产品通常包括高吸收性聚合物以增强体液吸收。高吸收性聚合物也在医疗、食品、和农业中具有各种应用。
高吸收性聚合物从各种起始材料形成和用于各种应用。U.S.5126382(Hollenberg)公开了金属离子交联的高吸收性聚合物。Hollenberg公开的是由如下方式制备高吸收性聚合物:提供高分子量聚合物如碱溶性聚电解质的乳液,向乳液中加入金属离子交联剂,和然后向乳液中加入挥发性碱以带来聚合物的原位增溶。水的随后蒸发提供高吸收性聚合物。Hollenberg进一步公开了在聚合物的原位增溶之前,向混合物中加入低分子量多羧基化(polydroxylated)化合物。
U.S.4808637(Boardman等人)公开了可水溶胀,水不溶性高吸收性丙烯酸酯类组合物。
U.S.5079034(Miyaka等人)描述了从水溶液制备吸收复合材料的方法,该水溶液包括水溶性自由基聚合引发剂和水溶性烯属不饱和单体。
U.S.5693707(Cheng等人)公开了在水中的含水聚合物乳液,该乳液包括10wt%-40wt%共聚物。该共聚物由20wt%-90wt%α,β-烯属不饱和羧酸单体和至少一种足够数量的软化单体组成,使得共聚物的Tg小于140℃。软化单体,当形式为均聚物时,显示小于35℃的Tg。采用碱金属氢氧化物或碱土金属氢氧化物将Cheng等人的含水聚合物乳液调节到4-6的pH。将二价或三价金属交联化合物加入到含水聚合物组合物中以得到根据Cheng等人的高吸收性聚合物。
U.S.6284367(Gruhn等人)公开了用于电缆制造的非织造水阻断带的制备方法。该带子可包括非织造基材和在基材表面上的涂层。涂层包括由多价离子交联剂部分交联的水溶性聚合物。由Gruhn等人公开的水溶性聚合物包括如下物质的聚合物和共聚物:丙烯酸、甲基丙烯酸、衣康酸、马来酸酐、羧甲基纤维素、2-丙烯酰胺-2-甲基丙磺酸、多糖和羧甲基淀粉。
U.S.4721647(Nakanishi等人)描述了间断结合到纤维性基础材料上的吸水性聚合物。
U.S.5489469(Kobayashi等人)公开了包括吸水性聚合物,水不溶性无机材料和水不溶性亲水性纤维性材料的吸收复合材料。
概述
在一个方面,本发明的特征为包括如下层的多层构造物:包括水敏感热塑性聚合物的第一层,和布置在第一层上的第二层,该第二层包括高吸收性聚合物。在一个实施方案中,热塑性聚合物包括聚酰胺。在另一个实施方案中,热塑性聚合物包括聚氧化亚烷基二醇二元胺和选自如下的酸的反应产物:二羧酸、二羧酸酯及其结合物,聚氧化亚烷基二醇二元胺具有通式NH2--(CH2)x--(OCH2--CH2)y--O--(CH2)x--NH2其中2=X=3,和1=Y=2。在其它实施方案中,热塑性聚合物包括己二酸和聚氧化亚烷基二醇二元胺的反应产物。在另一个实施方案中,热塑性聚合物是水溶性的。
在一些实施方案中,高吸收性聚合物包括交联的聚丙烯酸酯。在其它实施方案中,高吸收性聚合物包括交联和至少部分中和的α,β-β烯属不饱和单体,该不饱和单体选自单羧酸单体、二羧酸单体、酸酐单体及其结合物。
在一个实施方案中,构造物显示的吸收速率大于在热塑性层不存在下高吸收性聚合物层的吸收速率。
在其它实施方案中,上述多层构造物是膜。在一个实施方案中,膜显示的吸收速率大于在热塑性层不存在下高吸收性聚合物层的吸收速率。在一些实施方案中,膜是柔性的。
在一些实施方案中,上述多层构造物是纤维。
在另一方面,本发明的特征为包括非织造纤网和布置在该纤网上的上述多层构造物的制品。
在一些方面,本发明的特征为包括如下组分的多组分纤维:包括水敏感热塑性聚合物的第一组分,和包括高吸收性聚合物的第二组分,第二组分布置在第一组分上。在一个实施方案中,第一组分包括芯和第二组分包括鞘。
在其它方面,本发明的特征为包括如下组分的多组分纱线:包括水敏感热塑性聚合物的第一组分,和包括高吸收性聚合物的第二组分,第二组分布置在第一组分上。在一些实施方案中,第一组分包括芯,该芯包括水敏感热塑性聚合物。在另一个实施方案中,第二组分包括鞘,该鞘包括高吸收性聚合物。
在另一个实施方案中,一次性制品(如尿布)包括上述多层构造物。
在另一方面,本发明的特征为制备多层构造物的方法,该方法包括在水敏感热塑性膜上涂敷含水的水溶性高吸收性聚合物组合物。
在一个实施方案中,该方法包括提供熔融的水敏感热塑性聚合物,和接触熔融的热塑性聚合物与含水水溶性高吸收性聚合物组合物。在另一个实施方案中,熔融热塑性聚合物的形式选自纤维、长丝及其结合物。在一些实施方案中,熔融热塑性聚合物的形式为膜。
本发明的特征为高吸收性自支撑膜,该膜能够在水中降解,可冲洗,和在污水系统中降解。也可构造该多层构造层以包括水溶性热塑性聚合物层和能够在水中溶解。本发明的特征也为多层构造物,该多层构造物可以布置在基材上或引入制品中以使制品为水溶性的,可水溶胀的,可水分散的或其结合。
多层构造物非常适用于个人卫生产品和可以引入这样的产品以使产品更能够在污水和废物处理系统中降解。
可以构造多层构造物以热粘合到基材上。
多层构造物,当形式为连续或间断膜时可允许液体通过构造物的层到第二层,如吸收芯,其中它然后可以被贮存。液体在第二层中的贮存允许离开用户的皮肤保持液体。
术语集
有关本发明,这些术语具有以下给出的意义:
“水敏感”表示水溶性、可水分散、可水溶胀、及其结合。
从优选实施方案的如下描述和从权利要求,其它特征和优点是显然的。
详细描述
多层构造物(如膜)包括布置在水敏感热塑性聚合物层上的高吸收性聚合物层。当多层构造物的高吸收层与含水组合物接触时,它形成凝胶和在与胶凝化高吸收层界面的热塑性层基本保持它作为高吸收层凝胶的整体性。可以构造多层构造物以在比如下胶凝化速率快的速率下胶凝化:在水敏感热塑性层不存在下由高吸收性聚合物层显著的胶凝化速率。
高吸收层包括形式优选为连续或间断涂层或膜的高吸收性聚合物。该高吸收性聚合物吸收许多倍它自身重量的水,优选至少50倍,更优选至少100倍,最优选至少150倍它重量的水。高吸收性聚合物吸收水的能力与高吸收性聚合物中存在的交联程度相关。增加交联程度增加了在负荷下高吸收性聚合物的总流体保持能力。优选优化交联程度以获得其中吸收速率和数量被优化的组合物。优选的高吸收性聚合物是至少10%,更优选约10%-约50%,最优选约20%-40%交联的。合适高吸收性聚合物的例子包括交联和聚合的α,β-β烯属不饱和单和二羧酸和酸酐单体,该单体包括如丙烯酸、甲基丙烯酸、巴豆酸、马来酸/酸酐、衣康酸、富马酸、及其结合物。
优选从水溶性高吸收性聚合物(即当交联时显示高吸收性能的聚合物)的含水组合物,和交联剂形成高吸收层。含水高吸收性聚合物组合物显示约7-约10的pH,优选大于7的pH,它可以通过向含水高吸收性聚合物组合物中加入pH调节剂(如碱)达到。有用pH调节剂的例子包括碱金属氢氧化物(如氢氧化钠和氢氧化钾)、碱金属醇盐、碱土金属氢氧化物(如氢氧化钙)、及其结合物。pH调节剂有助于中和水溶性高吸收性聚合物的酸基团。优选加入碱金属氢氧化物或碱土金属氢氧化物以中和约50%-约95%的羧基,优选大于65%到约95%的羧基,更优选约70%-约95%的羧基,更优选约70%-约85%的羧基,最优选约75%的羧基。然后采用挥发性碱进一步中和(如至少100%中和)水溶性高吸收性聚合物。当组合物干燥时挥发性碱从含水水溶性高吸收性聚合物组合物消散,它使得交联剂交联水溶性高吸收性聚合物以形成高分子量聚合物,即,高吸收性聚合物。合适挥发性碱的例子包括氨,如氢氧化铵,包括如下的胺:如甲胺和二甲胺、及其结合物。
选择含水水溶性高吸收性聚合物组合物的粘度以促进组合物在基材(如水溶性热塑性聚合物组分)上的涂敷。在室温(即25℃)下对于20wt%固体组合物,有用的含水水溶性高吸收性聚合物组合物的粘度为约50cPs-约50,000cPs,更优选以增加的优选顺序,约100cPs-约30,000cPs,约100cPs-约20,000cPs,约100cPs-约10,000cPs,约100cPs-约5000cPs,约100cPs-约2500cPs。优选水溶性高吸收性聚合物的分子量为约9000Mw-约4,000,000Mw,更优选约20,000Mw-约1,000,000Mw,最优选约100,000Mw-约200,000Mw。
含水水溶性高吸收性聚合物组合物包括5wt%-约65wt%,优选约10wt%-约50wt%,更优选约20wt%-约40wt%固体。
选择交联剂以与水溶性高吸收性聚合物的官能亲水性基团络合。一旦消散聚合物组合物的水相,优选的交联剂与水溶性高吸收性聚合物上的官能团络合。有用的交联剂包括,如二价和三价交联剂盐,该二价和三价交联剂盐包括,如锆盐、锌盐、铬盐、及其结合物、锆离子,它可以与铁铝离子、铬离子、钛离子、和氮丙啶、及其结合物混合。其它有用的交联剂描述于U.S.专利No.4090013和在此引入。有用的市售交联剂包括以商品名BACOTE 20和ZIRMEL 1000购自Magnesium Elektron,Inc.(Flemington,NJ)的碳酸氧锆铵,和以商品名NEOCRYL CX-100购自Zeneca Resins(Wilmington,MA)的氮丙啶交联剂。优选将交联剂以约2份-约10份,优选约2份-约8份,最优选约4份-6份的数量加入到含水高吸收性聚合物组合物中。
交联剂也可以从含水水溶性高吸收性聚合物组合物单独提供。在一些应用中,在两步骤工艺中在交联剂的施加之前或之后,将含水水溶性高吸收性聚合物组合物施加到水敏感热塑性层。当将含水水溶性高吸收性聚合物和交联剂单独施加时,优选将含水水溶性高吸收性聚合物组合物在与交联剂接触之前干燥。
优选的高吸收性聚合物能够由环境水分水塑化。水塑化的高吸收性聚合物提供了延伸性和柔韧性的柔顺膜。优选高吸收性聚合物从空气中在环境温度和50%相对湿度下,以至少约5wt%,更优选至少约10wt%,最优选至少约20wt%无水高吸收性聚合物的数量吸收水分。
含水水溶性高吸收性聚合物组合物也可包括少量水溶性单体,该水溶性单体包括,如丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、乙烯基吡咯烷酮、丙烯酰胺、甲基丙烯酰胺、乙烯基磺酸钠、和1-烯丙氧基-2-羟基丙磺酸酯。
有用的水敏感热塑性聚合物包括水溶性热塑性聚合物、可水分散热塑性聚合物和可水溶胀热塑性聚合物。合适的水敏感热塑性聚合物包括结晶水敏感热塑性聚合物和无定形水敏感热塑性聚合物。术语“结晶聚合物”表示在玻璃化转变以上保持它们的橡胶性弹性体或柔性性能,直到超过熔融温度的那些聚合物。结晶聚合物的熔融也伴随着结晶X射线衍射效应的损失。“无定形聚合物”是随着温度的增加,从固体相变到液体相而没有可识别转变点的聚合物。
合适的水溶性结晶热塑性聚合物包括聚氧化亚烷基二醇二元胺或聚氧化亚烷基二醇胺,和二羧酸或二羧酸酯的反应产物。优选的聚氧化亚烷基二醇二元胺具有如下通式:
NH2--(CH2)x--(OCH2--CH2)y--O--(CH2)x--NH2
其中2=X=3,和1=Y=2。合适聚氧化亚烷基二醇二元胺的例子包括三甘醇二元胺,其中X=2和Y=1,和四甘醇二元胺,其中2=X=3和Y=2。有用的市售聚氧化亚烷基二醇二元胺以商品名JEFFAMINEXTJ-504和JEFFAMINE EDR-192(四甘醇二元胺)购自HuntsmanChemical Co.(休斯敦,德克萨斯)。优选的二元胺是4,7,10-三氧杂十三烷-1,13-二元胺(TTD二元胺),其中X=3和Y=2,它购自BASF(Parsippany,N.J.)。
有用的聚氧化亚烷基二醇二元胺包括JEFFAMINE D-230、D-400、XTJ-500、XTJ-501、和XTJ-205,条件是在反应期间采用链终止剂酸或胺,和/或另外的成分如蜡、增粘剂、结晶聚合物、和一元酸随后与反应的聚酰胺结合。当己二酸与三氧十三烷-1,13-二元胺和JEFFAMINE D-230反应时,例如,相对于己二酸和三氧十三烷-1,13-二元胺的反应,获得的聚酰胺相对缓慢硬化。聚氧化亚烷基二醇二元胺与等化学计量比的二羧酸反应。
合适的二羧酸包括含有5-36个碳原子的那些二羧酸,其包括己二酸、庚二酸、壬二酸、癸二酸、辛二酸、十二烷二酸、对苯二甲酸、间苯二甲酸、叔丁基间苯二甲酸、二聚体酸、及其混合物。也可以使用这些酸的酯和酸酐。
特别有用的水溶性聚醚酰胺具有不大于190℃的熔点和包括,如,己二酸和JEFFAMINE XTJ-504的反应产物、己二酸和JEFFAMINEEDR-192的反应产物、己二酸和TTD二元胺的反应产物。
合适的结晶水溶性聚酰胺以商品名NP-2126、NP-2110、NP-2116、和NP-2068购自H.B.Fuller Company(St.Paul,Minnesota)。
合适的结晶可水分散聚合物包括,如购自UnionCarbide(Danbury,Conn.)的聚环氧乙烷和结晶聚酯。
合适的无定形水敏感热塑性聚合物包括,如聚乙烯醇、聚乙烯基吡咯烷酮、聚乙烯基吡咯烷酮/醋酸乙烯酯、聚乙烯基吡咯烷酮/丙烯酸、聚醚噁唑啉、及线性和支化可水分散聚酯。
合适的市售无定形可水分散热塑性聚合物包括,如,以商品名GROHSERAN L-301和GROHSERAN L-302购自Nippon Groshei(日本),和以商品名UNITKA购自Unitaka Ltd.(日本)的聚乙烯醇;购自BASF(Mount Olive,N.J.)和International Specialty Products(Wayne,N.J.)的聚乙烯基吡咯烷酮;以商品名ACRYLIDONE购得的聚乙烯基吡咯烷酮/醋酸乙烯酯共聚物和聚乙烯基吡咯烷酮/丙烯酸,两者购自ISP;以商品名PEOX购自The Dow Chemical Company(Freeport,德克萨斯),和以商品名AQUAZOL购自PCIIncorporated(Tucson,Arizona)的聚醚噁唑啉,以商品名AMOBOND购自Amoco Chemical Co.,的聚乙烯基甲基醚,以包括EASTMANAQ-14000、EASTMAN AQ-1950、和EASTMAN AQ-1045的商品名EASTMAN AQ购自Eastman ChemicalCompany(Kingsport,Tennessee)的线性聚酯、聚丙烯酰胺、和可水分散聚酯和共聚酯。
合适的可水分散聚酯和共聚酯以EASTMAN AQ商品名购得和包括线性聚酯或支化磺化共聚酯。这样的聚合物是盐水和体液不溶的,仍然可在自来水中分散。支化可水分散共聚酯的Tg为约-5℃~7℃,而线性聚酯的Tg为约30℃~约60℃。线性热塑性可水分散聚酯以包括,如EASTMAN AQ 35S(7,000Mn)、AQ 38S(10,000Mw)、和AQ55S(8,000Mn)的EASTMAN AQ系列商品名,都购自EastmanChemical Company(Kingsport,Tennessee)。支化的热塑性可水分散聚酯以包括如,EASTMAN AQ 1045、AQ 1350、AQ 1950、和AQ 14000的EASTMAN AQ系列商品名购自Eastman Chemical Company。
其它有用的水敏感聚合物以Hydromelt商品名购自H.B.FullerCompany(St.Paul,Minnesota)和包括NP2116、NP2055、NP2068、和NP2110。
有用的水敏感热塑性聚合物和它们的制造方法公开于,如U.S.专利Nos.3882090(Fagerberg等人)、5053484(Speranza等人)、5118785(Speranza等人)、5086162(Speranza等人)、5342812(Speranza等人)、5899675(Ahmed等人)、5863979(Ahmed等人)、5663286(Ahmed等人)、5869596(Ahmed等人),并在此引入。
水溶性热塑性聚合物层也可包括添加剂,该添加剂包括如蜡、增粘树脂、结晶聚合物、单羧酸、及其混合物以及单羧酸和一元胺。
优选取向多层构造物使得将高吸收性聚合物层曝露于要吸收的流体,如水、体液、及其结合物。
多层构造物可以采用各种形式存在,该形式包括,如纤维(如多组分纤维,如芯-鞘构造物)、纱线(如多组分纱线)、膜(如独立式膜)、基材(包括如织造和非织造基材、多孔基材、膜、纤维、和纱线)上的涂层、及其结合。多层构造物自身,以及多层构造物的层可以是连续或间断的,如有斑纹的、有点的、和有图案的。
多层构造物可以是独立的(如膜、纤维、和纱线)或与基材结合,如布置在基材上,该基材包括,如纤维、纱线、纤网(织造和非织造)、膜、脱除衬里、及其结合物。有用的纤维包括纤维素纤维和合成纤维,该纤维素纤维包括如木纸浆、棉、丝、和羊毛,该合成纤维包括,如尼龙、人造纤维、聚酯、丙烯酸类物、聚丙烯、聚乙烯、聚氯乙烯、聚氨酯、玻璃、及其结合物。多层构造物可以采用各种形式布置在基材上,该形式包括如连续和间断(如有斑纹的、有点的、和有图案的)涂层、层压材料、及其结合物。
可以使用各种技术将构造物的层同时或按顺序施加到基材上或形成于基材上,该技术包括如,浸入、浸泡、浸渍、喷涂、挤出(如共挤出)、层压、涂敷(如浸涂、槽涂、凹版印刷、刀涂、和接触涂敷)、及其结合。多孔基材例如可以按顺序采用含水高吸收性聚合物和水敏感热塑性聚合物浸渍。
优选将含水水溶性高吸收性聚合物组合物施加到构造物的水敏感组分上,同时水敏感热塑性组分在更高的温度下,如在熔融状态或水敏感热塑性聚合物熔融温度范围中的温度,相对于含水高吸收性聚合物组合物。在其中水敏感组分由挤出形成的情况下,例如,可以当挤出水敏感组分时将含水水溶性高吸收性聚合物组合物施加到水敏感组分上,和在纤维和长丝的情况下,可以在或靠近这样的点将含水水溶性高吸收性聚合物组合物施加到纤维或长丝上,在该点将纤维或长丝从纤维或长丝形成孔脱除。当水敏感热塑性组分从孔口挤出时,由水敏感热塑性组分显示的相对更高温度增加了施加到其上的含水水溶性高吸收性聚合物组合物的含水组分的消散速率。
多层构造物适用于各种制品,该制品包括,如吸收制品如尿布、卫生巾、绷带、创伤护理产品、医疗垫、帘子、和睡衣以及各种纸产品如纸巾、卫生纸、和面巾纸、电缆包、和包装物。
一种有用的制品包括纤维性非织造纤网和布置在纤网上的多层构造物。该多层构造物可包括孔眼以允许液体通过构造物到第二层,如非织造纤网。
该多层构造物也可被引入吸收制品,其包括如体液渗透顶片,获得层,吸收层(如纤维性芯),体液不透过底片,和其结合。获得层优选能够分散液体到吸收层的表面。吸收层可包括疏松纤维,通过粘结剂保持在一起的纤维,压缩纤维,和其结合。吸收层的纤维可以是天然纤维(如木纸浆、黄麻、棉、丝、和羊毛、及其结合物)、合成纤维(包括如尼龙、人造纤维聚酯、丙烯酸类物、聚丙烯、聚乙烯、聚氯乙烯、聚氨酯、及其结合物)、及其结合物。多层构造物的形式可以为在任何组分之间布置的层。
在一种吸收制品中,将多层构造物穿孔和布置在吸收制品的穿用者和吸收层之间,使得热塑性层是用于与液体接触的多层构造物的第一层。孔眼允许液体从热塑性层通过多层构造物到高吸收层。高吸收层然后在与水的接触时凝胶化和吸收制品的吸收层吸收水。
现在通过如下实施例描述本发明。除非另外说明,所有的比例和百分比按重量计。
实施例
实施例
将FULATEX PD8081H含水聚丙烯酸溶液聚合物和碳酸氧锆铵组合物(H.B.Fuller Company,St.Paul,Minnesota)涂敷在50μm厚NP2116聚酰胺膜(H.B.Fuller Company)上并干燥以形成膜构造物,该膜构造物包括在50μm聚酰胺膜上的15μm高吸收性聚合物涂层。
使用滴眼器将水滴滴在膜构造物的高吸收性聚合物表面上。观察处理的膜。水快速吸附和然后由高吸收性聚合物吸收并在五秒内形成凝胶。水然后由膜构造物的热塑性层吸收。在三分钟之后,膜构造物在水滴的位置溶解。
Claims (14)
1.一种多层构造物,包括:
包含水敏感热塑性聚合物的第一层;和
包含高吸收性聚合物的第二层,该第二层布置在所述第一层上。
2.权利要求1的多层构造物,其中所述热塑性聚合物包括聚酰胺。
3.权利要求1的多层构造物,其中所述水敏感热塑性聚合物包括聚氧化亚烷基二醇二元胺和选自如下的酸的反应产物:二羧酸、二羧酸酯及其结合物,该聚氧化亚烷基二醇二元胺具有通式NH2--(CH2)x--(OCH2--CH2)y--O--(CH2)x--NH2,其中2=X=3,和1=Y=2。
4.权利要求1的多层构造物,其中所述水敏感热塑性聚合物包括己二酸和聚氧化亚烷基二醇二元胺的反应产物。
5.权利要求1的多层构造物,其中所述水敏感热塑性聚合物溶于水。
6.权利要求1的多层构造物,其中所述高吸收性聚合物包括交联和至少部分中和的α,β-β烯属不饱和单体,该不饱和单体选自单羧酸单体、二羧酸单体、酸酐单体及其结合物。
7.权利要求1的多层构造物,其中所述构造物显示的吸收速率大于在所述热塑性层不存在下高吸收性聚合物层的吸收速率。
8.权利要求1的多层构造物,进一步包括孔眼。
9.权利要求1的多层构造物,其形式选自膜、纤维或纱线。
10.权利要求9的多层构造物,其中所述构造物的形式为包括如下组分的多组分纤维:
包含芯的第一组分,该芯包括所述水敏感热塑性聚合物层和所述高吸收性聚合物层之一;和
布置在所述芯上包含鞘的第二组分,该鞘包括所述水敏感热塑性聚合物层和所述高吸收性聚合物层的另一个。
11.一种包括权利要求1的多层构造物的膜,该膜包括孔眼。
12.一种制品,包括:
选自非织造纤网、吸收层、及其结合物的基材;和
布置在该基材上的权利要求1的多层构造物。
13.一种包括权利要求1的多层构造物的制品,该制品选自一次性制品、尿布、卫生巾、绷带、创伤护理产品、纸产品、及其结合物。
14.一种制备权利要求1的多层构造物的方法,该方法包括:
提供熔融的水敏感热塑性聚合物;和
使该熔融的热塑性聚合物与含水的水溶性高吸收性聚合物组合物接触。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10/121,171 | 2002-04-11 | ||
US10/121,171 US7135135B2 (en) | 2002-04-11 | 2002-04-11 | Superabsorbent water sensitive multilayer construction |
Publications (1)
Publication Number | Publication Date |
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CN1646313A true CN1646313A (zh) | 2005-07-27 |
Family
ID=28790263
Family Applications (1)
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CNA038081385A Pending CN1646313A (zh) | 2002-04-11 | 2003-04-08 | 高吸收性水敏感多层构造物 |
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US (2) | US7135135B2 (zh) |
EP (1) | EP1492670A1 (zh) |
CN (1) | CN1646313A (zh) |
AU (1) | AU2003223713A1 (zh) |
CA (1) | CA2480153A1 (zh) |
MX (1) | MXPA04009903A (zh) |
WO (1) | WO2003086755A1 (zh) |
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-
2002
- 2002-04-11 US US10/121,171 patent/US7135135B2/en not_active Expired - Fee Related
-
2003
- 2003-04-08 AU AU2003223713A patent/AU2003223713A1/en not_active Abandoned
- 2003-04-08 EP EP20030719913 patent/EP1492670A1/en not_active Withdrawn
- 2003-04-08 CA CA 2480153 patent/CA2480153A1/en not_active Abandoned
- 2003-04-08 MX MXPA04009903A patent/MXPA04009903A/es unknown
- 2003-04-08 WO PCT/US2003/012669 patent/WO2003086755A1/en not_active Application Discontinuation
- 2003-04-08 CN CNA038081385A patent/CN1646313A/zh active Pending
-
2006
- 2006-10-05 US US11/544,911 patent/US20070031637A1/en not_active Abandoned
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CN110366377A (zh) * | 2017-02-28 | 2019-10-22 | 欧莱雅 | 适用于外部施用的非织造固体材料 |
Also Published As
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US20030194558A1 (en) | 2003-10-16 |
WO2003086755A1 (en) | 2003-10-23 |
EP1492670A1 (en) | 2005-01-05 |
MXPA04009903A (es) | 2004-12-07 |
CA2480153A1 (en) | 2003-10-23 |
AU2003223713A1 (en) | 2003-10-27 |
US20070031637A1 (en) | 2007-02-08 |
US7135135B2 (en) | 2006-11-14 |
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