CN1239747A - 固结纤维材料的纤维粘结用粉末组合物 - Google Patents
固结纤维材料的纤维粘结用粉末组合物 Download PDFInfo
- Publication number
- CN1239747A CN1239747A CN99109153A CN99109153A CN1239747A CN 1239747 A CN1239747 A CN 1239747A CN 99109153 A CN99109153 A CN 99109153A CN 99109153 A CN99109153 A CN 99109153A CN 1239747 A CN1239747 A CN 1239747A
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- Prior art keywords
- powder composition
- fiber
- vinyl
- fiber bonding
- bonding powder
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 28
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Classifications
-
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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Abstract
一种用于固结纤维材料的纤维粘结用粉末组合物，它包括：a)基于一种或多种单体的聚乙烯醇稳定化聚合物的聚合物粉末，这些单体选自具有1—12个碳原子的支化或未支化羧酸的乙烯基酯，丙烯酸和甲基丙烯酸与具有1—12个碳原子的支化或未支化醇的酯，芳族乙烯基化合物，卤化乙烯，烯烃和二烯烃，和b)无机化合物，它在室温下为固体并在所述粉末被引入水中后与聚乙烯醇的OH基团形成化学键。
Description
本发明涉及用于固结纤维材料的纤维粘结用粉末组合物和涉及使用该纤维粘结用粉末组合物的固结方法。
由通常的生产无纺织物的方法例如气流成网、湿法成网或纺丝成网方法生产的纺织片状材料需要粘结剂来耐久地固结纤维和提高对机械应力的耐受能力。这些粘结剂通常是基于合成的高分子化合物，根据现有技术，它们能够以固体形式，例如作为粉末、粒料或纤维形式，或以液体形式如聚合物水分散体或溶液形式施用。无纺织物增高的强度是纤维被聚合物粘结的结果，聚合物粘结于纤维和因此增强了纤维结构。
当纤维由湿法成网方法成网时，通常希望将粘结剂与纤维一起引入到含水的液体中。在这种情况下，粘结剂体系需要满足特殊的要求。首先，粘结剂应该与纤维一起非常精细地分散到水中，为此必须确保常常为粒状的粘结剂分散或悬浮于水中。其次，粘结剂甚至在含水的液体中也应该具有非常良好的纤维粘附性，以使得在纤维的铺置过程中粘结剂不会被含水的液体洗掉。因为，在升高的温度下，更常见的情况是超过了粘结剂的玻璃化转变温度或熔化温度，因而需要粘结剂有耐久的化学交联，以使纤维结构甚至在较高温度下仍具有尺寸稳定性。为此，粘结剂应该借助于化学交联反应来确保纤维在纺织品片状材料中的耐久固结。该性能对于湿法成网的玻璃纤维的预粘结来说是特别有利的。
WO-A90/14457公开了一种处理方法，其中玻璃纤维在梳理步骤之后与热塑性塑料粉末例如聚丙烯、聚酯或聚酰胺混合，然后纤维结构在升高温度和减压下固结。湿法成网方法据说是不可取的，因为存在粘结剂被洗掉的危险。AU-B 36659/89同样描述了借助于热塑性塑料粉末来固结玻璃纤维材料的方法，建议使用聚酯或聚苯乙烯。然而，该粘结剂体系不适用于湿法成网方法。尤其是，例如，如此粘结的纤维结构在与水或溶剂接触后的低强度是极其不利的。
可用作纤维粘结剂的基于乙烯基酯共聚物或(甲基)丙烯酸酯共聚物的自交联再分散性分散粉末在EP-B 687317(US-A 5668216)已有描述。该粘结剂体系的缺点是其在含水体系中较良好的再分散性。因此，在纤维成网过程中，粘结剂被含水的液体洗掉并且不再粘结纤维。
EP-A 721004公开了一种用于聚合物膜和涂层中的可交联、水分散性粉末，这些粉末包括具有至少一个官能团的成膜聚合物以及那些在分散于水中后相互之间形成非离子型化学键的反应活性化合物。更具体地说，在粘结剂分散于水中之后这一聚合物混合物可用于涂敷应用中。在该专利申请中没有提及纤维粘结在有关无纺织物中的任何用途。这些粘结体系的缺点是它们在水中良好的再分散性，结果使得在湿法成网过程中，粘结剂在粘结于纤维之前已被洗掉。
用于粘结剂和结构材料化学产品的水再分散性聚合物粉末已从DE-A 19545608中获知。粉末用聚乙烯醇加以稳定并包括水溶性、双官能度、封闭的醛作为交联剂组分。醛官能团的解封闭可任选地通过添加布朗斯特(Bronstedt)和路易斯酸来促进。
本发明的目的是提供一种使湿法成网纤维材料(特别是玻璃纤维材料)固结的粘结剂，该粘结剂能够与纤维一起被引入到含水的液体中，而且在纤维铺置之后，将确保纺织纤维片状材料的耐久固结。本发明的又一个目的是开发一种粉末形式的粘结剂，在干燥成网方法(气流铺置，梳理)中，它能够与纤维混合并与纤维一起铺置，然后由湿化步骤(浸泡、轧、汽蒸)活化成粘结剂以确保纺织片状材料的耐久固结。
这一目的可通过开发出一种易悬浮于含水的液体中的粘结剂来实现，且该粘结剂基于干燥、粉状的热塑性聚合物制备料，后者进而基于聚乙烯醇稳定化的聚合物和基于能够与聚乙烯醇形成永久化学键的反应活性组分。
本发明因此提供一种用于固结纤维材料的纤维粘结用粉末组合物，它包括：
a)基于一种或多种单体的聚乙烯醇稳定化聚合物的聚合物粉末，这些单体选自具有1-12个碳原子的支化或未支化羧酸的乙烯基酯，丙烯酸和甲基丙烯酸与具有1-12个碳原子的支化或未支化醇的酯，芳族乙烯基化合物，卤代乙烯，烯烃和二烯烃，和
b)无机化合物，它在室温(23℃)下为固体并在粉末被引入水中后与聚乙烯醇的OH基团形成化学键。
优选的乙烯基酯是乙酸乙烯酯，丙酸乙烯基酯，丁酸乙烯基酯，2-乙基己酸乙烯基酯，月桂酸乙烯基酯，乙酸1-甲基乙烯基酯，新戊酸乙烯基酯和具有9-11个碳原子的α支化单羧酸的乙烯基酯，例如VeoVa9R和VeoVa10R(Shell的商标)。乙酸乙烯基酯是特别优选的。
优选的甲基丙烯酸酯或丙烯酸酯是丙烯酸甲酯，甲基丙烯酸甲酯，丙烯酸乙酯，甲基丙烯酸乙酯，丙烯酸丙基酯，甲基丙烯酸丙基酯，丙烯酸正丁基酯，甲基丙烯酸正丁基酯，丙烯酸2-乙基己酯。特别优选丙烯酸甲酯，甲基丙烯酸甲酯，丙烯酸正丁基酯和丙烯酸2-乙基己酯。
优选的芳族乙烯基化合物是苯乙烯，甲基苯乙烯，和乙烯基甲苯。优选的卤代乙烯是氯乙烯。优选的烯烃是乙烯，丙烯，优选的二烯烃是1，3-丁二烯和异戊二烯。
任选地，聚合物可进一步含有基于单体总重量的0.05-10.0wt％共聚单体，该共聚单体选自烯属不饱和单-和二-羧酸和它们的酰胺，例如丙烯酸，甲基丙烯酸，马来酸，富马酸，衣康酸，丙烯酰胺，甲基丙烯酰胺，烯属不饱和磺酸和它们的盐类，优选乙烯基磺酸，2-丙烯酰胺基丙烷磺酸盐和N-乙烯基吡咯烷酮。以所述量使用的共聚单体的其它例子是烷氧基硅烷官能化单体，如丙烯酰基丙氧基三(烷氧基)-和甲基丙烯酰基丙氧基三(烷氧基)-硅烷，乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷，优选乙烯基三乙氧基硅烷和γ-甲基丙烯酰基丙氧基三乙氧基硅烷。也合适的是诸如丙烯酰胺基乙醇酸(AGA)、甲基丙烯酰胺基乙醇酸甲酯(MAGME)，N-羟甲基丙烯酰胺(NMA)，N-羟甲基甲基丙烯酰胺(NMMA)，N-羟甲基氨基甲酸烯丙基酯，N-羟甲基-丙烯酰胺或N-羟甲基甲基丙烯酰胺的烷基醚及它们的异丁氧基醚或正丁氧基醚的助交联剂。
聚合物组成一般经选择后应使其玻璃化转变温度Tg为-40℃至+90℃。聚合物的玻璃化转变温度Tg能够由差示扫描量热法(DSC)按照熟知方式进行测定。Tg还能够借助于Fox公式来粗略地估算。根据Fox T.G.，美国物理学会公告(Bull.Am.Physics Soc.)1，3，123页(1956)：1/Tg＝x1/Tg1＋x2/Tg2＋…＋xn/Tgn，其中xn是单体n的质量分数(wt％/100)和Tgn是该单体n的均聚物以开尔文(K)度计的玻璃化转变温度。均聚物的Tg值列于“聚合物手册”第三版，J.Wiley&Sons，New York(1989)。
优选下面所列举的聚合物，它们的重量百分数，选择性地包括共聚单体含量，总计为100wt％：
乙烯基酯聚合物类：
乙酸乙烯聚合物；乙烯含量为1-60wt％的乙酸乙烯-乙烯共聚物；乙烯含量为1-40wt％和氯乙烯含量为20-90wt％的乙烯基酯-乙烯-氯乙烯共聚物，该乙烯基酯优先包括乙酸乙烯酯和/或丙酸乙烯基酯和/或一种或多种可共聚合的乙烯基酯如月桂酸乙烯基酯，新戊酸乙烯基酯，2-乙基己酸乙烯基酯，α-支化羧酸的乙烯基酯，尤其维萨(Versatate)乙烯基酯(VeoVa9R，VeoVa10R，VeoVa11R)；具有1-50wt％一种或多种可共聚合的乙烯基酯类与乙酸乙烯的共聚物，它们选择性地另外含有1-40wt％乙烯，乙烯基酯类可以是月桂酸乙烯基酯，新戊酸乙烯基酯，2-乙基己酸乙烯基酯，α-支化羧酸的乙烯基酯，尤其是维萨(Versatate)乙烯基酯(VeoVa9R，VeoVa10R，VeoVa11R)；含有30-90wt％乙烯基酯，尤其是乙酸乙烯酯，和1-60wt％丙烯酸酯，尤其是丙烯酸正丁基酯或丙烯酸2-乙基己基酯的乙烯基酯-丙烯酸酯共聚物，它选择性地另外还含有1-40wt％的乙烯；含有30-75wt％的乙酸乙烯酯，1-30wt％的月桂酸乙烯基酯或α-支化羧酸的乙烯基酯，尤其是维萨酸(Versatate)乙烯基酯，1-30wt％的丙烯酸酯，尤其丙烯酸正丁基酯或丙烯酸2-乙基己酯的乙烯基酯—丙烯酸酯共聚物，它选择性地还含有1-40wt％的乙烯。
(甲基)丙烯酸聚合物类：丙烯酸正丁基酯或丙烯酸2-乙基己酯的聚合物；甲基丙烯酸甲酯与丙烯酸正丁基酯和/或丙烯酸2-乙基己酯的共聚物。
氯乙烯聚合物类：以及上述的乙烯基酯-氯乙烯-乙烯共聚物，氯乙烯-乙烯共聚物和氯乙烯-丙烯酸酯共聚物。
苯乙烯聚合物类：苯乙烯-丁二烯共聚物和苯乙烯-丙烯酸酯共聚物类如苯乙烯含量为10—70wt％的苯乙烯-丙烯酸正丁基酯或苯乙烯-丙烯酸2-乙基己酯。
聚合物的制备是按照常规方式由乳液聚合方法来进行的，随后根据EP-B 687317中所述的方法，通过喷雾干燥来干燥所获得的聚合物水分散体，该专利文献的公开内容被引入本文供参考。
聚合物通过使用部分水解或完全水解的聚乙烯醇，优选水解度为75-99mol％和Hppler粘度(4％强度水溶液，DIN 532015，在20℃下的Hppler方法)为1-60mPas、优选4-35mPas的部分水解的聚乙烯醇来稳定化。一般，聚乙烯醇组分是聚合物的1—30wt％。聚乙烯醇组分能够在聚合过程中加入或在聚合结束后加入，即在喷雾干燥之前或过程中。
无机化合物b)选自硼，铝，铬和锆的水溶性化合物，它们在室温下呈粉末状且在标准条件下它们在水中的溶解度不低于1g/每升水。例子是硼酸，氯化铝，氯氧化锆和乙酸锆。优选硼酸(B(OH)3)，硼砂(Na2B4O7x10H2O)以及有双-和多个配位基配位体的硼酸配合物，例如有脂族和脂环族多元醇的硼酸配合物，如硼酸与季戊四醇和酒石酸的配合物。
反应活性无机组分b)的量取决于聚乙烯醇所需要的交联度。用量一般是0.1-30wt％、优选1-15wt％，各百分含量是基于纤维粘结用粉末组合物的总重量。
纤维粘结用粉末组合物可选择性地另外包括常规量的颜料，抗氧化剂，染料，增塑剂，缓冲剂，成膜助剂，填料，阻燃剂，泡沫形成助剂，泡沫抑制剂，润湿剂，热敏剂，抗静电剂，杀虫剂和手感改进剂。优选包括粉末状、水溶性的物质作为PH缓冲剂。
纤维粘结用粉末组合物可用于固结天然和合成纤维材料。对于纤维材料的选择没有特别的限制，可在无纺织物工业中使用的所有纤维原料都可考虑，例如聚酯，聚酰胺，聚丙烯，聚乙烯，玻璃，陶瓷，粘胶，碳，纤维素，棉，羊毛和木纤维。优选聚酯，聚酰胺，玻璃，纤维素，棉，羊毛和木纤维。纤维材料能够以纤维，纱，毡布，稀松平纹织物或机织纺织品(机织品)。
纤维粘结用粉末组合物能够用于湿法成网方法中，也用于一种随后要加湿和使纤维材料层压成形的干法成网方法中。该纤维粘结用粉末组合物的组分a)和b)经混合后或分别加入到纤维材料中。在湿法成网或干法成网方法中，纤维粘结剂的用量是1-50wt％、优选5-30wt％，在每种情况下都基于纺织片状材料的总重量。对于层压，叠加重量一般是在1-1000g/m2，优选在5-100g/m2和特别优选在10-50g/m2范围内。
在优选的实施方案中，纤维粘结用粉末组合物用于粘结纤维材料的方法中，其中
A)该纤维粘结用粉末组合物和该纤维材料被悬浮于水中，然后铺置形成纺织片状材料，然后，如此获得的纺织片状材料通过热处理而选择性地加以干燥和热固结，或
B)该纤维粘结用粉末组合物和该纤维材料进行干混，混合物被悬浮于水中，然后铺置形成纺织片状材料，如此获得的片材借助于热处理来干燥和选择性地热固结，或
C)纤维粘结用粉末组合物和纤维材料进行干混，混合物随后被干铺展而形成纺织片状材料并用水加湿，或该纤维粘结用粉末组合物被抛洒在铺置的纤维材料上并用水加湿，如此获得的片材借助于热处理来干燥和选择性地热固结，或
D)该纤维材料以片状形式铺展开，然后抛洒纤维粘结用粉末组合物于其上，然后加湿并选择性地使用升高的温度和升高的压力层压到另一基板上。
在湿法成网方法A)的变化形式中，纤维和纤维粘结用粉末组合物，或纤维粘结用粉末组合物的各组分以连续或间歇方式按照任何顺序被悬浮到水中。纤维的悬浮可选择性地借助于离子或非离子表面活性剂来进行。优选这样一种方法，其中纤维和纤维粘结用粉末组合物的各组分与水在搅拌罐中分批混合而形成母料，然后选择性地用其它添加剂来调节到某些指定的性能。固含量优选为0.01-5wt％的悬浮液然后(优选连续地)在湿法成网方法中铺置成片状结构。
在湿法成网方法B)的变化形式中，纤维和纤维粘结用粉末组合物的各组分通过机械混合或在扰动的气流中进行连续或间歇式干混，干混物选择性地借助于离子或非离子表面活性剂被悬浮于水中。固含量优选为0.01-5wt％的悬浮液然后(优选连续地)在湿法成网方法中被铺置形成片状结构。
如果在干法成网方法C)的变化形式中使用纤维粘结用粉末组合物，纤维粘结用粉末组合物的纤维和各组分通过机械混合或在扰动气流中进行连续或间歇式干混。混合物然后以干法工艺铺置形成纺织片状材料，例如气流铺置方法或梳理方法。连续气流成网方法也是适合的，也就是在预成形的、未粘结的网上铺撒纤维粘结用粉末组合物，然后再打开并再进行气动成网过程。另一种可能性是纤维在梳理机上进行梳理形成网，随后在该网上铺撒纤维粘结用粉末组合物和铺撒的粉末借助于针而转移至网的内部。选择性地，如此梳理过的网也能够由交叉层叠加形成较厚的网。
借助于干法成网方法的各种变化形式铺置的纤维结构随后用液态或汽态水加湿而使纤维粘结用粉末活化。一般地，加湿是用5-60wt％，优选10-35wt％的水来进行的，在每种情况下都基于纤维和粉末的总重。加湿能够借助水蒸汽或借助于饱和、浸泡、喷射和轧的方法，任选地甚至将这些方法组合来进行。厚的网材料选择性地被汽蒸处理。还有可能如下进行：与纤维一起干法铺置纤维粘结用粉末组合物的唯一一种组分，优选组分a)，然后在加湿过程中以水溶液形式添加其它组分，优选组分b)。
在方法A)-C)的所有变化形式中，纤维材料的干燥和固结一般是在80—260℃、优选120—200℃的温度下，任意地在至多为100巴压力下进行，在这种情况下干燥温度和所使用的压力主要取决于纤维材料的性质。
对于层压，纤维或纤维织物如机织织物和无纺织物如稀松平纹织物被铺平并在其上面以区域、点或图案形式铺撒纤维粘结用粉末组合物。粘结剂通过按照上述方式加湿活化，然后在上面放置一个另一基板。层压件同样在以上规定的温度和压力条件下固结。
有用的基板包括机织织物和无纺织物，如玻璃纤维织物和玻璃纤维网，塑料膜如聚酯膜或电晕处理聚烯烃膜，木纤维板如硬刨花板或中等密度纤维(MDF)板，发泡片状材料如聚氨酯泡沫和聚乙烯醇泡沫。
有可能将两种相同或不同的片状纤维结构层压在一起。例子是汽车工业中的绝缘件，它由再生棉组成并与表面毡布持久地层压在一起。类似地有可能将纤维结构粘附于非纤维基材上。例子是在建筑绝缘部件中玻璃纤维粘附于的装饰面材上或在制鞋工业中机织织物粘附于皮革上。
所述纤维粘结用粉末组合物由两种以一种非常有利的形式并存的有反应活性的固体组分组成，它们在该种形式下可以无限期地贮存并且仅仅在与水接触后被活化。在含水的环境中引发的反应是自发和快速的。与相关现有技术中讨论的粉末不同，本发明的纤维粘结用粉末组合物在悬浮于水中之后立即进行交联。而且，在本发明的聚合物中，它是在颗粒表面上发生的与保护胶体的交联反应而不是在颗粒内部发生的与官能团的非常缓慢的反应。
令人惊奇的地方是纤维粘结用粉末组合物在水中的良好悬浮性或分散性以及粘结用粉末在纤维表面上的均匀分布。两种效果是令人惊奇的，因为，由于在粉末制剂中存在的两种组分之间有快速的交联反应，可以预计到在与水接触后结块(clumping)。
本发明将通过下面的实施例来更加详细地描述。
玻璃纤维与纤维粘结用粉末的粘结是在湿法成网方法中进行考察：
网的生产：
用移液管称重0.03g阳离子表面活性剂(Dehyquart SP)加入到玻璃烧杯中，然后与200g水混合。表面活性剂溶液在600rpm下搅拌。添加1.0g玻璃纤维。在大约1分钟的搅拌后，玻璃纤维悬浮液的搅拌速率提高到800rpm。然后添加纤维粘结用粉末组合物的两种组分a)和b)，并搅拌15分钟。测量悬浮液的PH值。在搅拌时间结束后，在贝纶(Perlon)筛上收集玻璃纤维悬浮液。放置湿玻璃纤维网在铝盘上并在150℃下干燥3小时。
下面的粉末用作组分a)：
a)：
聚合物粉末1：
有1wt％N-羟甲基丙烯酰胺的乙酸乙烯酯聚合物，用8wt％聚乙烯醇(Hppler粘度25mPas；水解度92％)加以稳定化。
聚合物粉末2：
有15wt％乙烯的乙烯-乙酸乙烯酯共聚物，用11wt％聚乙烯醇(Hppler粘度4mPas；水解度92％)加以稳定化。
聚合物粉末3：
用11wt％聚乙烯醇(Hppler粘度4mPas；水解度82％)加以稳定化的乙酸乙烯均聚物。
聚合物粉末4：
有1wt％N-羟甲基丙烯酰胺的乙酸乙烯酯聚合物，用8wt％的聚乙烯醇(Hppler粘度56mPas；水解度98％)加以稳定化。
聚合物粉末5：
有封闭醛(类似于DE-A 19545608的戊二醛双(亚硫酸氢钠))的聚乙酸乙烯酯粉末。
聚合物粉末6：
含有环氧交联剂的、乳化剂稳定的、含羧基的苯乙烯-丙烯酸酯粉末。
玻璃纤维网的强度：
玻璃纤维网的强度是用手判断并根据以下约定来评分：1＝非常良好，2＝良好，3＝不令人满意，4＝差。
试验结果列于表1中。
表1中结果显示了，与仅仅使用粘结剂a)的纤维粘结性相比，使用组分a)和b)的混合物的纤维粘结性得到了改进。传统的交联粘结剂混合物可在对比例15-21中用作对照物。本发明的混合物优异于利用环氧交联剂的传统粘结剂(对比例15-18)、传统的封闭类交联系统(对比例19)和没有保护胶体的环氧交联性粘结剂。
表1实施例 组分a) 量 组分b) 量 PH 评分C1 粉末1 0.25g 8 42 粉末1 0.25g 硼砂 0.0025g 8 23 粉末1 0.25g 硼砂 0.0125g 8 24 粉末1 0.25g 硼砂 0.025g 8 25 粉末1 0.25g 硼砂 0.05g 8 2C6 粉末2 0.25g 7 37 粉末2 0.25g 硼砂 0.0025g 8 2-38 粉末2 0.25g 硼砂 0.0125g 8 2C9 粉末3 0.25g 5 310 粉末3 0.25g 硼砂 0.0025g 8 2-311 粉末3 0.25g 硼砂 0.0125g 8 2C12 粉末4 0.25g 6 313 粉末4 0.25g 硼砂 0.0025g 8 2-314 粉末4 0.25g 硼砂 0.0125g 8 1-2C15 粉末1 0.25g 乙二醛 0.0025g 3.5 3-4C16 粉末1 0.25g 乙二醛 0.0125g 4.7 3-4C17 粉末1 0.25g 乙二醛 0.025g 4.8 3-4C18 粉末1 0.25g 乙二醛 0.05g 4.9 3-4C19 粉末5 0.25g AlCl3 0.0125g 4 3C20 粉末6 0.25g 6 4C21 粉末6 0.25g 硼砂 0.025g 8 4纤维粘结用粉末组合物的粘结力是在成形的纤维制品中测试的。
测试的纤维粘结用粉末组合物：
本发明实施例22：
950g聚合物粉末1(有1wt％N-羟甲基丙烯酰胺的乙酸乙烯聚合物，用8wt％的聚乙烯醇(Hppler粘度25mPas；水解度92％)加以稳定化)与50g硼砂在犁片混合机(plowshare mixer)中混合。
本发明实施例23：
将950g聚合物粉末1与50g三氯化铝六水合物在犁片混合机(plowshare mixer)中混合。
对比例24：
使用聚合物粉末1，但没有组分b)。成形纤维制品的制造：
为了生产标准的硬质纤维板，将118g再生棉与13.2g分别与来自本发明实施例22和23和对比例24的粘结用粉末混合，然后铺置来覆盖30×30cm的面积。纤维/粉末混合物然后用水加湿(通过喷雾)并随后立即在约180℃的温度和在约36巴的压力下加压5分钟，生产出厚度为2mm和重量为1390g/m2的板材。
本发明实施例25：
仅仅使用聚合物粉末1作为纤维粘结剂来制造成形纤维制品，但用5％强度的乙酸锆溶液喷雾，而不是用水喷雾。
试验方法：
测试最大拉伸强度UTS：
从加压成形的纤维制品上裁剪一尺寸为10×100mm的试样，然后根据DIN 53857在Zwick拉伸试验仪上在室温下进行测试。
测试吸水率：
尺寸为50×20mm的成形纤维制品在水中贮存1小时或24小时，然后根据比重来测定因水溶胀所导致的重量增加。
测试耐热性：
从成形纤维制品上切下240×20mm的样条并水平固定在一个平的表面上使其在该表面边缘以外有100mm的悬空并承受40g负荷。在T＝120℃下1小时之后通过测量挠度d来测定耐热性。挠度d是距离该表面100mm的样条端部在负荷下弯曲的量度。
试验结果列于表2中：
表2
实施例 UTS[N] 吸水率[％] 耐热性[mm]
22 954 59 22.0
23 964 59 21.0
C24 630 59 31.0
25 1081 57 23.5
表2中试验结果清楚地表明，与没有组分b)的粘结用粉末(对比例24)相比，使用纤维粘结用粉末组合物改进了机械强度(最高拉伸强度，耐热性)。
Claims (10)
1、一种用于固结纤维材料的纤维粘结用粉末组合物，它包括：
a)基于一种或多种单体的聚乙烯醇稳定化聚合物的聚合物粉末，这些单体选自具有1-12个碳原子的支化或未支化羧酸的乙烯基酯，丙烯酸和甲基丙烯酸与具有1-12个碳原子的支化或未支化醇的酯，芳族乙烯基化合物，卤代乙烯，烯烃和二烯烃，和
b)无机化合物，它在室温下为固体并在粉末被引入水中后与聚乙烯醇的OH基团形成化学键。
2、权利要求1的纤维粘结用粉末组合物，其中组分a)是基于选自下列聚合物的、用聚乙烯醇稳定化的聚合物粉末：
乙酸乙烯酯聚合物；乙烯含量为1-60wt％的乙酸乙烯酯-乙烯共聚物；乙烯含量为1-40wt％和氯乙烯含量为20-90wt％的乙烯基酯-乙烯-氯乙烯共聚物；具有1-50wt％一种或多种可共聚合的乙烯基酯类和选择性地含有1-40wt％乙烯的乙酸乙烯酯共聚物；含有30-90wt％乙烯基酯和1-60wt％丙烯酸酯以及选择性地还含有1-40wt％的乙烯的乙烯基酯-丙烯酸酯共聚物；含有30-75wt％的乙酸乙烯酯和1-30wt％的其它乙烯基酯以及选择性地还含有1-40wt％的乙烯的乙烯基酯—丙烯酸酯共聚物；丙烯酸正丁酯或丙烯酸2—乙基己酯的聚合物；甲基丙烯酸甲酯与丙烯酸正丁基酯和/或丙烯酸2-乙基己酯的共聚物；氯乙烯-乙烯共聚物；氯乙烯-丙烯酸酯共聚物；苯乙烯-丁二烯共聚物；以及在每种情况下苯乙烯含量为10—70wt％的苯乙烯-丙烯酸酯共聚物。
3、权利要求1或2的纤维粘结用粉末组合物，其中所述聚合物另外含有基于单体总重量的0.05-10.0wt％共聚单体，该共聚单体选自烯属不饱和单-和二-羧酸和它们的酰胺，烯属不饱和磺酸和它们的盐类，丙烯酰基丙氧基三(烷氧基)-和甲基丙烯酰基丙氧基三(烷氧基)-硅烷，乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷，N-羟甲基丙烯酰胺(NMA)，N-羟甲基甲基丙烯酰胺(NMMA)，N-羟甲基氨基甲酸烯丙基酯，N-羟甲基-丙烯酰胺或N-羟甲基甲基丙烯酰胺的烷基醚及它们的异丁氧基醚或正丁氧基醚。
4、权利要求1—3中任何一项的纤维粘结用粉末组合物，其中聚乙烯醇是水解度为75-99mol％和hppler粘度为1—60mPas的部分水解聚乙烯醇。
5、权利要求1—4中任何一项的纤维粘结用粉末组合物，其中组分b)是选自硼，铝，铬和锆的水溶性化合物的无机化合物，它们在室温下呈粉末状且在标准条件下它们在水中的溶解度不低于1g/每升水。
6、权利要求1—4中任何一项的纤维粘结用粉末组合物，其中组分b)是选自硼酸，硼砂，有双-和多个配位基配位体的硼酸配合物，硝酸铝，氯化铝，氯氧化锆和乙酸锆的无机化合物。
7、权利要求1—6中任何一项的纤维粘结用粉末组合物，其中包括粉末状水溶性物质作为PH缓冲剂。
8、使用权利要求1-7中任何一项所述的纤维粘结用粉末组合物固结纤维材料的方法，它包括在湿法成网方法中进行固结，在干法成网方法中先铺置随后加湿，然后将纤维材料层压成形的固结方法。
9、权利要求8的方法，其中所述纤维粘结用粉末组合物的组分a)和b)经混合后加入或分别加入到纤维材料中。
10、权利要求8或9的方法，其中
A)该纤维粘结用粉末组合物和该纤维材料被悬浮于水中，然后铺置形成纺织片状材料，然后，如此获得的纺织片状材料通过热处理和选择性地加以干燥和热固结，或
B)该纤维粘结用粉末组合物和该纤维材料进行干混，混合物被悬浮于水中，然后铺置形成纺织片状材料，如此获得的片材借助于热处理来干燥和选择性地热固结，或
C)纤维粘结用粉末组合物和纤维材料进行干混，混合物随后在干燥状态下被铺置而形成纺织片状材料并用水加湿，或该纤维粘结用粉末组合物被抛洒在铺置的纤维材料上并用水加湿，如此获得的片材借助于热处理来干燥和选择性地热固结，或
D)该纤维材料以片状形式铺展开，然后抛洒该纤维粘结用粉末组合物于其上，然后加湿和选择性地使用升高的温度和升高的压力层压到另一基板上。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19827475A DE19827475A1 (de) | 1998-06-19 | 1998-06-19 | Faserbindepulver-Zusammensetzung zur Verwendung für die Verfestigung von Fasermaterialien |
| DE19827475.0 | 1998-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1239747A true CN1239747A (zh) | 1999-12-29 |
Family
ID=7871474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99109153A Pending CN1239747A (zh) | 1998-06-19 | 1999-06-18 | 固结纤维材料的纤维粘结用粉末组合物 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6511561B1 (zh) |
| EP (1) | EP0965672B1 (zh) |
| JP (1) | JP3305677B2 (zh) |
| KR (1) | KR20000006154A (zh) |
| CN (1) | CN1239747A (zh) |
| CA (1) | CA2275834A1 (zh) |
| DE (2) | DE19827475A1 (zh) |
| PL (1) | PL333808A1 (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103228839A (zh) * | 2010-12-17 | 2013-07-31 | 瓦克化学股份公司 | 包含苯乙烯-丁二烯共聚物和/或苯乙烯-丙烯酸酯共聚物和乙酸乙烯酯-乙烯共聚物的组合的纸张涂布浆料 |
| CN105648835A (zh) * | 2015-12-30 | 2016-06-08 | 华南理工大学 | 一种高性能防潮纸及其制备方法与应用 |
| CN114364832A (zh) * | 2019-09-10 | 2022-04-15 | 株式会社钟化 | 阻燃性纤维复合体和阻燃性工作服 |
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| DE10103213A1 (de) * | 2001-01-25 | 2002-08-14 | Wacker Polymer Systems Gmbh | Verfahren zur Herstellung von wiederverwertbaren Formkörpern |
| JP4167834B2 (ja) | 2002-01-25 | 2008-10-22 | 久光製薬株式会社 | 粘着剤およびこれを用いてなる貼付製剤 |
| USRE45936E1 (en) | 2002-01-25 | 2016-03-22 | Hisamitsu Pharmaceutical Co., Inc. | Pressure-sensitive adhesive and patch employing the same |
| US7354503B2 (en) | 2003-06-20 | 2008-04-08 | Sierra Pine Ltd. | Fire retardant composite panel product and a method and system for fabricating same |
| US9169364B2 (en) | 2006-06-16 | 2015-10-27 | Georgia-Pacific Chemicals Llc | Binder compositions and methods for making and using same |
| US20110165398A1 (en) * | 2009-12-02 | 2011-07-07 | Georgia-Pacific Chemicals Llc | Binder compositions for making fiberglass products |
| US9217065B2 (en) | 2006-06-16 | 2015-12-22 | Georgia-Pacific Chemicals Llc | Binder compositions for making fiberglass products |
| DE102008042407A1 (de) * | 2008-09-26 | 2010-04-01 | Wacker Chemie Ag | Bindemittel für Mineralfasermatten |
| JP5691182B2 (ja) * | 2010-01-28 | 2015-04-01 | 日信化学工業株式会社 | 無機繊維マットの製造方法 |
| BR112012032834A2 (pt) * | 2010-06-25 | 2016-11-08 | Celanese Emulsions Gmbh | composições aglutinantes de copolímero de acetato de vinila plastificado para manta de fio picado. |
| WO2013142194A1 (en) * | 2012-03-20 | 2013-09-26 | Georgia-Pacific Chemicals Llc | Lignocellulose based composite products made with modified aldehyde based binder compositions |
| CN102926201B (zh) * | 2012-11-28 | 2015-02-04 | 福州大学 | 一种除蚊缓释布的整理方法 |
| FR3027546B1 (fr) | 2014-10-24 | 2017-07-21 | Porcher Ind | Meches poudrees par procede electrostatique |
| EP3856823A4 (en) * | 2018-09-24 | 2022-06-29 | Owens-Corning Intellectual Capital, LLC | Ceiling board and tile with reduced discoloration |
| US11813833B2 (en) | 2019-12-09 | 2023-11-14 | Owens Corning Intellectual Capital, Llc | Fiberglass insulation product |
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| US3112235A (en) * | 1959-12-31 | 1963-11-26 | Borden Co | Method of adhering surfaces |
| US3438808A (en) * | 1965-04-22 | 1969-04-15 | Air Reduction | Polyvinyl alcohol-boric acid-containing composition,treatment of paper web therewith and the treated paper web |
| US3689314A (en) * | 1970-02-24 | 1972-09-05 | Kimberly Clark Co | Method for fabricating improved flushable wrappers for absorbent pads and product obtained thereby |
| ZA739228B (en) | 1972-12-15 | 1974-11-27 | Hoechst Ag | Polyvinyl ester adhesive |
| JPS51125446A (en) * | 1975-04-08 | 1976-11-01 | Kuraray Co Ltd | Powder composition for use in molding |
| JPS61236866A (ja) * | 1985-04-15 | 1986-10-22 | Kurita Water Ind Ltd | 野積石炭堆積物のコーティング剤 |
| AU612496B2 (en) | 1988-10-06 | 1991-07-11 | Owens-Corning Fiberglas Corporation | Preformable mat |
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| DE3942813A1 (de) * | 1989-12-23 | 1991-06-27 | Akzo Gmbh | Laminat |
| DE4306808A1 (de) | 1993-03-04 | 1994-09-08 | Wacker Chemie Gmbh | Vernetzbare Dispersionspulver als Bindemittel für Fasern |
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-
1998
- 1998-06-19 DE DE19827475A patent/DE19827475A1/de not_active Ceased
-
1999
- 1999-06-02 DE DE59900263T patent/DE59900263D1/de not_active Expired - Lifetime
- 1999-06-02 EP EP99109377A patent/EP0965672B1/de not_active Expired - Lifetime
- 1999-06-14 KR KR1019990022035A patent/KR20000006154A/ko active IP Right Grant
- 1999-06-17 PL PL99333808A patent/PL333808A1/xx not_active Application Discontinuation
- 1999-06-18 US US09/336,272 patent/US6511561B1/en not_active Expired - Fee Related
- 1999-06-18 CN CN99109153A patent/CN1239747A/zh active Pending
- 1999-06-18 JP JP17314999A patent/JP3305677B2/ja not_active Expired - Fee Related
- 1999-06-21 CA CA002275834A patent/CA2275834A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103228839A (zh) * | 2010-12-17 | 2013-07-31 | 瓦克化学股份公司 | 包含苯乙烯-丁二烯共聚物和/或苯乙烯-丙烯酸酯共聚物和乙酸乙烯酯-乙烯共聚物的组合的纸张涂布浆料 |
| CN103228839B (zh) * | 2010-12-17 | 2016-08-03 | 瓦克化学股份公司 | 包含苯乙烯-丁二烯共聚物和/或苯乙烯-丙烯酸酯共聚物和乙酸乙烯酯-乙烯共聚物的组合的纸张涂布浆料 |
| CN105648835A (zh) * | 2015-12-30 | 2016-06-08 | 华南理工大学 | 一种高性能防潮纸及其制备方法与应用 |
| CN114364832A (zh) * | 2019-09-10 | 2022-04-15 | 株式会社钟化 | 阻燃性纤维复合体和阻燃性工作服 |
| CN114364832B (zh) * | 2019-09-10 | 2023-06-02 | 株式会社钟化 | 阻燃性纤维复合体和阻燃性工作服 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0965672A1 (de) | 1999-12-22 |
| EP0965672B1 (de) | 2001-09-19 |
| PL333808A1 (en) | 1999-12-20 |
| CA2275834A1 (en) | 1999-12-19 |
| DE19827475A1 (de) | 1999-12-23 |
| US6511561B1 (en) | 2003-01-28 |
| KR20000006154A (ko) | 2000-01-25 |
| DE59900263D1 (de) | 2001-10-25 |
| JP3305677B2 (ja) | 2002-07-24 |
| JP2000096017A (ja) | 2000-04-04 |
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