CN102459385B - 含有可塑变形硬质聚氨酯泡沫、粘合剂和覆盖材料的复合部件 - Google Patents
含有可塑变形硬质聚氨酯泡沫、粘合剂和覆盖材料的复合部件 Download PDFInfo
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- CN102459385B CN102459385B CN201080024562.XA CN201080024562A CN102459385B CN 102459385 B CN102459385 B CN 102459385B CN 201080024562 A CN201080024562 A CN 201080024562A CN 102459385 B CN102459385 B CN 102459385B
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- moisture
- adhesive
- cure
- thermoformable
- isocyanate
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- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
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- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种生产复合部件的方法,其中提供可热成型硬质聚氨酯泡沫并与覆盖材料粘附结合,其中使用通过与催化剂水溶液接触而固化的湿固化聚氨酯粘合剂作为粘合剂。本发明进一步涉及一种可通过这种方法得到的复合部件,和该复合部件在车辆中,更特别地作为车顶衬里的用途。
Description
本发明涉及一种通过引入可热成型硬质聚氨酯泡沫并将它粘附结合在衬里材料上而生产复合部件的方法,所用粘合剂为通过与催化剂水溶液接触而固化的湿固化聚氨酯粘合剂,所用催化剂水溶液为碱金属硅酸盐水溶液。本发明进一步涉及一种可通过这种方法得到的复合部件,和该复合部件在车辆中,更特别地作为车顶衬里的用途。
可塑变形硬质聚氨酯泡沫,下文也称为可热成型硬质聚氨酯泡沫,和它们在机动车辆中作为内部装饰的用途是已知的,且例如描述于“Kunststoffhandbuch,第7卷,Polyurethane”,Carl Hanser Verlag,1993年第3版,第6.5.4.1部分中。在该申请中,将用于生产内部装饰的可塑变形硬质聚氨酯泡沫在模具中塑性变形,并在成型步骤期间或在进行成型以后用衬里材料层压。所用衬里材料例如为增强材料如玻璃纤维毡和/或装饰材料如无纺布。在塑料变形期间或以后,将这些衬里材料借助粘合剂,通常聚氨酯基粘合剂粘附在硬质聚氨酯泡沫上。这里具体优点是用衬里材料层压可在一个步骤中与塑料变形一起进行。这种可塑变形硬质聚氨酯泡沫,和这些可热成型硬质聚氨酯泡沫与衬里材料的层压例如描述于EP 437787和DE 4333795中。
通常,使用基于聚氨酯的粘合剂以将硬质聚氨酯泡沫和衬里材料粘附结合。特别地,尤其优选湿固化单组分粘合剂。在这种情况下,将粘合剂应用于尚未被压缩的硬质泡沫上,将泡沫用水喷雾并用衬里材料层压,并将层压材料在升高的温度下在模具中压缩。
所用湿固化单组分粘合剂优选为已提供有催化剂的异氰酸酯封端聚氨酯预聚物。包含锡基催化剂或叔胺催化剂的这种湿固化单组分粘合剂例如描述于EP 464483中。这类粘合剂的缺点是它们仅具有有限的储存稳定性,且常常仅具有短的加工寿命。此外,从毒物学立场看,有机锡化合物是有害的。
WO 2004/033519描述了一种具有铋基催化剂的湿固化聚氨酯组合物。尽管铋化合物比有机锡化合物毒性小,但铋催化的湿固化体系也仅具有低储存稳定性和短加工寿命。此外,胺基、锡基和铋基催化剂的使用导致在密闭空间如汽车的客室内产生气味公害的物质的排放。
关于安装在汽车内部且最常用作车顶区域的饰件(称为车顶衬里)的可塑变形硬质聚氨酯泡沫所施加的要求是多样的。因此,需要它们具有一定硬度且必须不排放任何例如导致气味的有害物质。车顶衬里的特别重要的功能是它对声学的贡献。这里的具体任务是降低空气噪音。这些车顶衬里性能的品质关键取决于所用可塑变形硬质聚氨酯泡沫的性能以及所用粘合剂。就良好的空气噪音吸收而言,具有非常高的空气渗透性的车顶衬里是理想的。
因此,本发明的目的是提供一种生产包含可热成型硬质聚氨酯泡沫、衬里材料和粘合剂的复合部件的方法,其中所述粘合剂用很少或优选不用毒物学有害催化剂固化,所述部件具有长储存和加工寿命,且通过最小的排放水平对成品部件上的低气味公害有贡献。本发明的另一目的是提供饰件,尤其是汽车的车顶衬里,其具有显著的声学性能且不导致客室中的气味公害。
本发明的目的已通过一种通过引入可热成型硬质聚氨酯泡沫并将它粘附结合在衬里材料上而生产复合部件的方法实现,所用粘合剂为通过与催化剂水溶液接触而固化的湿固化聚氨酯粘合剂,所用催化剂水溶液为碱金属硅酸盐水溶液。
在本文中所用衬里材料优选为用于衬垫可热成型硬质聚氨酯泡沫的常规材料。这些材料包括玻璃纤维毡、柔性泡沫层、织品如机织物、针织物,和无纺布,以及常规衬里材料的组合。
作为可热成型硬质聚氨酯泡沫,可使用任何常规可热成型硬质聚氨酯泡沫。这种硬质聚氨酯泡沫例如描述于EP 437787、DE 4333795和DE102004062540中。它们优选为开孔的,且优选不发出任何导致气味形成的物质。在一个优选实施方案中,可热成型硬质聚氨酯泡沫在本发明意义上通过将a)有机多异氰酸酯与b)聚醚醇、任选c)增链剂和/或交联剂、d)发泡剂、e)催化剂和任选f)辅助剂和添加剂混合以得到反应混合物并使该反应混合物反应而得到,其中所述聚醚醇包含b1)羟值为150-650且伯羟基含量大于70%的2至4官能聚氧化烯多元醇和b2)羟值为25-40且伯羟基含量大于70%的2至3官能聚氧化烯多元醇。
本发明可热成型硬质聚氨酯泡沫可优选在80-160℃,更优选100-150℃的模具温度下可塑变形。所用成分a)-f)为聚氨酯化学中已知的常规成分。聚氧化烯多元醇b1)优选包含至少30重量%,更优选至少50重量%的氧化乙烯。聚氧化烯多元醇b2)优选包含至少50重量%,更优选至少80重量%的氧化丙烯。
除所述聚氧化烯多元醇b1)和b2)外,也可使用其它多羟基化合物,例如其它聚醚醇、聚酯醇或其它异氰酸酯反应性化合物如聚硫醇或聚胺。作为组分b)总重量的比例,化合物b1)和b2)的重量分数优选为至少50重量%,更优选至少70重量%,更特别地至少80重量%。聚氧化烯多元醇b1)与b2)之比优选为0.8∶1-1.5∶1。
作为用于制备可热成型硬质聚氨酯泡沫的增链剂和/或交联剂c),优选使用二丙二醇和/或三丙二醇。
湿固化聚氨酯粘合剂在本发明上下文中为包含含有异氰酸酯基团的预聚物的混合物,或含有异氰酸酯基团的预聚物本身,该混合物含有至少50重量%,优选至少80重量%,更特别地至少95重量%的含有异氰酸酯基团的预聚物。另外,本发明湿固化聚氨酯粘合剂可包含其它添加剂如表面活性物质,抑制剂如二甘醇双氯甲酸酯或正磷酸,增塑剂,无机填料如砂、高岭土、白垩、硫酸钡、二氧化硅,氧化稳定剂,染料和颜料,稳定剂一例如对水解、光、热或变色,有机和/或无机填料,乳化剂,阻燃剂,老化抑制剂、附着力促进剂和增强剂,以及聚氨酯化学中常用的催化剂。本发明湿固化聚氨酯粘合剂的粘度根据DIN 53 018在25℃下测量优选位于500-5000mPas,更优选1000-3000mPas的范围内。
含有异氰酸酯基团的预聚物在本发明上下文中应当理解为多异氰酸酯与含有至少两个异氰酸酯反应性基团的相对高分子量化合物、任选的具有一个异氰酸酯反应性基团的化合物,以及任选的增链剂和/或交联剂的反应产物,其中多异氰酸酯过量使用。
可用于制备含异氰酸酯基团的预聚物的多异氰酸酯为所有现有技术脂族、脂环族和芳族二官能或多官能异氰酸酯,以及其任何所需混合物。优选使用芳族二官能或多官能异氰酸酯。实例为4,4’、2,4’和2,2’二苯基甲烷二异氰酸酯、单体二苯基甲烷二异氰酸酯的混合物,和二苯基甲烷二异氰酸酯的高级多环同系物(聚合MDI)、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、1,5-萘二异氰酸酯(NDI)、2,4,6-甲苯三异氰酸酯和2,4-和2,6-甲苯二异氰酸酯(TDI)或其混合物。
特别优选使用2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯和4,4’-二苯基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯的高级多环同系物(聚合MDI)、以及这些异氰酸酯的混合物,更特别是2,4’-二苯基甲烷二异氰酸酯和4,4’-二苯基甲烷二异氰酸酯的混合物作为多异氰酸酯(a)。
作为具有至少两个异氰酸酯反应性基团的相对高分子量异氰酸酯反应性化合物,为制备含异氰酸酯基团的预聚物,可使用具有至少两个对异氰酸酯基团呈反应性的基团的所有化合物。这些化合物具有至少400g/mol的分子量。优选使用聚酯醇、聚醚醇或聚醚-聚酯醇,其可通过将聚酯烷氧基化而得到。
聚醚醇通过已知方法制备,例如如通过用碱金属氢氧化物或碱金属醇盐作为催化剂并加入至少一种包含2-5,优选2-4,更优选2-3,更特别是2个结合形式的反应性氢原子的起动剂分子阴离子聚合,或通过用路易斯酸如五氯化锑或三氟化硼醚化合物由一种或多种在亚烷基中具有2-4个碳原子的氧化烯阳离子聚合。另外,作为催化剂,也可使用多金属氰化物化合物,称为DMC催化剂。合适氧化烯的实例包括四氢呋喃、1,3-氧化丙烯、1,2-和/或2,3-氧化丁烯以及优选氧化乙烯和1,2-氧化丙烯。氧化烯可以单独地、连续交替地或作为混合物使用。优选使用1,2-氧化丙烯、氧化乙烯或1,2-氧化丙烯和氧化乙烯的混合物。
预期的起动剂分子优选为水或二-和三元醇如乙二醇、1,2-或1,3-丙二醇、二甘醇、二丙二醇、1,4-丁二醇、甘油和三羟甲基丙烷。
优选的聚醚多元醇,更优选聚氧化丙烯多元醇或聚氧化丙烯-聚氧化乙烯多元醇具有2-5,更优选2-3的官能度,和400-9000,优选1000-6000,更优选1500-5000,更特别地2000-4000g/mol的分子量。作为聚醚多元醇,特别优选使用重均分子量为1500-2500g/mol的聚丙二醇。
除具有至少两个对异氰酸酯基团呈反应性的基团的相对高分子量化合物外,可使用仅具有一个异氰酸酯反应性基团的化合物。这些优选为聚醚一元醇,其类似于上述聚醚醇,起始于单官能起动剂分子得到,如乙二醇一甲醚。聚醚一元醇的分子量优选为100-1000g/mol。如果使用聚醚一元醇,则聚醚一元醇与聚醚多元醇的重量比优选为1∶30-4∶1。
任选,也可使用增链剂和/或交联剂制备含有异氰酸酯基团的预聚物。增链剂和/或交联剂可在加入多元醇以前、一起或以后加入。所用增链剂和/或交联剂为分子量优选小于400g/mol,更优选60-350g/mol的物质,其中增链剂具有两个异氰酸酯反应性氢原子,交联剂具有三个异氰酸酯反应性氢原子。这些化合物可单独或以混合物的形式使用。如果使用增链剂,则特别优选1,3-和1,2-丙二醇、二丙二醇、三丙二醇和1,3-丁二醇。
如果使用增链剂、交联剂或其混合物,则它们有利地以基于多异氰酸酯、相对高分子量异氰酸酯反应性化合物和增链剂和/或交联剂的重量1-60重量%,优选1.5-50重量%,更特别地2-40重量%的量使用。
异氰酸酯预聚物可通过使过量的上述多异氰酸酯在例如30-100℃的温度下,优选在约80℃下与具有至少两个异氰酸酯反应性基团的相对高分子量化合物、任选的具有一个异氰酸酯反应性基团的化合物以及任选的增链剂和/或交联剂反应以得到预聚物而得到。将多异氰酸酯、具有至少两个异氰酸酯反应性基团的相对高分子量化合物、任选的具有一个异氰酸酯反应性基团的化合物以及任选的增链剂和/或交联剂优选以1.5∶1-15∶1,优选1.8∶1-8∶1的异氰酸酯基团与异氰酸酯反应性基团之比相互混合。特别优选异氰酸酯预聚物通过将具有至少两个异氰酸酯反应性基团的相对高分子量化合物、任选的具有一个异氰酸酯反应性基团的化合物以及任选的增链剂和/或交联剂以使得所制备预聚物的NCO含量基于所制备异氰酸酯预聚物的总重量为5-30重量%,更特别地10-25重量%的比相互混合而制备。随后,可优选将挥发性异氰酸酯优选通过薄膜蒸馏而分离。在这种情况下,异氰酸酯预聚物的粘度在25℃下优选为100-5000mPas。基于甲苯二异氰酸酯的本发明异氰酸酯预聚物通常具有500-3000mPas的粘度,而基于二苯基甲烷二异氰酸酯的本发明异氰酸酯预聚物通常具有600-3000mPas的粘度,每种情况下在25℃下。异氰酸酯预聚物的平均异氰酸酯官能度优选为2.0-2.9,更优选2.1-2.6。
湿固化聚氨酯粘合剂还可包含催化剂。这些催化剂例如包括脒如2,3-二甲基-3,4,5,6-四氢嘧啶,叔胺如三乙胺、三丁胺、二甲基苄胺,N-甲基-、N-乙基-、N-环己基吗啉、N,N,N′,N′-四甲基乙二胺、N,N,N′,N′-四甲基丁二胺、N,N,N′,N′-四甲基己二胺、五甲基二亚乙基三胺、四甲基二氨基乙醚、双(二甲基氨基丙基)脲、二甲基哌嗪、1,2-二甲基咪唑、1-偶氮双环[3.3.0]辛烷,以及优选1,4-二氮杂双环[2.2.2]辛烷,和链烷醇胺化合物如三乙醇胺、三异丙醇胺、N-甲基-和N-乙基-二乙醇胺,和二甲基乙醇胺。还预期作为催化剂的有有机金属化合物,优选有机锡化合物如有机羧酸的锡(II)盐,例如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II),和有机羧酸的二烷基锡(IV)盐,实例为二乙酸二丁锡、二月桂酸二丁锡、马来酸二丁锡和二乙酸二辛锡,以及羧酸铋如新癸酸铋(III)、2-乙基己酸铋和辛酸铋,或其混合物。有机金属化合物可单独或与碱性胺组合使用。
优选加入基于含有异氰酸酯基团的预聚物的重量小于2重量%,更优选小于1重量%,特别是不加入催化剂或催化剂组合。
在本发明复合部件的生产中,每平方米可热成型硬质聚氨酯泡沫优选使用20-300g,更优选50-200g的湿固化聚氨酯粘合剂。
湿固化聚氨酯粘合剂通过与催化剂水溶液接触而固化。后者包括碱金属硅酸盐水溶液。
可使用的碱金属水溶液为已知和市售的通式M2O·SiO2碱金属硅酸盐(其一般称为“水玻璃”,且其中M为碱金属且M2O∶SiO2比可变)的水溶液。所用碱金属优选为钠。也可使用不同碱金属硅酸盐的混合物,实例为包含硅酸钠和硅酸钾的混合物,其中Na2O∶K2O比优选为99.5∶0.5-25∶75。M2O与SiO2的摩尔比可在常规范围内变化,通常为4-0.2,优选1.5-3。如果使用优选的硅酸钠,则Na2O与SiO2的重量比例如由1∶1.6至1∶4,优选由1∶2至1∶3.5,更特别地由1∶2至1∶3.3变化。
水溶液中碱金属硅酸盐的浓度可根据在粘度或所需水含量方面的具体要求调整,且通常为0.01-80重量%,优选0.1-80重量%,更优选10-50重量%,更特别地15-35重量%在水溶液中的碱金属硅酸盐。此处优选使用不饱和的碱金属硅酸盐溶液。这种溶液通过将水加入饱和碱金属硅酸盐溶液中而得到。
催化剂水溶液与湿固化聚氨酯粘合剂的重量比通常为1∶2-5∶1,优选1∶1-2∶1。这相应于待粘附结合的可热成型硬质聚氨酯泡沫每侧应用10-150g/m2。
在本发明复合部件的生产中,它通常首先引入可热成型硬质聚氨酯泡沫。然后将泡沫在一侧或优选两侧上用湿固化聚氨酯粘合剂涂覆,并用碱金属硅酸盐溶液喷雾。随后应用衬里材料并将复合材料在模具中在升高的温度下,优选60-180℃下,更优选100-150℃下成型,并将湿固化聚氨酯粘合剂固化。如果观察优选比例,则该加工产生湿固化聚氨酯粘合剂的起泡,由此不会不利地影响可热成型硬质聚氨酯泡沫的开孔性质。
本发明还提供一种可通过本发明方法得到的复合部件。
本发明复合部件优选用作陆地、水和空中交通工具中的饰件,更优选作为汽车中的饰件,尤其作为车顶衬里。
本发明方法可在现有生产线上进行。因为湿固化聚氨酯粘合剂中存在相对少或没有催化剂,湿固化聚氨酯预聚物粘合剂的用途满足长期储存稳定性以及在室温或轻微升高的温度下具有长加工寿命。
令人惊讶地发现本发明方法还导致热成型硬质聚氨酯泡沫的有利变硬。此外,本发明方法产生更快的脱模时间,因此使待使用的生产单元更具有成本效益。
下面通过实施例阐述本发明。
原料
多元醇1:起始于丙二醇制备且主要具有伯OH基团(组成:80%氧化丙烯,20%氧化乙烯)的聚醚多元醇(OHN 30mg KOH/g)
多元醇2:甲基聚乙二醇(OHN 113mg KOH/g)
异氰酸酯:聚合的二异氰酸基二苯基甲烷(PMDI)
催化剂1:有机锡酯
催化剂2:硅酸钠M2O∶SiO2比:SiO2∶Na2O 3.3∶1
抑制剂1:二甘醇双氯甲酸酯(DIBIS)
抑制剂2:正磷酸,85%
实施例:
聚氨酯粘合剂的制备:
将搅拌罐中装入70重量份PMDI和0.01重量份抑制剂1,并将该初始进料加热至80℃,同时搅拌。向其中缓慢加入29.6重量份多元醇1和多元醇2(重量比1∶2)的混合物。加入结束后搅拌另外120分钟,冷却至25℃,并排出。所得聚氨酯预聚物的NCO含量和粘度分别为21%和500mPas。随后加入0.02重量份抑制剂1和0.03重量份抑制剂2。
由聚氨酯粘合剂制备泡沫
将91.8重量份聚氨酯粘合剂和8.2重量份催化剂2水溶液(50%浓度)相互混合,并使反应混合物反应以得到聚氨酯泡沫。由此得到开孔和粗孔泡沫。
比较例:
聚氨酯粘合剂的制备:
进行实施例的程序,其中还加入0.2份催化剂1。
由聚氨酯粘合剂制备泡沫:
将91.8重量份根据比较例的聚氨酯粘合剂与8.2重量份水混合,并使反应混合物反应以得到聚氨酯泡沫。由此得到开孔和粗孔泡沫。
用于根据实施例和比较例制备聚氨酯泡沫的反应混合物的反应性和在55℃下在水浴下搅拌2小时以后根据实施例和比较例的聚氨酯粘合剂的粘度和粘度提高列于表1中:
表1:
该表显示该实施例的泡沫以及所需开孔和粗孔结构具有更快的反应速率。延长的起动时间和具有较短上升时间的设置时间导致改善的加工性能和更快的循环时间。此外,本发明聚氨酯粘合剂在应用前条件下显示出显著更好的稳定性,称为侧倾稳定性(roll stability),通过在55℃下在水浴下搅拌2小时模拟它。
通过湿固化聚氨酯粘合剂并使用本发明催化剂(实施例)以及根据比较例催化,生产车顶衬里。为此所用的层顺序如下:
1.无纺布190g/m2 Fytisa(1.1mm)
2.磨砂玻璃纤维100+/-10g/m2 Owens Corning Vetrotex
3.水25g/m2
4.粘合剂100g/m2
5.可热成型硬质聚氨酯泡沫RG20Elastofiex E 3943/120 10.6mm
6.粘合剂100g/m2
7.水25g/m2
8.磨砂玻璃纤维100+/-10g/m2 Owens Corning Vetrotex
9.在非面中具有LDPE的无纺布PET(45g/m2 PET纤维+15g/m2LDPE)Fytisa(0.25mm)
在模具中在130℃下将材料压缩模塑至12mm的厚度,并根据ASTMD790 J949测定所生产的车顶衬里的硬度。表2显示所生产的车顶衬里的机械性能:
表2
根据实施例的完全车顶衬里具有比来自比较试验的车顶衬里更大的硬度(9.6N/mm2)和弹性模量(5881kPa)。
Claims (25)
1.一种通过引入可热成型硬质聚氨酯泡沫并将它粘附结合在衬里材料上而由可热成型硬质聚氨酯泡沫和衬里材料生产复合部件的方法,所用粘合剂为通过与催化剂水溶液接触而固化的湿固化聚氨酯粘合剂,所用催化剂水溶液为碱金属硅酸盐水溶液。
2.根据权利要求1的方法,其中所用碱金属硅酸盐为硅酸钠。
3.根据权利要求1的方法,其中所述碱金属硅酸盐水溶液包含0.1-80重量%的碱金属硅酸盐。
4.根据权利要求2的方法,其中所述碱金属硅酸盐水溶液包含0.1-80重量%的碱金属硅酸盐。
5.根据权利要求1-4中任一项的方法,其中所述催化剂水溶液以10-150g/m2可热成型硬质聚氨酯泡沫的量应用。
6.根据权利要求1-4中任一项的方法,其中湿固化聚氨酯粘合剂包含基于湿固化聚氨酯粘合剂的总重量为至少80重量%的异氰酸酯封端预聚物,所述预聚物通过将化学计量过量的芳族异氰酸酯与具有至少两个异氰酸酯反应性基团的相对高分子量化合物,和任选的仅具有一个异氰酸酯反应性基团的化合物,以及任选的增链剂和/或交联剂混合而得到。
7.根据权利要求5的方法,其中湿固化聚氨酯粘合剂包含基于湿固化聚氨酯粘合剂的总重量为至少80重量%的异氰酸酯封端预聚物,所述预聚物通过将化学计量过量的芳族异氰酸酯与具有至少两个异氰酸酯反应性基团的相对高分子量化合物,和任选的仅具有一个异氰酸酯反应性基团的化合物,以及任选的增链剂和/或交联剂混合而得到。
8.根据权利要求6的方法,其中所述异氰酸酯封端预聚物具有5-30重量%的NCO含量。
9.根据权利要求1-4中任一项的方法,其中除碱金属硅酸盐水溶液外,没有使用其它催化剂以固化粘合剂。
10.根据权利要求5的方法,其中除碱金属硅酸盐水溶液外,没有使用其它催化剂以固化粘合剂。
11.根据权利要求6的方法,其中除碱金属硅酸盐水溶液外,没有使用其它催化剂以固化粘合剂。
12.根据权利要求8的方法,其中除碱金属硅酸盐水溶液外,没有使用其它催化剂以固化粘合剂。
13.根据权利要求1-4中任一项的方法,其中湿固化聚氨酯粘合剂以20-300g/m2可热成型硬质聚氨酯泡沫的量使用。
14.根据权利要求5的方法,其中湿固化聚氨酯粘合剂以20-300g/m2可热成型硬质聚氨酯泡沫的量使用。
15.根据权利要求6的方法,其中湿固化聚氨酯粘合剂以20-300g/m2可热成型硬质聚氨酯泡沫的量使用。
16.根据权利要求8的方法,其中湿固化聚氨酯粘合剂以20-300g/m2可热成型硬质聚氨酯泡沫的量使用。
17.根据权利要求9的方法,其中湿固化聚氨酯粘合剂以20-300g/m2可热成型硬质聚氨酯泡沫的量使用。
18.根据权利要求1-4中任一项的方法,其中可热成型聚氨酯泡沫、衬里材料和湿固化聚氨酯粘合剂在模具温度为60-180℃的模具中结合。
19.根据权利要求5的方法,其中可热成型聚氨酯泡沫、衬里材料和湿固化聚氨酯粘合剂在模具温度为60-180℃的模具中结合。
20.根据权利要求6的方法,其中可热成型聚氨酯泡沫、衬里材料和湿固化聚氨酯粘合剂在模具温度为60-180℃的模具中结合。
21.根据权利要求8的方法,其中可热成型聚氨酯泡沫、衬里材料和湿固化聚氨酯粘合剂在模具温度为60-180℃的模具中结合。
22.根据权利要求9的方法,其中可热成型聚氨酯泡沫、衬里材料和湿固化聚氨酯粘合剂在模具温度为60-180℃的模具中结合。
23.根据权利要求13的方法,其中可热成型聚氨酯泡沫、衬里材料和湿固化聚氨酯粘合剂在模具温度为60-180℃的模具中结合。
24.一种可通过根据权利要求1-23中任一项的方法得到的复合部件。
25.根据权利要求24的复合部件在车辆中的用途。
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US9272489B2 (en) * | 2011-11-28 | 2016-03-01 | Basf Se | Composite parts comprising plastically deformable rigid polyurethane foam, adhesive and covering material |
EP2597107A1 (de) * | 2011-11-28 | 2013-05-29 | Basf Se | Verbundteile enthaltend plastisch verformbaren Polyurethanhartschaumstoff, Klebstoff und Abdeckmaterial |
EP2700669A1 (de) * | 2012-08-21 | 2014-02-26 | Basf Se | Plastisch verformbarer Polyurethan-Polyamid-Hartschaumstoff |
CN113292930A (zh) * | 2014-03-12 | 2021-08-24 | 重庆利尔达科技开发有限公司 | 一种用于环保复合树脂、胶粘剂或涂料的组合物及其制备方法 |
CA3086249A1 (en) * | 2017-12-21 | 2019-06-27 | Basf Se | Method for producing polyurethane sandwich moldings |
EP3931233A1 (de) | 2019-02-26 | 2022-01-05 | Covestro Intellectual Property GmbH & Co. KG | Zwei- oder mehrschichtaufbauten und verfahren zu deren herstellung |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US3975316A (en) * | 1972-05-04 | 1976-08-17 | Thiokol Corporation | Curing liquid polyurethane prepolymers |
FR2654385A1 (fr) * | 1989-11-10 | 1991-05-17 | Nat Starch Chem Sa | Procede de production d'articles isolants rigides a l'aide d'un adhesif de polyurethanne. |
Family Cites Families (2)
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JP2001047544A (ja) * | 1999-08-04 | 2001-02-20 | Sumitomo Bayer Urethane Co Ltd | サンドウィッチ構造を有する自動車内装材の製造方法 |
BRPI0409968A (pt) * | 2003-05-15 | 2006-04-25 | Huntsman Int Llc | adesivo baseado em poliisocianato, mistura de reação para preparar um adesivo baseado em poliisocianato, e, painel em sanduìche |
-
2010
- 2010-06-02 CN CN201080024562.XA patent/CN102459385B/zh active Active
- 2010-06-02 WO PCT/EP2010/057675 patent/WO2010139708A1/de active Application Filing
- 2010-06-02 JP JP2012513603A patent/JP2012528743A/ja not_active Withdrawn
- 2010-06-02 EP EP10724451.9A patent/EP2438101B1/de active Active
- 2010-06-02 KR KR1020127000369A patent/KR20120061046A/ko not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3975316A (en) * | 1972-05-04 | 1976-08-17 | Thiokol Corporation | Curing liquid polyurethane prepolymers |
FR2654385A1 (fr) * | 1989-11-10 | 1991-05-17 | Nat Starch Chem Sa | Procede de production d'articles isolants rigides a l'aide d'un adhesif de polyurethanne. |
Also Published As
Publication number | Publication date |
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KR20120061046A (ko) | 2012-06-12 |
WO2010139708A1 (de) | 2010-12-09 |
EP2438101A1 (de) | 2012-04-11 |
CN102459385A (zh) | 2012-05-16 |
EP2438101B1 (de) | 2013-05-15 |
JP2012528743A (ja) | 2012-11-15 |
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