CN1421313A - 金属-聚氨酯层压品 - Google Patents
金属-聚氨酯层压品 Download PDFInfo
- Publication number
- CN1421313A CN1421313A CN02152796A CN02152796A CN1421313A CN 1421313 A CN1421313 A CN 1421313A CN 02152796 A CN02152796 A CN 02152796A CN 02152796 A CN02152796 A CN 02152796A CN 1421313 A CN1421313 A CN 1421313A
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- Prior art keywords
- reactant mixture
- metal
- laminate
- thickness
- metal level
- Prior art date
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Images
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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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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Landscapes
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- Laminated Bodies (AREA)
Abstract
本发明涉及包含金属和密实或蜂窝聚氨酯树脂的层压品,用于生产这些层压品的工艺,和包括这些层压品的模塑制品的生产。
Description
技术领域
本发明提供由金属和密实或蜂窝聚氨酯树脂组成的层压品及其生产工艺。
背景技术
由钢和聚丙烯组成的层压品已用于构造汽车,例如,用于挡泥板托、顶板、仪表板、外壳部件、罩等。在此,由于热塑性内衬材料,耐热性在许多情况下仍然不充分;另外,为了获得足够强的聚丙烯-钢结合,需要显著的费用。
WO 98/21029公开了用于造船的层压夹层元件,其中两块钢板通过聚氨酯弹性体核粘结在一起。该钢板具有6-25mm厚度;聚氨酯弹性体具有的拉伸强度为20-55MPa,弯曲模量为2-104MPa,伸长率为100-800%和硬度为Shore 70A至Shore 80D。
WO 99/64233公开了具有以下层结构的层压板:金属(2-20mm)/密实聚异氰酸酯加聚产品(10-100mm)/金属(2-20mm)。该聚异氰酸酯加聚产品在-45℃至+50℃的温度范围内的弹性模量>275MPa,金属粘附性>4MPa,在-45℃至+50℃的温度范围内的伸长率>30%,拉伸强度>20MPa和压缩强度>20MPa。
US 6,050,208公开了用于造船的层压板,其中弹性体层的弹性模量≥250MPa。
这些层压品不适用于建造非海运工具。尤其是,它们不能通过深拉进行处理,且金属和弹性体之间的粘附性仍不足。
发明内容
本发明涉及具有至少一个复合层的层压板,该复合层包括以下顺序的层:
B1)金属层,0.05-1.0mm厚,
A)聚氨酯树脂层,0.05-10mm厚,和
B2)金属层,0.05-1.0mm厚。
这些层压板是可模压的,即能够深拉。
本发明也涉及用于生产这些层压板的工艺,其中A)具有厚度0.05-10mm的聚氨酯树脂层位于两个金属层B1)和B2)之间,其中每个金属层具有厚度0.05-1.0mm。生产这些层压板的任何工艺都导致与上述相同的材料顺序。
一种工艺包括:
(1)将反应混合物施用到两个金属层B1)和B2)之间,其中每个金属层具有所需厚度,
和
(2)将反应混合物固化形成聚氨酯树脂层,这样形成层压品。
所得层压品中的聚氨酯树脂层如上所述优选具有厚度0.05-10mm。
另一工艺包括:
(1)将反应混合物施用到特征在于厚度为0.05-1.0mm的第一金属层B1)上,
(2)将第二金属层B2)放在该反应混合物上,其中金属层B2)具有厚度0.05-1.0mm,
和
(3)固化该反应混合物,这样形成层压品。
在该实施方案中,所得层压品中的聚氨酯树脂层也如上所述优选具有厚度0.05-10mm。
形成聚氨酯树脂的优选的反应混合物包含:
a)聚异氰酸酯组分,
b)多元醇组分,
和任选地,一种或多种:
c)选自交联剂、扩链剂及其混合物的组分,
d)催化剂,
e)发泡剂
f)选自填料和增强材料的化合物,
和
g)辅助物质和添加剂。
本发明也涉及一种生产适用于汽车和/或飞机建造的模塑制品的工艺。该工艺是一种真空成型工艺,其中金属层位于模具的内部之上并在模具内的位置上真空成型,该衬里模具填充有形成聚氨酯树脂的反应混合物,随后固化,并从模具中移出模塑制品。
层压板的外层B1)和B2)优选包含相同的金属材料且优选具有相同的厚度。如果外层B1)和B2)包含相同的金属材料,它们的表面可任选地进行不同改性。适用作B1)和/或B2)的金属可以是常用于建造空运、水运或地面运输工具,例如,用于车体片材的任何金属材料。尤其是,金属如钢、铝、镁和普通合金和这些金属的改性体,包括本领域熟练技术人员已知的所有种类的表面改性体(表面涂层)。这些表面涂层通过例如阳极化、磷化、铬化、镀锌而制成,且为本领域熟练技术人员所已知。优选的金属是车体钢。可以使用未改性和表面改性的车体钢。表面改性可通过用无机试剂通过例如阳极化、磷化、铬化、镀锌,或用有机试剂环氧树脂或聚氨酯树脂处理而实现。
该层压品的内层A)包含密实和/或蜂窝聚氨酯树脂。适用于本发明的聚氨酯树脂是通过以下物质的反应而制成的那些:a)聚异氰酸酯组分,b)多元醇组分,和任选地,c)一种或多种交联剂和/或扩链剂,任选地,d)一种或多种催化剂,任选地,e)发泡剂,优选水作为发泡剂,任选地,f)一种或多种填料和增强材料,和任选地g)其它的辅助物质和添加剂。优选的是,本发明层压板的聚氨酯树脂层具有厚度0.05-10mm。
适用作本发明起始组分a)的化合物包括脂族、环脂族、芳脂族、芳族和杂环聚异氰酸酯,例如,由W.Siefken描述于Justus LiebigsAnnalen der Chemie,562,75-136页,例如,对应于下式的那些:
Q(NCO)n,
其中:
n等于2-4的数,优选2,
和
Q表示具有2-18个碳原子、优选具有6-10个碳原子的脂族烃基团,具有4-15个碳原子、优选具有5-10个C原子环脂族烃基团,具有6-15个碳原子、优选具有6-13个碳原子的芳香烃基团,或具有8-15个碳原子、优选具有8-13个碳原子的芳脂族烃基团。
优选使用技术上易得的聚异氰酸酯,例如,甲苯2,4-和2,6-二异氰酸酯和这些异构体(TDI)的任何混合物,通过苯胺-甲醛缩合并随后光气化而制成的聚苯基聚亚甲基聚异氰酸酯(“粗MDI”),二苯基甲烷二异氰酸酯系列的高级芳族异氰酸酯(pMDI型)和包含碳二亚胺基团、氨基甲酸乙酯基团、脲基甲酸酯基团、异氰尿酸酯基团、脲基团或缩二脲基团的聚异氰酸酯(“改性的聚异氰酸酯”),尤其是衍生自甲苯2,4-和2,6-二异氰酸酯或衍生自二苯基甲烷4,4’-和/或2,4’-二异氰酸酯的改性聚异氰酸酯。萘1,5-二异氰酸酯或上述聚异氰酸酯的混合物也是合适的。粗MDI特别优选用于本发明。
包含至少两个对异氰酸酯基团具有反应性的H(即氢)原子的多元醇适用作本发明中的多元醇组分b)。优选使用聚酯多元醇和聚醚多元醇,其中聚醚多元醇是尤其优选的。这些聚醚多元醇可通过已知的工艺,例如,通过氧化烯在催化剂碱氢氧化物或碱醇盐存在下的阴离子聚合反应并加入至少一种包含键接的反应性氢原子的起始物分子,或通过氧化烯在Lewis酸如五氯化锑或三氟化硼醚合物存在下的阳离子聚合反应而制成。合适的氧化烯在亚烷基基团中包含例如2-4个碳原子。一些例子是四氢呋喃,1,3-环丙烷,1,2-或2,3-亚丁基氧;优选使用环氧乙烷和/或1,2-环氧丙烷。氧化烯可单独或者相互顺序地或作为混合物使用。优选的混合物由1,2-环氧丙烷和环氧乙烷组成,其中环氧乙烷以10-50%的量用作环氧乙烷末端嵌段(即“EO封端”),这样所得多元醇具有超过的70%伯OH末端基团。起始物分子的合适例子包括水或多元醇,如乙二醇、1,2-丙烷二醇和1,3-丙烷二醇、二甘醇、二丙二醇、1,4-丁二醇、甘油、三羟甲基丙烷、季戊四醇、山梨醇、蔗糖等。合适的聚醚多元醇,优选聚氧丙烯-聚氧乙烯多元醇具有官能度2-8和数均分子量800-18,000g/mol,优选1,000-4,000g/mol。
合适的聚酯多元醇可例如由具有2-12个碳原子的有机二羧酸、优选具有4-6个碳原子的脂族二羧酸,和具有2-12个碳原子、优选2个碳原子的多元醇,优选二醇制成。合适的二羧酸的例子是:琥珀酸,戊二酸,己二酸,辛二酸,壬二酸,癸二酸,癸烷二羧酸,马来酸,富马酸,邻苯二甲酸,间苯二甲酸和对苯二甲酸。在此,二羧酸可单独或以相互的混合物使用。除了游离的二羧酸,可以使用相应的二羧酸衍生物,例如,具有1-4个碳原子的醇的二羧酸单-和/或二酯,或二羧酸酐。优选使用具有比例例如为20-35/35-50/20-32重量份的琥珀酸、戊二酸和己二酸的二羧酸混合物,尤其是己二酸。二元和多元醇的例子是乙二醇、二甘醇、1,2-和1,3-丙二醇、二丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、1,10-癸二醇、甘油、三羟甲基丙烷和季戊四醇。优选用作二元和多元醇的化合物是1,2-乙二醇、二甘醇、1,4-丁二醇、1,6-己二醇、甘油、三羟甲基丙烷或至少两个上述二醇的混合物,尤其是乙二醇、1,5-丁二醇和1,6-己二醇的混合物,甘油和/或三羟甲基丙烷是优选的。也可使用由内酯,例如,ε-己内酯,或由羟基羧酸,例如,ω-羟基己酸和羟基乙酸得到的聚酯多元醇。
为了制备聚酯多元醇,有机聚羧酸和/或其衍生物与多元醇,有利地是以摩尔比1∶1-1∶1.8,优选1∶1.05-1∶1.2一起缩聚。所得聚酯多元醇的官能度优选为2-3,更优选2-2.6,且数均分子量为400-6,000,优选800-3,500。
也可提及的合适的聚酯多元醇包括包含羟基基团的聚碳酸酯。包含羟基基团的合适的聚碳酸酯是本身已知的种类,例如可通过二醇如1,2-丙二醇、1,4-丁二醇、1,6-己二醇、二甘醇、三氧基乙二醇和/或四氧基乙二醇与碳酸二芳基酯例如碳酸二苯酯或光气的反应而制成。
为了生产按照本发明的PU弹性体,除了多元醇组分,即上述的组分b),可以使用一种或多种低分子量二官能扩链剂、一种或多种低-分子量(优选三-或四官能)交联剂或扩链剂和交联剂的混合物作为组分c)。
这些扩链剂和交联剂即组分c)是为了改变PU弹性体的力学性能、尤其是硬度而包括在反应混合物中的。合适的扩链剂,例如烷烃二醇、二亚烷基二醇和聚亚烷基多元醇,和交联剂,例如三-或四元醇和具有官能度3-4的低聚聚亚烷基多元醇(可以是例如环氧乙烷和/或环氧丙烷在具有高OH值的三羟甲基丙烷或甘油上的加成物)通常具有分子量<800,优选18-400和更优选60-300。优选用作扩链剂的化合物是具有2-12个碳原子、和优选2、4或6个碳原子的烷烃二醇,例如乙二醇、1,3-丙二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇,和尤其是1,4-丁二醇和具有4-8个碳原子的二亚烷基二醇例如二甘醇和二丙二醇以及聚氧亚烷基二醇。具有通常不超过12个碳原子的支链和/或不饱和烷烃二醇也是适用于组分c)的化合物。一些这样的化合物包括例如:1,2-丙二醇,2,2-二甲基-1,3-丙二醇,2-丁基-2-乙基-1,3-丙二醇,2-丁烯-1,4-二醇和2-丁炔-1,4-二醇,对苯二甲酸和具有2-4个碳原子的二醇的二酯,例如二(乙二醇)对苯二甲酸酯或二(1,4-丁二醇)对苯二甲酸酯,对苯二酚或间苯二酚的羟基亚烷基醚,例如1,4-二(β-羟基乙基)对苯二酚或1,3-(β-羟基乙基)-间苯二酚,具有2-12个碳原子的烷醇胺,如乙醇胺、2-氨基丙醇胺和3-氨基-2,2-二甲基丙醇,N-烷基二烷醇胺,例如N-甲基-和N-乙基二乙醇胺,具有2-15个碳原子的(环)脂族二胺,如1,2-乙二胺、1,3-丙二胺,1,4-丁二胺和1,6-六亚甲基二胺、异佛尔酮二胺,1,4-环六亚甲基-二胺和4,4’-二氨基二环己基甲烷,在N-烷基基团中具有1-20个碳原子、优选1-4个碳原子的也可在芳环上被烷基基团取代的N-烷基-、N,N’-二烷基-取代的-和芳族二胺,如N,N’-二乙基-、N,N’-二-仲戊基-、N,N’-二-仲己基-,N,N’-二-仲癸基-和N,N’-二环己基、对-或间-苯二胺、N,N’-二甲基-、N,N’-二乙基-、N,N’-二异丙基-、N,N’-二-仲丁基-、N,N’-二环己基-4,4’-二氨基-二苯基甲烷、N,N’-二-仲丁基联苯胺、亚甲基二(4-氨基-3-苯甲酸,甲基酯)、2,4-氯-4,4’-二氨基二苯基甲烷、2,4-和2,6-甲苯二胺。
构成组分c)的任何化合物可以混合物形式或单独使用。也可使用一种或多种扩链剂和一种或多种交联剂的混合物。
为了调节PU弹性体的硬度,组成组分b)和c)可以较宽比例变化。一般来说,PU弹性体的硬度和刚度随着组分c)在反应混合物中的含量的增加而增加。
根据所需性能例如粘附、深拉质量、耐热性等,组成组分b)和c)的所需量可容易地由实验确定。有利的是使用1-100重量份、优选3-50重量份的扩链剂和/或交联剂c),基于100重量份的较高分子化合物b)。
组分b)和c)还优选选择使得它们共同具有OH值为100-500mgKOH/g和官能度为2-8。
聚氨酯化学领域已知的催化剂可用作组分d)。合适的催化剂的一些例子包括催化剂例如叔胺,如三乙基胺,三丁基胺,N-甲基吗啉,N-乙基吗啉,N,N,N’N’-四甲基乙二胺,五甲基二乙三胺和高级同系物(例如,描述于DE-OS 26 24 527和26 24 528),1,4-二氮杂双环[2.2.2]辛烷,N-甲基-N’-二甲基氨基乙基-哌嗪,二(二甲基氨基烷基)哌嗪(例如,描述于DE-OS 26 36 787),N,N-二甲基苄胺,N,N-二甲基-环己基胺,N,N-二乙基苄胺,己二酸二(N,N-二乙基氨基乙基)酯,N,N,N’,N’-四甲基-1,3-丁二胺,N,N-二甲基-β-苯基乙基胺,二(二甲基氨基丙基)脲,1,2-二甲基咪唑,2-甲基咪唑,单环和二环脒(例如,描述于DE-OS 17 20 633),二(二烷基氨基)烷基醚(例如,描述于在此将其作为参考并入本发明的U.S.专利3,330,782,DE-AS 10 30 558,DE-OS 18 04 361和26 18 280)以及例如描述于DE-OS 25 23 633和27 32 292的包含酰胺基团(优选甲酰胺基团)的叔胺。本身已知的得自仲胺如二甲基胺,和得自醛、优选甲醛,或得自酮如丙酮、甲基乙基酮或环己酮和得自酚类如苯酚、壬基苯酚或双酚的Mannich碱也适用作本发明的催化剂。包含对异氰酸酯基团具有活性的氢原子的合适的叔胺催化剂包括例如三乙醇胺,三异丙醇胺,N-甲基二乙醇胺,N-乙基二乙醇胺,N,N-二甲基乙醇胺,它们与氧化烯如环氧丙烷和/或环氧乙烷的反应产物,以及例如描述于DE-OS 27 32 292的仲-叔胺。例如描述于U.S.专利3620 984(在此将其作为参考并入本发明)的包含碳-硅键的硅胺也可用作催化剂。这些化合物包括例如2,2,4-三甲基-2-硅吗啉和1,3-二乙基氨基甲基四甲基二硅氧烷。另外合适的是含氮碱如四烷基氢氧化铵,以及碱氢氧化物如氢氧化钠,碱性酚盐如苯酚钠,或碱性醇盐如甲醇钠。六氢三嗪也可用作催化剂(参见DE-OS 17 69 043)。NCO基团和Zerewitinoff活性氢原子之间的反应也极大地被内酰胺和氮杂内酰胺加速,在开始时形成内酰胺和包含酸氢的化合物之间的缔合物。这些缔合物和其催化作用描述于例如DE-OS 20 62 286、20 62 289、21 17 576、21 29 198、23 30 175和23 30 211。根据本发明,有机金属化合物也可用作催化剂。有机锡化合物是本发明优选的催化剂。除了含硫化合物如硫醇二-正辛基锡(例如描述于U.S.专利3,645,927,在此将其作为参考并入本发明),合适的有机锡化合物优选包括羧酸的锡(II)盐,如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II),和锡(IV)化合物例如***、二丁锡化二氯、二乙酸二丁锡、二月桂酸二丁锡、马来酸二丁锡或二乙酸二辛锡。
所有的上述催化剂当然可作为混合物使用。在本发明中特别有价值的是有机金属化合物和脒、氨基吡啶或肼基吡啶的组合(例如描述于DE-OS 24 34 185、26 01 082和26 03 834)。
适用于本发明的催化剂的其它例子以及该催化剂的作用模式细节描述于:R.Vieweg,A.Hchtlen(编辑)“Kunststoff-Handbuch”,VII卷,Carl Hanser Verlag,Munich 1966,96-102页。
催化剂或催化剂组合的用量一般为约0.001-10wt.%,优选0.01-1wt.%,基于包含至少两个对异氰酸酯具有反应性的氢原子的化合物的总量。
根据本发明,密实聚氨酯树脂可在不存在水分和起物理或化学作用的发泡剂的情况下制成。为了生产蜂窝,优选微蜂窝聚氨酯树脂,所用的发泡剂e)优选为水。发泡剂与有机聚异氰酸酯a)或与包含异氰酸酯基团的预聚物原位反应形成二氧化碳和氨基基团,并由于它们的原因继续与其它的异氰酸酯基团反应形成脲基团,从而用作扩链剂。如果将水另外加入聚氨酯配方中以生产具有所需密度的聚氨酯树脂,其用量一般为0.01-2.0wt%,优选0.2-1.2wt.%,基于组成组分b)和c)的总重。也可使用能产生均匀多沫泡沫的胺的二氧化碳盐,如碳酸盐或氨基甲酸盐(氨基甲酸的盐)。合适的胺的例子是氨基乙醇和短链聚醚多元胺。
填料和增强材料f)也可任选地加入到用于生产聚氨酯树脂的反应混合物中。合适的填料和增强材料的例子是含硅矿物如片材硅酸盐,如叶蛇纹石、蛇纹石、角闪石、闪石、液状石蜡、滑石;金属氧化物,如高岭土、氧化铝、氧化钛、钛酸盐和氧化铁;金属盐如白垩、重晶石和无机颜料,如硫化镉、硫化锌,以及玻璃,石棉粉等。优选使用天然和合成纤维矿物如石棉、硅灰石,尤其是可任选地施胶的具有各种长度的玻璃纤维。填料可单独或混合使用。填料(如果存在)有利地是以最高50wt.%,优选最高30wt.%的量加入反应混合物,基于组分b)和c)的总重。
添加剂g)也可任选地加入用于生产聚氨酯树脂的反应混合物中。可以提及的这些添加剂的一些例子是表面活性添加剂,如乳化剂,泡沫稳定剂,单元调节剂(cell regulator),阻燃剂,成核剂,氧化抑制剂和热稳定剂,稳定剂,润滑剂和脱模剂,染料,分散剂和颜料。合适的乳化剂是例如硫酸盐化蓖麻油的钠盐或脂肪酸与胺的盐,如油酸二乙基胺或硬脂酸二乙醇胺。磺酸(如十二烷基苯磺酸或二萘基甲烷-二磺酸)或脂肪酸(如蓖麻油酸)或聚合脂肪酸的碱金属盐或铵盐也可伴随用作表面活性添加剂。聚醚硅氧烷,尤其是水溶性代表物是最合适的泡沫稳定剂。这些化合物一般构成使得环氧乙烷和环氧丙烷的共聚物键接到聚二甲基硅氧烷基团上。这些泡沫稳定剂例如描述于U.S.专利2,834,748、2,917,480和3,629,308,在此将其作为参考并入本发明。特别有价值的是例如描述于DE-OS 25 58 523的通过脲基甲酸酯基团多支化的聚硅氧烷-聚氧化烯共聚物。其它的有机聚硅氧烷,乙氧基化烷基酚,乙氧基化脂肪醇,石蜡油,蓖麻酯,Turkey红油和花生油和单元调节剂如石蜡,脂肪醇和二甲基聚硅氧烷也是合适的。另外,具有聚氧化烯基团和氟烷烃基团作为侧基的低聚聚丙烯酸酯适用于改进和/或稳定乳化作用、填料的分散和单元结构。表面活性物质的用量通常是0.01-5重量份,基于100重量份的多元醇b)。也可加入反应抑制剂例如酸反应物质如氢氯酸,或有机酸和酰卤,本身也是已知的单元调节剂如石蜡或脂肪醇或二甲基聚硅氧烷,以及颜料或染料或本身已知的阻燃剂,例如,磷酸三(氯乙基)酯,磷酸三甲酚酯或磷酸铵和聚磷酸铵,以及抗老化和风化作用的稳定剂,增塑剂和抗真菌和抗细菌物质。合适的抗氧化热稳定剂的例子是本领域技术人员已知的二苯基胺、BHT、HALS、苯并***等类型的化合物。这些化合物例如得自Ciba和Goldschmidt公司。
可任选地用于本发明的表面活性添加剂和泡沫稳定剂,和单元调节剂,反应抑制剂,稳定剂,阻燃剂,增塑剂,染料和填料以及抗真菌和抗细菌物质的其它例子,以及涉及这些添加剂的施用方法和作用模式的细节描述于R.Vieweg,A.Hchtlen(编辑)“Kunststoff-Handbuch”,VII卷,Carl Hanser Verlag,Munich 1966,103-113页。
根据本发明的聚氨酯树脂可通过各种程序制成。因此,例如使多元醇b)和任选地扩链剂和/或交联剂c)、任选地催化剂d)、任选地e)水、任选地f)填料和增强材料和/或任选地g)辅助物质和添加剂的混合物与有机聚异氰酸酯a)反应。在该工艺的另一实施方案中,使通过聚异氰酸酯组分a)与多元醇组分b)反应制成的包含异氰酸酯基团的预聚物与扩链剂和/或交联剂c),或与给定比例的多元醇组分b)和扩链剂和/或交联剂c)的混合物,或给定比例的多元醇组分b)、扩链剂和/或交联剂c)和水的混合物,或优选与扩链剂和/或交联剂c)和水的混合物反应。
根据本发明的聚氨酯树脂可通过描述于文献的工艺,例如,通过一次注射工艺或预聚物工艺而制成,其中利用原则上为本领域技术人员所已知的混合设备。它们优选通过一次注射工艺制成。
各组分反应的量使得聚异氰酸酯a)的NCO基团与组分b)和c)的对异氰酸酯基团具有反应性的氢原子和任选的e)水的总和的当量比率是0.5∶1-2∶1,优选0.8∶1-1.2∶1和尤其是0.8∶1-0.9∶1。
如果它们在没有填料和增强材料的情况下生产,按照本发明的聚氨酯树脂平均密度为0.3-1.1g/cm3。较高的密度例如1.1-1.3g/cm3可通过在聚氨酯形成反应混合物中使用填料和增强材料而实现。所得聚氨酯树脂具有弹性模量<250MPa(20℃)。它们具有耐热性>200℃;即在200℃下回火30分钟时,它们的质量损失<1wt.%。可以实现低于0.3g/cm3的密度,但发现它们不适合预期的用途。
按照本发明的层压板可通过将聚氨酯反应混合物放在两金属层B1)和B2)之间并在此对其进行固化而制成,其中每个金属层的厚度是0.05-1.0mm。为此,例如,顶层B1)和B2)可在模具中以所需距离间隔地或利用间隔物和填充有反应混合物的间隙而放置。在该工艺的连续变型中,将反应混合物连续施用到两个连续导向的金属片材之间。所得层压板随后经过辊,这样被调节至所需厚度。或者,反应混合物可首先施用到金属层B1)上,并随后覆盖以层B2)。在所有的生产方法中,反应混合物在放置或施用到两个金属层B1)和B2)之间之后固化,并从而粘结到金属层上。聚氨酯树脂层在层压板中的厚度为0.05-10mm。
为了提高聚氨酯树脂和金属层之间的粘附性,金属层的接触表面可用粘附性底漆预处理。合适的基于聚氨酯和环氧化物的底漆原则上是已知的。无机底漆如,例如原硅酸钠(水玻璃),或例如水分散体形式的无机底漆和有机聚合物的混合物也是合适的。
根据本发明的层压品优选用于汽车建造和飞机建造,例如,用于生产车体部件、仪表板、外壳部件、罩、顶板等。
根据本发明的层压品与完全由金属制成的结构部件或与已有技术的钢-塑料层压品相比产生显著的优点。即,它们的优点是伴随相等或更大刚度具有较低重量(尤其是其中施用蜂窝聚氨酯树脂时)。重量下降伴随较低的燃料消耗,并因此增加节约资源。它们具有比已有技术的钢-塑料层压品明显更好的耐温度性。由于所用的聚氨酯树脂具有弹性模量<250MPa,按照本发明的层压品有利地通过深拉进行处理,这是三维制品如汽车部件(罩等)所必需的。另外,按照本发明的层压品与纯金属部件或包含较高弹性模量塑料的钢-塑料层压品相比具有较好的吸声性能。与以前在文献中描述的用于造船的钢层压品相比,按照本发明的层压品具有提高的深拉质量,即没有内聚破裂且在180°弯曲时没有从壁上脱离。
本发明由以下实施例进一步说明而无意于受限,除非另有所指,其中所有的分数和百分数都是重量计的。
附图说明
图1给出了通过在加热速率5K/min下对样品在氮气气氛下进行TGA分析而得到的图(实施例1)。
图2给出了通过在加热速率5K/min下对样品在氮气气氛下进行DTA分析而得到的图(实施例2)。
具体实施方式
实施例1:层压品的生产:
为了生产层压品,使用以下聚氨酯反应体系:
多元醇配方(组分A):
70.30重量份聚醚多元醇,它起始自甘油,具有数均摩尔质量6011g/mol,包含82.3wt.%PO和17.7wt.%末端EO嵌段,
20.00重量份聚氧丙烯多元醇,起始自三羟甲基丙烷,具有数均摩尔质量306g/mol,
7.00重量份1,4-丁二醇,
2.00重量份能够引入的聚合催化剂(Bayfill添加剂VP.PU59IF08,Bayer AG)
多元醇配方具有OH值221。
异氰酸酯组分(组分B):
粗MDI,包含1-5wt.%2,4’-MDI,44-55wt.%4,4’-MDI和40-55%聚亚甲基聚(苯基异氰酸酯)。
组分A:组分B的发泡比率是100∶52份,对应于参考数(即异氰酸酯指数)100。
PU材料利用BD 1型(0.6×32)静电混合器混合。该设备具有喷嘴直径6mm;将加工材料在喷嘴排出之前剪切32次。在约600g/min的排出容量下,将包括加料和排出过程的注射时间限为10秒。
利用实验室试验,为上述处理设立以下反应时间:长丝拉伸时间3分钟,不剥落(tack-free)时间3.5分钟。
为了生产按照本发明的试验层压品(钢片材/PU/钢片材),使用电镀的锌涂覆钢片材,其中每个片材具有厚度0.25mm和尺寸约20cm×30cm。将这两个金属片材在一面上涂以常规的市售单组分底漆(VP13808,IGP GmbH,D-48249,Dülmen)。将金属片材放在70℃干燥炉中约15分钟以通风和烘烤底漆。将PU反应混合物冷却至室温并随后施用到金属片材之一的涂漆面上,并在施用之后,立即覆盖以第二金属片材。PU材料层厚度调节至1mm并将该层压品在室温下储存约15分钟,随后在约70℃下储存约30分钟。
按照DIN EN 1464测定的所得层压品的耐剥离性是45.6N/cm。成型可加工性利用弯曲试验检查。为此,将层压品弯曲90°并随后再次弯回。没有观察到树脂从金属上脱离。
为了确立所用PU材料的力学和热力学数据,在实验室中生产出试验板。为此,将组分A和B以比率100∶52在合适的容器中称出并利用Pendraulik混合器在搅拌速度4200转/分钟下混合15秒。然后,将350g混合物放在一个预热至70℃的平整模具(具有尺寸200mm×200mm×10mm)中,闭合该模具并排气。在该混合物已放在模具中约5分钟时,可以释放成品板,其体密度是约875kg/m3。板在室温下储存24小时之后,确定以下力学和热性能:
DIN 527-1 | 在20℃下的耐撕裂性[N/mm2] | 7.87 |
DIN 527-1 | 在20℃下的撕裂伸长率[%] | 41.38 |
DIN 527-1 | 在20℃下的拉伸模量[N/mm2] | 119 |
DIN 53423 | 在20℃下的弯曲模量[N/mm2] | 61 |
DIN 53423 | 在80℃下的弯曲模量[N/mm2] | 7 |
DIN 53505 | 硬度[Shore D] | 52 |
PU材料的分解温度利用TGA(热重分析)进行热重确定。在加热速率20K/min下,在347℃下观察到分解开始,而在加热速率5K/min下,则为326℃。图1给出了通过在加热速率5K/min下对样品在氮气气氛下进行TGA分析而得到的图。
实施例2:层压品的生产:
为了生产层压品,使用以下聚氨酯反应体系:
多元醇配方(组分A):
69.30重量份的聚醚多元醇,起始自甘油,具有数均摩尔质量6011g/mol,包含82.3wt.%PO和17.7wt.%末端EO嵌段,
11.80重量份的聚氧丙烯多元醇,起始自三羟甲基丙烷,具有数均摩尔质量306g/mol,
10.00重量份乙二醇,
7.80重量份聚乙二醇,具有数均摩尔质量600g/mol,
0.05重量份二月桂酸二丁基锡,
16.70重量份硅灰石型填料,
多元醇配方具有OH值241。
异氰酸酯组分(组分B):
粗MDI,包含1-5wt.%2,4’-MDI,44-55wt.%4,4’-MDI和40-55%聚亚甲基聚(苯基异氰酸酯)。
组分A:组分B的发泡比率是100∶57份,对应于参考数(即异氰酸酯指数)100。
PU材料利用BD 1型(0.6×32)静电混合器混合。该设备具有喷嘴直径6mm;将加工材料在喷嘴排出之前剪切32次。在约600g/min的排出容量下,将包括加料和排出过程的注射时间限为10秒。
利用实验室试验,为上述处理设立以下反应时间:长丝拉伸时间3分钟,不剥落时间3.5分钟。
为了生产按照本发明的试验层压品(钢片材/PU/钢片材),使用电镀的锌涂覆钢片材,其中每个片材具有厚度0.25mm和尺寸约20cm×30cm。将这两个金属片材在一面上涂以常规的市售单组分底漆(VP13808,IGP GmbH,D-48249,Dülmen)。将金属片材放在70℃干燥炉中约15分钟以通风和烘烤底漆。将PU反应混合物冷却至室温并随后施用到金属片材之一的涂漆面上,并在施用之后,立即覆盖以第二金属片材。PU材料层厚度调节至1mm并将该层压品在室温下储存约15分钟,随后在约70℃下储存约30分钟。
按照DIN EN 14 64测定的所得层压品的耐剥离性是21.3N/cm。成型可加工性利用弯曲试验检查。为此,将层压品弯曲90°并随后再次弯回。没有观察到树脂从金属上脱离。
为了确立所用PU材料的力学和热力学数据,在实验室中生产出试验板。为此,将组分A和B以比率100∶52在合适的容器中称出并利用Pendraulik混合器在搅拌速度4200转/分钟下混合15秒。然后,将350g混合物放在一个预热至70℃的平整模具(具有尺寸200mm×200mm×10mm)中,闭合该模具并排气。在该混合物已放在模具中约5分钟时,可以释放成品板,其体密度是约875kg/m3。板在室温下储存24小时之后,确定以下力学和热性能:
DIN 527-1 | 在20℃下的耐撕裂性[N/mm2] | 7.75 |
DIN 527-1 | 在20℃下的撕裂伸长率[%] | 21.63 |
DIN 527-1 | 在20℃下的拉伸模量[N/mm2] | 222 |
DIN 53423 | 在20℃下的弯曲模量[N/mm2] | 180 |
DIN 53423 | 在80℃下的弯曲模量[N/mm2] | 12.2 |
PU材料的分解温度利用TGA(热重分析)进行热重确定。在加热速率20K/min下,在277℃下观察到分解开始,而在加热速率5K/min下,则为253℃。图2给出了通过在加热速率5K/min下对样品在氮气气氛下进行DTA分析而得到的图。
尽管本发明已在前述中为说明目的进行了详细描述,但可以理解,这些细节仅用于此目的且本领域技术人员可在不背离本发明的主旨和范围的情况下进行其中的变化,而本发明可由权利要求所限定。
Claims (5)
1.层压板,包括
B1)具有厚度0.05-1.0mm的第一金属层,
A)具有厚度0.05-10mm的聚氨酯树脂层,
和
B2)具有厚度0.05-1.0mm的第二金属层,
其中所述聚氨酯树脂层位于所述第一金属层和所述第二金属层之间。
2.根据权利要求1的层压板,其中所述聚氨酯树脂层的弹性模量小于250MPa。
3.一种生产在两层金属层B1)和B2)之间具有A)聚氨酯树脂层的层压板的工艺,该工艺包括
(1)将一种反应混合物施用到两金属层B1)和B2)之间,其中每个金属层具有厚度0.05-1.0mm,且反应混合物包含:
a)聚异氰酸酯组分,
b)多元醇组分,
和任选地,一种或多种
c)选自交联剂、扩链剂及其混合物的组分,
d)催化剂,
e)发泡剂,
f)选自填料和增强材料的化合物,
和
g)辅助物质和添加剂,
和
(2)固化所述反应混合物,由此形成层压板。
4.一种生产在两金属层B1)和B2)之间具有A)聚氨酯树脂层的层压板的工艺,所述工艺包括:
(1)将一种反应混合物施加到具有厚度0.05-1.0mm的第一金属层B1)上,其中所述反应混合物包含:
a)聚异氰酸酯组分,
b)多元醇组分,
和任选地,一种或多种
c)选自交联剂、扩链剂及其混合物的组分,
d)催化剂,
e)发泡剂,
f)选自填料和增强材料的化合物,
和
h)辅助物质和添加剂,
(2)将第二金属层B2)放在反应混合物上,其中第二金属层B2)具有厚度0.05-1.0mm,
和
(3)固化该反应混合物,由此形成层压板。
5.一种用于生产模塑制品的工艺,包括,将第一层材料定位在模具的一个内侧部分上,并将第二层材料定位在模具的另一内侧部分上,将材料层真空成型到模具中,闭合该模具,将模具填充以一种反应混合物,固化该反应混合物,打开模具,然后取出模塑部件,改进之处在于,第一层材料包含具有厚度0.05-1.0mm的金属,第二层材料包含具有厚度0.05-1.0mm的金属材料,且反应混合物包含一种能形成聚氨酯树脂的反应混合物。
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DE10158491.1 | 2001-11-28 | ||
DE10158491A DE10158491A1 (de) | 2001-11-28 | 2001-11-28 | Metall-Polyurethan-Laminate |
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CN1421313A true CN1421313A (zh) | 2003-06-04 |
Family
ID=7707336
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CN02152796A Pending CN1421313A (zh) | 2001-11-28 | 2002-11-28 | 金属-聚氨酯层压品 |
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US (1) | US20030104241A1 (zh) |
EP (1) | EP1316414A1 (zh) |
JP (1) | JP2003211584A (zh) |
KR (1) | KR20030043750A (zh) |
CN (1) | CN1421313A (zh) |
BR (1) | BR0204867A (zh) |
CA (1) | CA2412510A1 (zh) |
DE (1) | DE10158491A1 (zh) |
HK (1) | HK1054350A1 (zh) |
MX (1) | MXPA02011739A (zh) |
RU (1) | RU2002131903A (zh) |
ZA (1) | ZA200208648B (zh) |
Cited By (4)
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CN1921966B (zh) * | 2004-02-19 | 2010-09-01 | 阿赛洛法国公司 | 制造复合部件的方法 |
CN104582963A (zh) * | 2012-07-31 | 2015-04-29 | 陶氏环球技术有限责任公司 | 制造耐火泡沫隔热板的方法 |
CN106794668A (zh) * | 2014-07-31 | 2017-05-31 | 巴斯夫欧洲公司 | 用于建筑物立面的基于聚氨酯硬质泡沫的热复合*** |
CN112805151A (zh) * | 2018-09-14 | 2021-05-14 | 巴斯夫欧洲公司 | 由金属和由热塑性聚氨酯制成的聚合物中间层组成的层压制件 |
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DE10340541A1 (de) * | 2003-09-01 | 2005-03-24 | Basf Ag | Verbundelemente, insbesondere Karosserieteile |
US20070123681A1 (en) * | 2003-10-10 | 2007-05-31 | Nikko Materials Co., Ltd. | Resin composition |
JP2005120279A (ja) * | 2003-10-17 | 2005-05-12 | Daicel Chem Ind Ltd | ポリウレタンフォームの製造方法 |
CN1957029A (zh) * | 2004-05-19 | 2007-05-02 | 弗莱康股份有限公司 | 用于涂布和印刷基材的液体制剂 |
WO2009009207A2 (en) * | 2007-04-23 | 2009-01-15 | University Of Alabama At Birmingham | Thermoplastic composite/metal laminate structures and methods of making thermoplastic composite/metal laminate structures |
JP2009090522A (ja) * | 2007-10-05 | 2009-04-30 | Kobe Steel Ltd | 複合板および複合成形体 |
CN101332693B (zh) * | 2008-06-20 | 2012-04-18 | 上海力申科学仪器有限公司 | 内衬金属板的聚氨酯板及其发泡方法 |
US20110111192A1 (en) * | 2009-11-11 | 2011-05-12 | Juan Lloveras Calvo | Porcelain laminate and procedure for manufacturing it |
DE102014208415A1 (de) | 2014-05-06 | 2015-11-12 | Evonik Degussa Gmbh | Herstellung eines auf Stahl und Polyurethan basierenden Faserverbundbauteils |
DE102014208423A1 (de) | 2014-05-06 | 2015-11-12 | Evonik Degussa Gmbh | Herstellung eines auf Aluminium und Polyurethan basierenden Faserverbundbauteils |
DE102014108187A1 (de) * | 2014-06-11 | 2015-12-17 | Thyssenkrupp Steel Europe Ag | Fahrzeugaußenhautteil |
JP6080876B2 (ja) * | 2015-02-04 | 2017-02-15 | 日新製鋼株式会社 | 塗装金属素形材と化学繊維を含む布とが接合された複合体およびその製造方法 |
DE102015203128A1 (de) * | 2015-02-20 | 2016-08-25 | Thyssenkrupp Ag | Fahrwerkkomponente, Verfahren zu seiner Herstellung und Verwendung |
PL3749699T3 (pl) * | 2018-02-07 | 2022-07-04 | Basf Se | Elementy kompozytowe wykonane z materiału termoizolacyjnego, kleju i warstwy wierzchniej |
DE102018122898A1 (de) * | 2018-09-18 | 2020-03-19 | Kay-Johannes Wrede | Verfahren zum Auftragen und Formen einer formbaren Beschichtungsmasse |
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JPS5746237A (en) * | 1980-09-04 | 1982-03-16 | Hitachi Ltd | Screen for projection and its manufacture |
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DE19825085A1 (de) * | 1998-06-05 | 1999-12-09 | Basf Ag | Verbundelemente enthaltend kompakte Polyisocyanat-Polyadditionsprodukte |
US6177173B1 (en) * | 1998-07-01 | 2001-01-23 | 3M Innovative Properties Company | Damped laminates having welded through holes and/or edges with decreased spring back and improved fastener force retention and, a method of making |
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-
2001
- 2001-11-28 DE DE10158491A patent/DE10158491A1/de not_active Withdrawn
-
2002
- 2002-10-25 ZA ZA200208648A patent/ZA200208648B/xx unknown
- 2002-11-15 EP EP02025571A patent/EP1316414A1/de not_active Withdrawn
- 2002-11-22 CA CA002412510A patent/CA2412510A1/en not_active Abandoned
- 2002-11-22 US US10/302,569 patent/US20030104241A1/en not_active Abandoned
- 2002-11-26 BR BR0204867-1A patent/BR0204867A/pt not_active Application Discontinuation
- 2002-11-26 JP JP2002342267A patent/JP2003211584A/ja active Pending
- 2002-11-27 MX MXPA02011739A patent/MXPA02011739A/es unknown
- 2002-11-27 KR KR1020020074216A patent/KR20030043750A/ko not_active Application Discontinuation
- 2002-11-27 RU RU2002131903/04A patent/RU2002131903A/ru not_active Application Discontinuation
- 2002-11-28 CN CN02152796A patent/CN1421313A/zh active Pending
-
2003
- 2003-09-16 HK HK03106652.3A patent/HK1054350A1/zh unknown
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1921966B (zh) * | 2004-02-19 | 2010-09-01 | 阿赛洛法国公司 | 制造复合部件的方法 |
CN104582963A (zh) * | 2012-07-31 | 2015-04-29 | 陶氏环球技术有限责任公司 | 制造耐火泡沫隔热板的方法 |
CN104582963B (zh) * | 2012-07-31 | 2016-11-09 | 陶氏环球技术有限责任公司 | 制造耐火泡沫隔热板的方法 |
CN106794668A (zh) * | 2014-07-31 | 2017-05-31 | 巴斯夫欧洲公司 | 用于建筑物立面的基于聚氨酯硬质泡沫的热复合*** |
CN112805151A (zh) * | 2018-09-14 | 2021-05-14 | 巴斯夫欧洲公司 | 由金属和由热塑性聚氨酯制成的聚合物中间层组成的层压制件 |
Also Published As
Publication number | Publication date |
---|---|
CA2412510A1 (en) | 2003-05-28 |
MXPA02011739A (es) | 2005-08-26 |
JP2003211584A (ja) | 2003-07-29 |
EP1316414A1 (de) | 2003-06-04 |
ZA200208648B (en) | 2003-10-27 |
HK1054350A1 (zh) | 2003-11-28 |
RU2002131903A (ru) | 2004-05-20 |
US20030104241A1 (en) | 2003-06-05 |
DE10158491A1 (de) | 2003-06-12 |
KR20030043750A (ko) | 2003-06-02 |
BR0204867A (pt) | 2004-06-15 |
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