CN112867745B - 分散体胶粘剂 - Google Patents
分散体胶粘剂 Download PDFInfo
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- CN112867745B CN112867745B CN201980063599.4A CN201980063599A CN112867745B CN 112867745 B CN112867745 B CN 112867745B CN 201980063599 A CN201980063599 A CN 201980063599A CN 112867745 B CN112867745 B CN 112867745B
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Abstract
本发明涉及基于水性聚氨酯或聚氨酯‑脲分散体的水性分散体胶粘剂的配制品和所述胶粘剂配制品用于通过喷雾凝聚法胶粘泡沫基底的用途。
Description
本发明涉及基于水性聚氨酯或聚氨酯-脲分散体的水性分散体胶粘剂的配制品、涉及其制备方法并涉及所述分散体胶粘剂用于通过喷雾凝聚法胶粘泡沫基底的用途。
当将泡沫基底胶粘到其它基底上时,例如对于泡沫-泡沫、泡沫-木材和泡沫-塑料的组合,主要在喷雾凝聚法中使用聚氯丁烯分散体胶粘剂。在这种方法中,将胶粘剂和凝聚剂分开传送到喷枪中,在喷雾射流中混合并凝聚。由于直到在喷雾射流中才发生混合,不需要考虑适用期。此外,凝聚的胶粘剂保留在待胶粘的基底表面上并且不扩撒或仅少部分地扩散到泡沫基底的孔隙结构中。这通常实现高的初始强度、足够长的开放时间和良好的耐热性。
这种喷雾凝聚法的重要应用领域是床垫和座椅家具的生产。特别在斯堪的纳维亚国家,需要聚氯丁烯分散体胶粘剂的无氯替代品,以例如能够满足北欧白天鹅环保图标的要求。此外,它们应该以高的初始强度、足够长的开放时间和良好的耐热性为特征。由于座椅家具,特别是办公椅的生产经常涉及使用非极性基底,如聚丙烯基底或粒子填充的聚丙烯基底,足够好的附着力不仅是泡沫在泡沫上和泡沫在木材上的胶粘所需的,还特别是泡沫在非极性表面上的胶粘所需的。
基于水性聚氨酯分散体的胶粘剂已在高要求的工业应用中在全世界获得认可,例如在制鞋、机动车内部部件的胶粘、膜层压或织物基底的胶粘的情况下。
在此类基于水性聚氨酯分散体的胶粘剂用于胶粘基底的情况下,通常在热活化过程后进行。在这种情况下,将分散体施加到基底上,并在水完全蒸发后,通过加热,例如使用红外辐射器活化胶粘剂层,并转化成能胶粘的状态。胶粘剂膜变得发粘的温度被称为活化温度。
但是,当使用聚氨酯或聚氨酯-聚脲分散体时,也可使用湿胶粘法进行,即在施加胶粘剂后立即进行胶粘。在这种情况下必须机械固定待接合的部件直至胶粘剂凝固。这种方法常用于木材或织物基底的胶粘。
热活化法和湿胶粘法都较不适用于泡沫基底的胶粘。水的缓慢蒸发特别要求在胶粘剂的施加和胶粘过程之间的长等待时间,或适当的干燥装置。此外,该胶粘剂的并非微不足道的部分可在干燥前或在干燥过程中扩散到泡沫基底的孔隙中并随后不再可用于实际胶粘。
市场上已确立的基于水性聚氨酯分散体的胶粘剂通常不适合于使用喷雾凝聚法,因为它们经常没有足够快地凝聚并且特别在困难的基底,例如具有高恢复力的泡沫上,没有表现出足够的附着力和强度。由于分散聚合物含有氨基甲酸酯基团和脲基团作为极性基团,以及离子或非离子亲水基团,特别在将泡沫胶粘到聚丙烯基底上时不实现或仅实现不足的附着力。
WO 2013/053786 A1描述了水性聚氨酯分散体,其聚合物具有根据DIN 65467在20K/min的加热速率下通过差示扫描量热法测定的30℃至50℃的熔融温度,其中所述聚合物可由两种不同结晶的聚酯多元醇以预定用量比获得。这些聚氨酯分散体主要适合作为冷接触胶粘剂,但也可通过喷雾凝聚法使用。但是,由此可实现的强度对大多数泡沫胶粘应用而言不足。特别在非极性表面上没有实现足够的附着力。
来自BASF AG (德国Ludwigshafen)的Luphen® D DS 3548提供了环氧树脂改性的聚氨酯分散体,其尤其也应适用于喷雾凝聚法。此处所用的环氧树脂的基础是双酚A二缩水甘油醚。由于双酚A和由其形成的后续产物因其对内分泌系统的可能影响而特别令最终消费者极为不满并因此通常受到排斥,市场需要不含双酚A的胶粘剂和其它产品。
WO 2014/182170 A1描述了使用特定的无气喷涂法进行喷雾凝聚法。为此,使用聚氯丁烯分散体和增粘剂分散体的混合物以及聚氨酯分散体和增粘剂分散体的混合物。但是,这些在该文献中没有进一步规定。所提到的应用领域是在床垫和家具制造行业中的泡沫胶粘。同样没有描述如何能够在非极性表面上实现附着力。
US 2015/0079339 A1描述了通过在100至200℃的温度范围内使用聚氨酯分散体胶粘制成的也尤其由泡沫基底组成的多层制品。为了防止胶粘剂分散体渗入基底的孔隙,可任选加入凝聚剂,但其中不使用喷雾凝聚法。没有指出是否也能够在非极性表面上实现附着力。
本发明的目的因此是提供通过喷雾凝聚法胶粘泡沫基底的聚氯丁烯分散体胶粘剂的无氯且无双酚A的替代品,其没有表现出现有技术的缺点并且甚至在困难的基底上,尤其是在具有高恢复力的泡沫的情况下也表现出足够的附着力和强度,并且另外以在非极性表面上的附着力为特征。
现在已经令人惊讶地发现,含有水性聚氨酯或聚氨酯-脲分散体、增塑剂树脂和增粘剂树脂的混合物的水性胶粘剂配制品适用于通过喷雾凝聚法胶粘泡沫基底,没有表现出现有技术的缺点并且也能够将泡沫基底胶粘到具有非极性表面的基底上。
本发明的主题因此是含有以下组分的混合物的配制品
I. 水性聚氨酯或聚氨酯-脲分散体,其含有在干燥后为部分结晶或结晶的并具有30至80℃的熔融温度和≥ 35 J/g的熔化焓的聚合物A)作为分散相,
II. 至少一种增塑剂树脂B),
III. 至少一种增粘剂树脂C),
其特征在于基于包含的总固体计,所述混合物含有
60重量% - 90重量%的聚合物A),
5重量% - 20重量%的增塑剂树脂B)和
5重量% - 20重量%的增粘剂树脂C),
并且A)、B)和C)的用量比例合计为100重量%。
基于包含的总固体计,该混合物优选含有
66重量% - 85重量%的聚合物A),
8重量% - 18重量%的增塑剂树脂B)和
7重量% - 16重量%的增粘剂树脂C),
其中A)、B)和C)的用量比例合计为100重量%。
基于固体计,该混合物特别优选含有
70重量% - 81重量%的聚合物A),
10重量% - 16重量%的增塑剂树脂B)和
9重量% - 14重量%的增粘剂树脂C),
其中A)、B)和C)的用量比例合计为100重量%。
在本发明的一个非常特别优选的实施方案中,基于固体计,该混合物含有
72重量% - 80重量%的聚合物A),
10重量% - 15.5重量%的增塑剂树脂B)和
10重量% - 12.5重量%的增粘剂树脂C),
其中A)、B)和C)的用量比例合计为100重量%。
关于本发明被称为聚氨酯分散体的分散体含有可为狭义上的聚氨酯的聚合物,即通过多元醇和多异氰酸酯的聚合获得的那些聚合物作为分散相,但也可以是其中使用单胺和/或二胺作为形成组分、任选作为扩链剂的那些。可根据本发明使用的分散体因此被称为水性聚氨酯或聚氨酯-脲分散体。
当其在根据DIN 65467在20 K/min的加热速率下的DSC测量中具有熔融峰时,聚合物被称为部分结晶或结晶的。熔融峰由聚合物中的规则子结构的熔融造成。由根据本发明的配制品获得的聚合物或聚合物层的熔融温度在这种情况下优选在35℃至80℃,特别优选40℃至70℃,非常特别优选42℃至55℃的范围内。由根据本发明的配制品获得的聚合物层的熔化焓为≥ 35 J/g,优选≥ 40 J/g,特别优选≥ 45 J/g。评估第一次加热,从而也检测缓慢结晶的聚合物。
尽管本发明的教导原则上可用各种分散的聚氨酯或聚氨酯-脲聚合物作为聚合物A)实现,但根据本发明,聚合物A)优选由以下组分形成
A(i). 至少一种结晶或部分结晶的双官能聚酯多元醇,其具有至少400 g/mol的数均分子量和至少35℃的熔融温度和至少35 J/g的熔化热,
A(ii). 任选至少一种具有62至399 g/mol的数均分子量的双官能多元醇组分,
A(iii). 异氰酸酯组分,
A(iv). 至少一种带有至少一个离子基团或潜在离子基团的异氰酸酯反应性组分,
和
A(v). 任选其它异氰酸酯反应性组分。
本发明的水性分散体含有15重量%至60重量%的聚合物和40重量%至85重量%的水,优选30重量%至50重量%的聚合物和50重量%至70重量%的水,特别优选40重量%至50重量%的聚合物和50重量%至60重量%的水。
该聚合物含有50重量%至95重量%的成分A(i)、0重量%至10重量%的成分A(ii)、4重量%至25重量%的成分A(iii)、0.5重量%至10重量%的成分A(iv)和0重量%至30重量%的成分A(v),其中成分的总数合计为100重量%。
在本发明的一种优选形式中,该聚合物含有65重量%至92重量%的成分A(i)、0重量%至5重量%的成分A(ii)、6重量%至15重量%的成分A(iii)、0.5重量%至5重量%的成分A(iv)和0重量%至25重量%的成分A(v),其中成分的总数合计为100重量%。
在本发明的一种特别优选的形式中,该聚合物含有75重量%至92重量%的成分A(i)、0重量%至5重量%的成分A(ii)、8重量%至15重量%的成分A(iii)、0.5重量%至4重量%的成分A(iv)和0重量%至15重量%的成分A(v),其中成分的总数合计为100重量%。
在本发明的一种非常特别优选的形式中,该聚合物含有80重量%至90重量%的成分A(i)、0重量%至3重量%的成分A(ii)、8重量%至14重量%的成分A(iii)、0.5重量%至3重量%的成分A(iv)和0重量%至10重量%的成分A(v),其中成分的总数合计为100重量%。
可考虑的结晶或部分结晶的双官能聚酯多元醇A(i)特别是基于二羧酸和/或其衍生物,如酐、酯或酰基氯的线性或轻微支化的聚酯多元醇,优选脂族线性多元醇。二羧酸和/或其衍生物的混合物也是合适的。合适的二羧酸是例如己二酸、丁二酸、癸二酸或十二烷二酸。优选的是丁二酸、己二酸和癸二酸和这些的混合物,特别优选的是丁二酸和己二酸和这些的混合物,非常特别优选的是己二酸。这些以基于所有羧酸的总量计至少90摩尔%,优选95至100摩尔%的量使用。
双官能聚酯多元醇A(i)可例如通过二羧酸与多元醇的缩聚制备。多元醇优选具有62至399 g/mol的分子量、由2至12个碳原子组成、优选未支化、双官能并优选具有伯OH基团。
可用于制备聚酯多元醇A(i)的多元醇的实例包括多元醇,例如乙二醇、二-、三-或四乙二醇、丙-1,2-二醇、二-、三-或四丙二醇、丙-1,3-二醇、丁-1,4-二醇、丁-1,3-二醇、丁-2,3-二醇、戊-1,5-二醇、己-1,6-二醇、2,2-二甲基丙-1,3-二醇、1,4-二羟基环己烷、1,4-二羟甲基环己烷、辛-1,8-二醇、癸-1,10-二醇、十二烷-1,12-二醇或这些的混合物。
用于聚酯多元醇A(i)的优选多元醇组分是乙-1,2-二醇、丁-1,4-二醇和己-1,6-二醇;特别优选的是丁-1,4-二醇和己-1,6-二醇,非常特别优选的是丁-1,4-二醇。
聚酯多元醇A(i)可由一种或多种多元醇形成。在本发明的一个优选实施方案中,它们由仅一种多元醇形成。
如果具有至少400 g/mol的数均分子量和至少35℃的熔融温度的结晶或部分结晶的双官能聚酯多元醇具有至少50 J/g的熔化热,则用其制成的聚合物经常具有≥ 35 J/g的熔化热。如果需要,可通过组成中的聚酯多元醇A(i)的含量的轻微修改或通过聚酯多元醇的熔化热的小变动来实现该聚合物的熔化热的调节。这些措施只需要探索性的实验并且完全在本领域普通技术人员的实践经验内。
聚酯多元醇A(i)的制备是现有技术中已知的。
聚酯多元醇A(i)的数均分子量优选在400至4000 g/mol之间,更优选在1000至3000 g/mol之间,特别优选在1500至2500 g/mol之间,非常特别优选在1800至2400 g/mol之间。
该结晶或部分结晶的聚酯多元醇的熔融温度通常为至少35℃,优选在40至80℃之间,特别优选在42至60℃之间,非常特别优选在45至52℃之间。熔化热为≥ 35 J/g,优选≥40 J/g,特别优选≥ 50 J/g。
适合作为形成组分A(ii)的具有62至399的分子量的双官能多元醇组分的实例包括所提到的用于制备聚酯多元醇A(i)的多元醇。低分子量聚酯二醇、聚醚二醇、聚碳酸酯二醇或其它聚合物二醇原则上也合适,只要它们具有62至399道尔顿的分子量。
合适的形成组分A(iii)是每分子具有至少两个游离异氰酸酯基团的任意有机化合物。优选使用二异氰酸酯Y(NCO)2,其中Y是具有4至12个碳原子的二价脂族烃基、具有6至15个碳原子的二价脂环族烃基、具有6至15个碳原子的二价芳族烃基或具有7至15个碳原子的二价芳脂族烃基。优选使用的此类二异氰酸酯的实例包括四亚甲基二异氰酸酯、甲基五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷、4,4'-二环己基甲烷二异氰酸酯、4,4'-二异氰酸根合-2,2-二环己基丙烷、1,4-苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯甲烷二异氰酸酯、2,2'-和2,4'-二苯甲烷二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、对苯二亚甲基二异氰酸酯、对-异亚丙基二异氰酸酯和由这些化合物组成的混合物。
也可以共同使用一定比例的本身在聚氨酯化学中已知的更高官能多异氰酸酯或本身已知的改性的且例如包含碳二亚胺基团、脲基甲酸酯基团、异氰脲酸酯基团、氨基甲酸酯基团和/或缩二脲基团的多异氰酸酯。
除这些简单二异氰酸酯外,在连接异氰酸酯基团的基团中含有杂原子和/或具有每分子多于2个异氰酸酯基团的官能度的多异氰酸酯也合适。前者是例如通过简单脂族、脂环族、芳脂族和/或芳族二异氰酸酯的改性制成的由至少两种二异氰酸酯形成且具有脲二酮、异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、缩二脲、碳二亚胺、亚氨基噁二嗪二酮和/或噁二嗪三酮结构的多异氰酸酯。每分子具有多于2个异氰酸酯基团的未改性多异氰酸酯的一个实例是4-异氰酸根合甲基辛烷1,8-二异氰酸酯(壬烷三异氰酸酯)。
特别优选的形成组分A(iii)是六亚甲基二异氰酸酯(HDI)和1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(IPDI)及其混合物。
优选的带有至少一个离子基团或潜在离子基团的异氰酸酯反应性组分A(iv)是单-和二羟基羧酸、单-和二氨基羧酸、单-和二羟基磺酸、单-和二氨基磺酸以及单-和二羟基膦酸或单-和二氨基膦酸和它们的碱金属盐和铵盐。实例是二羟甲基丙酸、二羟甲基丁酸、羟基特戊酸、N-(2-氨基乙基)-β-丙氨酸、N-(2-氨基乙基)-2-氨基乙磺酸、N-(2-氨基乙基)-2-氨基乙烷甲酸、乙二胺丙基-或-丁基磺酸、丙-1,2-或-1,3-二胺-β-乙基磺酸、苹果酸、柠檬酸、乙醇酸、乳酸、甘氨酸、丙氨酸、牛磺酸、赖氨酸、3,5-二氨基苯甲酸、IPDI和丙烯酸的加成产物(EP-A 0 916 647,实施例1)及其碱金属盐和/或铵盐;例如DE-A 2 446 440(第5-9页,式I-III)中描述的亚硫酸氢钠与丁-2-烯-1,4-二醇的加合物、聚醚磺酸酯、2-丁烯二醇和NaHSO3的丙氧基化加合物。非常适用于成盐的是钠、钾、锂和钙的氢氧化物和叔胺如三乙胺、二甲基环己基胺和乙基二异丙基胺。其它胺也可用于成盐,如氨、二乙醇胺、三乙醇胺、二甲基乙醇胺、甲基二乙醇胺、氨基甲基丙醇以及所述胺和其它胺的混合物。适宜地,这些胺仅在异氰酸酯基团基本上转化后才加入。
可通过酸的加入而转化成阳离子基团的单元,如N-甲基二乙醇胺也适合作为组分A(iv)。
特别优选的组分A(iv)是具有羧基和/或羧酸根基团和/或磺酸根基团的那些。
非常特别优选的是N-(2-氨基乙基)-2-氨基乙磺酸和N-(2-氨基乙基)-2-氨基乙烷甲酸的钠盐,尤其是N-(2-氨基乙基)-2-氨基乙磺酸的钠盐。此外,非常特别优选的是二羟甲基丙酸的盐。
异氰酸酯反应性组分A(v)可以例如是含有至少一个羟基或氨基的聚氧化烯醚。常用的聚环氧烷聚醚醇可以本身已知的方式通过合适的起始剂分子的烷氧基化获得。适用于烷氧基化反应的环氧烷尤其是环氧乙烷和环氧丙烷,它们可独自或一起用于烷氧基化反应。
异氰酸酯反应性组分A(v)的进一步实例是单胺、二胺和/或多胺,及其混合物。
单胺的实例是脂族和/或脂环族伯和/或仲单胺,如乙胺、二乙胺、异构丙基-和丁基胺、更高级的线性脂族单胺和脂环族单胺,如环己胺。进一步的实例是氨基醇,即在一个分子中含有氨基和羟基的化合物,例如乙醇胺、N-甲基乙醇胺、二乙醇胺或2-丙醇胺。二胺的实例是乙-1,2-二胺、己-1,6-二胺、1-氨基-3,3,5-三甲基-5-氨基甲基环己烷(异佛尔酮二胺)、哌嗪、1,4-二氨基环己烷和双(4-氨基环己基)甲烷。己二酸二酰肼、肼和水合肼也可考虑。进一步的实例是氨基醇,即在一个分子中含有氨基和羟基的化合物,例如1,3-二氨基-2-丙醇、N-(2-羟乙基)乙二胺或N,N-双(2-羟乙基)乙二胺。多胺的实例是二亚乙基三胺和三亚乙基四胺。
在本发明的一种优选形式中,根据本发明的聚合物含有至少一种单胺和/或至少一种二胺作为异氰酸酯反应性组分A(v)以调节摩尔质量。
该水性聚氨酯或聚氨酯-脲分散体优选不含外部乳化剂。
在本发明的一个特定实施方案中,聚合物A)含有己二酸和丁-1,4-二醇的聚酯作为组分A(i)、丁-1,4-二醇作为组分A(ii)、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(IPDI)作为组分A(iii)、N-(2-氨基乙基)-2-氨基乙磺酸的钠盐作为组分A(iv)和二乙醇胺作为组分A(v)。
“增塑剂”是指添加到聚合物中以使它们柔软、挠性、可延展和柔顺以便使用或进一步加工的化学物质。
所用增塑剂B)是带有极性基团的难挥发性低分子量化合物。优选增塑剂是二(苯氧基乙基)甲缩醛和基于芳族羧酸如邻苯二甲酸、间苯二甲酸、对苯二甲酸、苯甲酸、偏苯三酸;基于脂族羧酸如马来酸、富马酸、琥珀酸、乙酸、丙酸、丁酸、己二酸、壬二酸、癸二酸、柠檬酸、环己烷二甲酸,或基于脂肪酸如油酸、蓖麻油酸或硬脂酸的难挥发性酯;和磷酸酯、磺酸酯或烷基磺酸酯。也优选的是环氧化植物油,如环氧化亚麻籽油和环氧化大豆油。
特别优选的是二(苯氧基乙基)甲缩醛、对苯二甲酸二丁酯、酚的烷基磺酸酯和基于苯甲酸的酯。非常特别优选的是二(苯氧基乙基)甲缩醛、对苯二甲酸二丁酯和二丙二醇二苯甲酸酯。在本发明的一个非常特别优选的实施方案中,所用增塑剂B)是二(苯氧基乙基)甲缩醛。
在本发明的一个同样非常特别优选的实施方案中,所用增塑剂B)是二丙二醇二苯甲酸酯。
“增粘剂树脂”是指充当增粘剂并提高塑料或胶粘剂的粘附能力的树脂。
所用增粘剂树脂C)既可以是天然树脂,也可以是合成树脂,例如脂族、芳族改性、芳族且氢化的烃树脂、萜烯树脂、改性萜烯树脂和萜烯-酚树脂,或树木树脂衍生物,如松香树脂、改性松香树脂如基于松香的树脂酯(“松香酯”)、香脂树脂衍生物(“脂松香”)和妥尔油衍生物(“妥尔油松香”)。增粘剂树脂可独自或混合使用。
所用增粘剂树脂C)优选是松香树脂和改性松香树脂。特别优选使用基于松香树脂的树脂酯。增粘剂可作为100%树脂或作为在根据本发明的配制品中的分散体使用,只要提供相容性(例如防止相分离的稳定性)。在本发明的一个特别优选的实施方案中,作为组分C),使用松香树脂酯的水性分散体(“松香酯分散体”)。
根据本发明的配制品优选用于通过喷雾凝聚法进行胶粘。在这种方法中,将水性胶粘剂配制品和凝聚剂分开传送到双组分喷枪中并在喷雾射流中混合。通常使用雾化器空气在0.1-5巴的压力下进行喷涂;但是,也可以如例如WO 2015/137808中所述无气传送这两种组分的至少一种。在通往第一基底的表面的途中在喷雾射流中发生分散体的凝聚;胶粘剂分散体中包含的一部分水在该过程中已蒸发。在碰撞时,胶粘剂聚合物在第一基底的表面上形成膜,其在仍湿状态下立即发粘。由于直到在喷雾射流中才发生胶粘剂分散体和凝聚剂的混合,不需要考虑适用期。由于聚合物膜在湿状态下的粘性,可立即接合第二表面,其中理想地例如在基底上对着胶粘面施加压力。通过将两个基底表面压在一起而施加压力是有利的,因为其提高胶粘的强度。同样有利的是,两个基底的至少一个是多孔的或透水的,以便能够从凝固的胶粘接头中带走水。
可考虑的凝聚剂包括优选周期表的第一、第二和第三主族的金属的盐的水溶液,特别是如果它们具有良好的水溶性。优选使用基于二价或三价阳离子的盐。特别优选使用氯化钙、硫酸锌或硫酸铝。非常特别优选使用氯化钙。也可作为水溶液使用根据上文描述的不同盐的混合物。
适合作为凝聚剂的盐水溶液中的盐浓度通常为1重量%至20重量%,优选2重量%至10重量%,特别优选3重量%至4重量%。基于胶粘剂溶液 + 凝聚剂溶液的总和计,凝聚剂的水溶液的比例在0.1重量%至50重量%之间,优选在1重量%至30重量%之间,特别优选在8重量%至20重量%重量,非常特别优选在12重量%至18重量%之间。
或者,所用凝聚剂也可以是无机或有机酸,优选柠檬酸、磷酸或碳酸的水溶液,和一种或多种上述盐与一种或多种这些酸的混合物。
根据本发明的配制品优选通过将水性聚氨酯或聚氨酯-脲分散体与增塑剂树脂和增粘剂树脂混合来制备。这可以任意顺序进行。优选最先装载聚氨酯分散体,然后在搅拌下相继加入增粘剂树脂C)和增塑剂树脂B)。在此优选使用引入足够高的剪切力的搅拌器。合适的搅拌器是本领域技术人员已知的或可通过简单的预备实验确定。
用根据本发明的配制品通过喷雾凝聚法制成的胶粘在具有70 kg/m³和更高的高单位体积重量和因此相关的高恢复力的泡沫基底的情况下表现出足够的即时强度,以及对非极性表面,特别是对聚丙烯基底的附着力。
泡沫基底被理解为是指由泡沫材料制成的基底,其中泡沫材料通常是具有泡孔结构和低密度的人造物质。在此可区分开孔、闭孔和混合泡孔的泡沫材料。根据硬度,将泡沫材料分成硬质泡沫和软质泡沫。几乎所有塑料都适用于发泡。泡沫的一个重要特征数是单位体积重量,也称为密度。这以kg/m³表示并给出边长1 m的泡沫材料块的重量。单位体积重量被认为是用于区分泡沫材料的最重要的特征,其它性质在很大程度上取决于它。单位体积重量越高,恢复力越大,对胶粘剂的即时强度的要求越高。
原则上,根据本发明的配制品适用于通过喷雾凝聚法胶粘所有泡沫基底。优选胶粘开孔和混合泡孔的泡沫基底。在此甚至可胶粘具有高单位体积重量和高恢复力的泡沫基底。
在本发明的一个优选实施方案中,所述一个或多个泡沫基底由聚氨酯(例如聚醚和聚酯泡沫)和/或橡胶,例如天然橡胶(NR)、苯乙烯-丁二烯橡胶(SBR)、乙烯-丙烯-二烯聚合物(EPDM)、丁二烯-丙烯腈橡胶(NBR)或氯丁橡胶(CR)组成。
在本发明的一个特别优选的实施方案中,所述一个或多个泡沫基底由聚氨酯组成。
根据本发明的配制品还以对非常多样化的其它基底,例如对木材、纸、皮革、纺织品、软木和塑料(热塑性塑料、弹性体、热固性材料、复合材料),如不同的聚氯乙烯等级、聚氨酯、聚乙酸乙烯酯、ABS、橡胶、聚(乙烯-乙酸乙烯酯)、聚碳酸酯或聚烯烃,例如填充或未填充的聚丙烯的良好附着力为特征。令人惊讶地,借助根据本发明的配制品和甚至在非极性基底的情况下,通常不需要基底表面的预处理,该预处理例如通过上底漆、烧毛(Flämmen)或电晕处理。
含有根据本发明的配制品的胶粘剂组合物因此适用于优选由上述材料形成的任意基底的胶粘。
根据本发明的胶粘剂特别适用于泡沫在泡沫上、泡沫在木材上、泡沫在各种塑料上和织物在各种基底上的胶粘。
含有根据本发明的配制品的胶粘剂组合物非常特别适用于泡沫在非极性基底上,特别是在填充或未填充的聚丙烯上的胶粘。
在家具行业,尤其是座椅家具行业中,在此特别是在办公椅的生产中,这种基底组合具有重要的意义。使用根据本发明的配制品制成的该行业的典型制品,如椅子、沙发等因此也落在本发明的范围内。
包含使用根据本发明的配制品胶粘的基底和扁平结构的胶粘复合体同样是本申请的主题。
实施例
下面基于实施例更详细阐释本发明。在此使用以下方法和试验方法:
A) 喷雾凝聚法:
用于双组分分散体胶粘剂的标准喷枪,即来自Walther Pilot公司的PILOT III2K用于施加。将胶粘剂和凝聚剂CaCl2(3重量%水溶液)分开传送到喷枪中,在喷雾射流中混合并使胶粘剂凝聚。由于直到在喷雾射流中才发生混合,不需要考虑适用期。选择86重量%胶粘剂分散体和14重量% CaCl2溶液的比率。
喷枪的精确设定原则上是本领域技术人员已知的,并可为具体情况定制而没有过分高的支出,并可通过简单的预备实验确定。可通过将储器和基底重新称重来测定用量比和施加重量。
使用以下设定:
a.) 胶粘剂组分: 传送压力1.3巴
b.) 凝聚剂组分: 传送压力0.3巴
c.) 雾化器空气压力: 2.8巴
d.) 用于胶粘剂组分的孔(喷嘴): 1.0 mm
e.) 用于凝聚剂组分的孔(喷嘴): 0.4 mm
f.) 施加重量: 130 - 150 g/m²(湿)
B) 具有高单位体积重量和高恢复力的泡沫基底的初始强度的测定:
作为试验材料,使用具有10 x 5 x 3 cm的尺寸和70 kg/m³的单位体积重量的来自STN Schaumstoff Technik Nürnberg GmbH公司的PU泡沫材料体ST 13070。为了评估初始强度,在借助喷雾凝聚法施加胶粘剂(施加量130 - 150 g/m²湿)后立即使用轻掌压将试样中间对折并接合在一起。如果尽管存在恢复力但试样没有打开,则初始强度足够。
C) 对聚丙烯的附着力
(泡沫基底胶粘到聚丙烯基底上):
作为试验材料,使用具有20 kg/m³的单位体积重量和10 x 5 x 3 cm的尺寸的来自Recticel公司的PU泡沫材料体Recticel® T 20120(图1,(A))和具有20 x 10 x 0.4 cm的尺寸的来自SIMONA AG公司的聚丙烯塑料基底PP-DWST(图1,(B))。借助喷雾凝聚法(施加量130 - 150 g/m²湿)施加胶粘剂,在聚丙烯基底的情况下施加到顶面的整个表面(20 x10 cm)(图1,(BO)),在泡沫材料基底的情况下施加到底面的整个表面(10 x 5 cm)(图1,(C))并另外施加到短边面(5 x 3 cm)(图1,(D))。
在施加胶粘剂后,将泡沫材料接合到聚丙烯上。为此,用手在轻压下将泡沫的已带有胶粘剂的表面(C)接合到聚丙烯的已施加胶粘剂的面上(图1,(C)对着(BO))。然后,将泡沫材料的已带有胶粘剂的边面(图1.1,(D))同样用手在轻压下(图1.1,(F))接合到聚丙烯的经涂覆的面上(图1.2,(D)),以使泡沫材料试样在接合的边面(D)和表面(A)的区域中由于恢复力(图1.2,(FR))而处于高应力下。
在试样在室温下储存24小时后评估附着力:如果泡沫材料基底(图1.2,(A))的接合的边面(图1.2,(D))在湿状态下立即、在干燥过程中或在干燥后与聚丙烯基底(图1,(B))的表面(图1.2 (BO))脱开,则不存在足够的附着力。
D) 借助DSC确定玻璃化转变温度、熔融温度和熔化焓:
使用来自Perkin-Elmer公司的量热计Pyris Diamond DSC借助差示扫描量热法(DSC)测定玻璃化转变温度以及熔融温度和熔化焓。为此,通过将分散体以100 µm湿膜厚度刮涂到玻璃板上而制造膜,通风2小时之久,然后将该膜与玻璃板一起在干燥箱中在室温和0%相对室内湿度下干燥3天。然后,使用10毫克来自该膜的样品材料在下列测量条件下记录DSC曲线:迅速冷却到起始温度-100℃、然后开始在氦气气氛下以20 K/min的加热速率和320 K/min的冷却速率从-100℃至+150℃加热三次,并用液氮冷却。玻璃化转变温度对应于在玻璃化转变的一半高度处的温度,其中评估第三次加热。对于熔融温度和熔化焓的测定,评估第一次加热。
E) 原料
聚酯I: 由丁-1,4-二醇和己二酸形成的聚酯二醇,OH值 = 50
聚酯II: 由己-1,6-二醇和邻苯二甲酸酐形成的聚酯二醇,OH值 = 56
Desmodur® H: 六亚甲基1,6-二异氰酸酯(德国Leverkusen的CovestroDeutschland AG)
Desmodur® I: 异佛尔酮二异氰酸酯(德国Leverkusen的Covestro DeutschlandAG)
Luphen® DDS 3548: 来自德国Ludwigshafen的BASF AG的环氧树脂改性的聚氨酯分散体,具有45重量%的固含量。包含的聚合物在干燥后为部分结晶的,具有41.5℃的熔融温度和34.4 J/g的熔化焓
Desavin®: 二(苯氧基乙基)甲缩醛(德国Leverkusen的Covestro DeutschlandAG)
(增塑剂树脂)
DBT: 对苯二甲酸二正丁酯(美国Kingsport的Eastman)
(增塑剂树脂)
Synegis® 9100: 二丙二醇二苯甲酸酯(比利时Mont-Saint-Guibert的Synegis)
(增塑剂树脂)
Aquatac® XR-4343: 具有60重量%固含量的水性松香酯分散体
(荷兰Almere的Kraton Corporation)(增粘剂树脂)。
实施例1:
水性聚氨酯或聚氨酯-脲分散体的制备
450克聚酯I在110℃和15毫巴下脱水1小时。在80℃下,加入30.11克Desmodur®H,然后20.14克Desmodur® I。该混合物在80至90℃下搅拌,直至达到1.15重量%的恒定异氰酸酯含量。将反应混合物溶解在750克丙酮中并在此冷却到48℃。在剧烈搅拌下向该均匀溶液中加入5.95克N-(2-氨基乙基)-2-氨基乙磺酸的钠盐和2.57克二乙醇胺在65克水中的溶液。在30分钟后,通过加入700克水进行分散。在丙酮的蒸馏脱除后获得具有40.0重量%的固含量的水性聚氨酯-聚脲分散体。
包含的聚合物在干燥后为部分结晶的,具有48℃的熔融温度和50.4 J/g的熔化焓。
实施例2:
水性聚氨酯或聚氨酯-脲分散体的制备
798.3克聚酯I在110℃和15毫巴下脱水1小时。然后,在80℃下,加入13.5克丁-1,4-二醇和157.0克Desmodur® I并在90至100℃下搅拌该混合物,直至达到1.72%的恒定异氰酸酯含量。将反应混合物溶解在1450克丙酮中并在此冷却到48℃。在搅拌下向该均匀溶液中加入16.5克N-(2-氨基乙基)-2-氨基乙磺酸的钠盐和7.7克二乙醇胺在195克水中的溶液,并在48℃下搅拌另外30分钟。然后通过在剧烈搅拌下加入1440克水进行分散。在丙酮的蒸馏脱除后获得具有38.0重量%的固含量的水性聚氨酯-聚脲分散体。
包含的聚合物在干燥后为部分结晶的,具有49.8℃的熔融温度和45.9 J/g的熔化焓。
实施例3:
水性聚氨酯或聚氨酯-脲分散体的制备。
1215克聚酯II在110℃和15毫巴下脱水1小时。在80℃下,加入4.6克己-1,6-二醇和179.0克Desmodur® H并在90℃下搅拌该混合物,直至达到2.28重量%的恒定异氰酸酯含量。将反应混合物溶解在2490克丙酮中并在此冷却到48℃。在剧烈搅拌下向该均匀溶液中加入31.9克N-(2-氨基乙基)-2-氨基乙磺酸的钠盐在300克水中的溶液。在30分钟后,通过加入1150克水进行分散。在丙酮的蒸馏脱除后获得具有50.0重量%的固含量的水性聚氨酯-聚脲分散体。
包含的聚合物在干燥后为非晶的(在DSC中没有熔融峰)。
实施例4:(对比)
用来自实施例1的分散体测定初始强度和对聚丙烯的附着力:对聚丙烯的附着力不足(见表1)。
实施例5:(对比)
由来自实施例1的PUD和增粘剂树脂分散体形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向91.7克来自实施例1的聚氨酯分散体中加入8.3克Aquatac® XR-4343,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有88.0重量%的聚氨酯聚合物和12.0重量%的增粘剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:对聚丙烯的附着力不足(见表1)。
实施例6:(对比)
由来自实施例1的PUD和增塑剂树脂形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向92.7克来自实施例1的聚氨酯分散体中加入7.3克Desavin®,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有83.6重量%的聚氨酯聚合物和16.4重量%的增塑剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:对聚丙烯的附着力不足(见表1)。
实施例7:(对比)
由来自实施例1的PUD和增塑剂树脂形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向93.5克来自实施例1的聚氨酯分散体中加入6.5克Synegis® 9100,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有85.2重量%的聚氨酯聚合物和14.8重量%的增塑剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:对聚丙烯的附着力不足(见表1)。
实施例8:(根据本发明)
由来自实施例1的PUD、增粘剂树脂和增塑剂树脂形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向85.6克来自实施例1的聚氨酯分散体中相继加入7.7克Aquatac® XR-4343和6.7克Desavin®,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有75.2重量%的聚氨酯聚合物、10.1重量%的增粘剂树脂和14.7重量%的增塑剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:初始强度和对聚丙烯的附着力都良好(见表1)。
实施例9:(根据本发明)
由来自实施例1的PUD、增粘剂树脂和增塑剂树脂形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向85.6克来自实施例1的聚氨酯分散体中相继加入7.7克Aquatac® XR-4343和6.7克DBT,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有75.2重量%的聚氨酯聚合物、10.1重量%的增粘剂树脂和14.7重量%的增塑剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:初始强度和对聚丙烯的附着力都良好(见表1)。
实施例10:(根据本发明)
由来自实施例1的PUD、增粘剂树脂和增塑剂树脂形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向84.0克来自实施例1的聚氨酯分散体中相继加入9.0克Aquatac® XR-4343和7.0克Synegis® 9100,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有73.0重量%的聚氨酯聚合物、11.7重量%的增粘剂树脂和15.2重量%的增塑剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:初始强度和对聚丙烯的附着力都良好(见表1)。
实施例11:(根据本发明)
由来自实施例2的PUD、增粘剂树脂和增塑剂树脂形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向87.0克来自实施例2的聚氨酯分散体中相继加入8.7克Aquatac® XR-4343和4.3克Desavin®,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有77.6重量%的聚氨酯聚合物、12.3重量%的增粘剂树脂和10.1重量%的增塑剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:初始强度和对聚丙烯的附着力都良好(见表1)。
实施例12:(对比)
由来自实施例1的PUD、增粘剂树脂和增塑剂树脂形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向78.0克来自实施例1的聚氨酯分散体中相继加入9.0克Aquatac® XR-4343和13.0克Synegis® 9100,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有62.9重量%的聚氨酯聚合物、10.9重量%的增粘剂树脂和26.2重量%的增塑剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:对聚丙烯的附着力不足(见表1)。
实施例13:(对比)
用来自实施例3的分散体测定初始强度和对聚丙烯的附着力:初始强度和对聚丙烯的附着力都不足(见表1)。
实施例14:(对比)
由来自实施例3的PUD、增粘剂树脂和增塑剂树脂形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向82.7克来自实施例3的聚氨酯分散体中相继加入9.3克Aquatac® XR-4343和5.0克Desavin®,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有79.6重量%的聚氨酯聚合物、11.8重量%的增粘剂树脂和9.6重量%的增塑剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:初始强度和对聚丙烯的附着力都不足(见表1)。
实施例15:(对比)
用Luphen® DDS 3548测定初始强度和对聚丙烯的附着力:初始强度和对聚丙烯的附着力都不足(见表1)。
实施例16:(对比)
由Luphen® DDS 3548、增粘剂树脂和增塑剂树脂形成的配制品的制备以及初始强度和对聚丙烯的附着力的测定。
在使用圆盘搅拌器剧烈搅拌下向83.9克Luphen® DDS 3548中相继加入8.6克Aquatac® XR-4343和7.5克Desavin®,搅拌另外4小时,随后在室温下储存12小时。基于固体计,该配制品含有74.9重量%的Luphen® DDS 3548聚合物、10.2重量%的增粘剂树脂和14.9重量%的增塑剂树脂。
用该配制品测定初始强度和对聚丙烯的附着力:初始强度和对聚丙烯的附着力都不足(见表1)。
表1: 根据本发明的实施例和对比例的评估
实施例 | 组成 | 初始强度(试验方法B) | 对PP的附着力(试验方法C) |
4(对比) | 来自实施例1的PUD | 是 | 否 |
5(对比) | 来自实施例1的PUD、Aquatac<sup>®</sup> XR-4343 | 是 | 否 |
6(对比) | 来自实施例1的PUD、Desavin<sup>®</sup> | 是 | 否 |
7(对比) | 来自实施例1的PUD、Synegis<sup>®</sup> 9100 | 是 | 否 |
8(根据本发明) | 来自实施例1的PUD、Aquatac<sup>®</sup> XR-4343、Desavin<sup>®</sup> | 是 | 是 |
9(根据本发明) | 来自实施例1的PUD、Aquatac<sup>®</sup> XR-4343、DBT | 是 | 是 |
10(根据本发明) | 来自实施例1的PUD、Aquatac<sup>®</sup> XR-4343、Synegis<sup>®</sup> 9100 | 是 | 是 |
11(根据本发明) | 来自实施例2的PUD、Aquatac<sup>®</sup> XR-4343、Desavin<sup>®</sup> | 是 | 是 |
12(对比) | 来自实施例1的PUD、Aquatac<sup>®</sup> XR-4343、Synegis<sup>®</sup> 9100 | 是 | 否 |
13(对比) | 来自实施例3的PUD | 否 | 否 |
14(对比) | 来自实施例3的PUD、Aquatac<sup>®</sup> XR-4343、Desavin<sup>®</sup> | 否 | 否 |
15(对比) | Luphen<sup>®</sup> DDS 3548 | 否 | 否 |
16(对比) | Luphen<sup>®</sup> DDS 3548、Aquatac<sup>®</sup> XR-4343、Desavin<sup>®</sup> | 否 | 否 |
Claims (20)
1.含有以下组分的混合物的配制品
I. 水性聚氨酯或聚氨酯-脲分散体,其含有在干燥后为部分结晶或结晶的并具有30至80℃的熔融温度和≥ 35 J/g的熔化焓的聚合物A)作为分散相,
II. 至少一种增塑剂B),
III. 至少一种增粘剂树脂C),
其特征在于基于包含的总固体计,所述混合物含有
60重量% - 90重量%的聚合物A),
5重量% - 20重量%的增塑剂B)和
5重量% - 20重量%的增粘剂树脂C),
并且A)、B)和C)的用量比例合计为100重量%。
2.如权利要求1中所述的配制品,其特征在于基于包含的总固体计,所述混合物含有
66重量% - 85重量%的聚合物A),
8重量% - 18重量%的增塑剂B)和
7重量% - 16重量%的增粘剂树脂C),
并且A)、B)和C)的用量比例合计为100重量%。
3.如权利要求1中所述的配制品,其特征在于基于包含的总固体计,所述混合物含有
70重量% - 81重量%的聚合物A),
10重量% - 16重量%的增塑剂B)和
9重量% - 14重量%的增粘剂树脂C),
并且A)、B)和C)的用量比例合计为100重量%。
4.如权利要求1中所述的配制品,其特征在于基于包含的总固体计,所述混合物含有
72重量% - 80重量%的聚合物A),
10重量% - 15.5重量%的增塑剂B)和
10重量% - 12.5重量%的增粘剂树脂C),
并且A)、B)和C)的用量比例合计为100重量%。
5.如权利要求1至4中任一项所述的配制品,其特征在于在干燥后为部分结晶或结晶的聚合物A)具有在35℃至80℃的范围内的熔融温度。
6.如权利要求1至4中任一项所述的配制品,其特征在于在干燥后为部分结晶或结晶的聚合物A)具有在40℃至70℃的范围内的熔融温度。
7.如权利要求1至4中任一项所述的配制品,其特征在于在干燥后为部分结晶或结晶的聚合物A)具有在42℃至55℃的范围内的熔融温度。
8.如权利要求1至4中任一项所述的配制品,其特征在于在干燥后为部分结晶或结晶的聚合物A)具有≥ 35 J/g的熔化焓。
9.如权利要求1至4中任一项所述的配制品,其特征在于在干燥后为部分结晶或结晶的聚合物A)具有≥ 40 J/g的熔化焓。
10.如权利要求1至4中任一项所述的配制品,其特征在于在干燥后为部分结晶或结晶的聚合物A)具有≥ 45 J/g的熔化焓。
11.如权利要求1至4中任一项所述的配制品,其特征在于作为增塑剂B),使用带有极性基团的难挥发性低分子量化合物。
12.如权利要求1至4中任一项所述的配制品,其特征在于作为增塑剂B),使用二(苯氧基乙基)甲缩醛、对苯二甲酸二丁酯、酚的烷基磺酸酯或基于苯甲酸的酯。
13.如权利要求1至4中任一项所述的配制品,其特征在于作为增粘剂树脂C),使用松香树脂和改性松香树脂。
14.如权利要求1至4中任一项所述的配制品,其特征在于作为增粘剂树脂C),使用基于松香的树脂酯。
15.如权利要求1至4中任一项所述的配制品,其特征在于作为增粘剂树脂C),使用松香树脂酯的水性分散体。
16.通过在双组分喷枪中将如权利要求1至15中任一项所述的配制品与凝聚剂混合而胶粘基底的方法,其中将凝聚剂单独传送到双组分喷枪中并在喷雾射流中混合,并在通往第一基底的表面的途中发生喷雾射流中的分散体的凝聚,在碰撞时在所述基底上形成在仍湿状态下立即发粘的膜并在湿状态下立即接合第二表面,其中在需要的情况下在基底上对着胶粘面施加压力。
17.如权利要求1至15中任一项所述的配制品用于泡沫在泡沫上、泡沫在木材上、泡沫在塑料上和织物在各种基底上的胶粘的用途。
18.如权利要求17中所述的用途,其特征在于至少一个待胶粘的基底是非极性基底。
19.如权利要求17中所述的用途,其特征在于至少一个待胶粘的基底是选自聚氨酯、橡胶泡沫的泡沫基底。
20.使用如权利要求1至15中任一项所述的配制品制成的家具。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18197310.8 | 2018-09-27 | ||
EP18197310.8A EP3628695A1 (de) | 2018-09-27 | 2018-09-27 | Dispersionsklebstoffe |
PCT/EP2019/075849 WO2020064829A1 (de) | 2018-09-27 | 2019-09-25 | Dispersionsklebstoffe |
Publications (2)
Publication Number | Publication Date |
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CN112867745A CN112867745A (zh) | 2021-05-28 |
CN112867745B true CN112867745B (zh) | 2022-11-15 |
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CN201980063599.4A Active CN112867745B (zh) | 2018-09-27 | 2019-09-25 | 分散体胶粘剂 |
Country Status (5)
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US (1) | US11441058B2 (zh) |
EP (2) | EP3628695A1 (zh) |
CN (1) | CN112867745B (zh) |
PL (1) | PL3856814T3 (zh) |
WO (1) | WO2020064829A1 (zh) |
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US20240101879A1 (en) | 2021-01-19 | 2024-03-28 | Covestro Deutschland Ag | Storage-Stable 1K Spray Adhesives Based on Polyurethane Dispersions |
EP4029891A1 (de) | 2021-01-19 | 2022-07-20 | Covestro Deutschland AG | Lagerstabile 1k-sprühklebstoffe auf basis von polyurethandispersionen |
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DE2446440C3 (de) | 1974-09-28 | 1981-04-30 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von wäßrigen Dispersionen von Sulfonatgruppen aufweisenden Polyurethanen |
DE19750186A1 (de) | 1997-11-13 | 1999-05-20 | Bayer Ag | Hydrophilierungsmittel, ein Verfahren zu dessen Herstellung sowie dessen Verwendung als Dispergator für wäßrige Polyurethan-Dispersionen |
US20070264462A1 (en) * | 2005-02-11 | 2007-11-15 | Invista North America S.A R.L. | Laminated fabric construction with heat activated polyurethaneurea compositions |
US20110082236A1 (en) * | 2008-06-03 | 2011-04-07 | Dow Global Technologies Inc. | Heat activated adhesive compositions and method of making the same |
JP6085303B2 (ja) | 2011-10-14 | 2017-02-22 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングBayer Intellectual Property GmbH | 低温触圧接着剤 |
KR102086441B1 (ko) | 2012-03-30 | 2020-03-09 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 우레아계 및 우레탄계 감압 접착제 블렌드 |
NL2010773C2 (en) | 2013-05-08 | 2014-11-13 | Saba Dinxperlo B V | A method of applying adhesive. |
JP6426738B2 (ja) * | 2013-07-30 | 2018-11-21 | エイチ.ビー.フラー カンパニー | ポリウレタン接着フィルム |
NL2012409B1 (en) | 2014-03-12 | 2015-11-26 | Saba Dinxperlo B V | Improved low pressure 2-K handheld spray gun. |
KR102528693B1 (ko) * | 2015-01-21 | 2023-05-08 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | 내화학성 폴리우레탄 접착제 |
ES2744571T3 (es) * | 2015-03-12 | 2020-02-25 | Henkel Ag & Co Kgaa | Dispersiones acuosas de poliuretano |
NL2015698B1 (en) * | 2015-10-30 | 2017-05-31 | Strongbond B V | Improved adhesive composition. |
US20180371147A1 (en) * | 2015-12-15 | 2018-12-27 | Basf Se | Aqueous polymer dispersion for adhesive compounds |
DE102015226482A1 (de) * | 2015-12-22 | 2017-06-22 | Tesa Se | Verfahren zur Verklebung eines Deckmaterials auf einem Formkörper |
CN106590506B (zh) * | 2016-12-08 | 2019-07-23 | 万华化学集团股份有限公司 | 一种水性真空吸塑胶及其制备方法 |
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- 2018-09-27 EP EP18197310.8A patent/EP3628695A1/de not_active Ceased
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- 2019-09-25 US US17/274,812 patent/US11441058B2/en active Active
- 2019-09-25 EP EP19772752.2A patent/EP3856814B1/de active Active
- 2019-09-25 WO PCT/EP2019/075849 patent/WO2020064829A1/de unknown
- 2019-09-25 PL PL19772752.2T patent/PL3856814T3/pl unknown
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WO2020064829A1 (de) | 2020-04-02 |
EP3856814C0 (de) | 2023-06-14 |
US20210317351A1 (en) | 2021-10-14 |
US11441058B2 (en) | 2022-09-13 |
CN112867745A (zh) | 2021-05-28 |
PL3856814T3 (pl) | 2023-10-30 |
EP3856814B1 (de) | 2023-06-14 |
EP3856814A1 (de) | 2021-08-04 |
EP3628695A1 (de) | 2020-04-01 |
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