CN112823174A - 一种聚氨酯组合物、其制备方法和应用 - Google Patents
一种聚氨酯组合物、其制备方法和应用 Download PDFInfo
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- CN112823174A CN112823174A CN201980055697.3A CN201980055697A CN112823174A CN 112823174 A CN112823174 A CN 112823174A CN 201980055697 A CN201980055697 A CN 201980055697A CN 112823174 A CN112823174 A CN 112823174A
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- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical group CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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Abstract
本发明涉及一种组合物、其制备和应用,以及用该组合物涂覆得到的产品。该组合物包含:(a)聚氨酯聚合物,所述聚氨酯聚合物是包含下列组分的反应产物:(a1)多异氰酸酯,(a2)具有异氰酸酯反应性基团的化合物,所述具有异氰酸酯反应性基团的化合物包含聚合物多元醇,所述聚合物多元醇选自下列的一种或多种:聚醚多元醇和聚烯烃多元醇,(a3)任选的乳化剂,(a4)任选的溶剂,和(a5)任选的反应性稀释剂;(b)有机抗氧化剂,所述抗氧化剂的量为0.01重量%‑2.4重量%,基于所述组合物的固体组分的总重量计;(c)螯合剂;和(d)水。根据本发明的组合物具有良好的耐高温黄变性。
Description
技术领域
本发明涉及一种组合物、其制备和应用,特别是在涂料和粘着剂领域中的应用,以及用该组合物涂覆的产品。
背景技术
聚氨酯聚合物和水可以混合形成水性聚氨酯分散体。水性聚氨酯分散体可以应用于涂料和粘着剂领域。在粘着剂领域中,通常将水性聚氨酯分散体施加到基材表面,然后加热以通过蒸发除去分散体中的水,随后热活化(例如红外线加热)涂层,最后将施加有分散体的基材表面与其他基材表面接触以得到粘接产品。在实践中,如果热活化所需温度高,那么不仅需要更多能源,而且增加了人工施涂和粘接的难度,因此,行业内希望寻找一种适用于在低温下热活化的粘着剂。
US 4870129A公开了一种粘着剂,包含含异氰酸酯官能团的交联剂和含羟基的水性聚氨酯分散体,其中通过该组合物形成的涂层需要的热活化温度是40℃-80℃。但是,该粘着剂的缺点是易黄变,不美观。
粘着剂的黄变常是因为其聚合物的氧化引起的。当粘着剂遇热或遇UV光时,氧化过程会加速,导致黄变加剧。粘着剂的黄变不仅会导致其粘接的产品外表不美观,还意味着粘着剂发生老化,通过使用该粘着剂得到的粘接产品的机械性能下降。在实践中,涂料和粘着剂常被应用于高温环境下。例如:将粘着剂应用在玻璃纤维上浆成型过程中,先将粘着剂施涂在玻璃纤维上,随后在高温下干燥以形成塑料板材。
EP0356655B1披露了一种应用于加强材料的组合物,包含至少一种可交联的聚氨酯、有机硅偶联剂、丙烯酸单体和可聚合单体的共聚物、交联剂、金属螯合剂和水,其中金属螯合剂是多齿化合物或具有式(RH2nCn)2N(CH2)xN(CnH2nR)2的化合物。用上述组合物处理玻纤增强的聚合物,使其甚至在长期暴露于溶剂、高温或UV后仍具有良好的机械性能。
EP0381125B1披露了一种不易氧化的组合物,该组合物可以应用于纤维上浆成型。该组合物包含:组分A包含热塑性聚酯、聚氧化烯、乙二醇、聚乙烯醇、聚烯烃胶乳、聚醋酸乙烯酯、环氧树脂、淀粉、环氧聚合物和聚乙烯醇的组合物、环氧聚合物和聚氨酯的组合物;组分B是金属螯合剂,选自多齿化合物或具有式(RH2nCn)2N(CH2)xN(CnH2nR)2的化合物;组分C和D都是抗氧化剂。用上述组合物处理纤维得到的产品在长期暴露于高温下后仍具有良好的机械性能。
AU A 60777/94披露了一种用作粘着剂的水性聚合物分散体,包含聚氨酯和螯合剂,螯合剂包含多价金属和多齿化合物。该粘着剂甚至在高温下仍具有高强度。
上述技术方案虽解决了涂料和粘着剂在高温下的老化和机械性能下降问题,但它们都没有解决涂料和粘着剂的遇热黄变的问题。
CN104387548公开了一种不易黄变的聚氨酯树脂,其由脂肪族聚醚多元醇、脂肪族聚酯多元醇、脂肪族异氰酸酯、脂肪族扩链剂和抗氧化剂来制备。
JP2009143765公开了一种玻璃纤维上浆成型用的粘着剂,该粘着剂在高温条件下不易黄变。该粘着剂包含焦磷酸盐和聚氨酯,其中焦磷酸盐的量为基于聚氨酯固体的重量计10重量% -75重量%。
CN106928422公开了一种制备耐黄变的聚氨酯的方法,包含步骤:(1)二异氰酸酯和二醇在催化剂存在下反应得到反应物;(2)将反应物与扩链剂反应得到扩链后的产品;(3)将扩链后的产品与环氧树脂反应得到耐黄变的聚氨酯产品。
US7091280公开了一种粘着剂,包含水性聚氨酯分散体和稳定剂。该粘着剂是耐黄变的。
因此,希望开发一种组合物,其形成的涂层具有良好的耐黄变性。
发明内容
本发明的目的是提供一种组合物,特别是一种耐黄变的涂料和粘着剂,其制备和应用,以及用该组合物涂覆得到的产品。
根据本发明的组合物包含:
(a)聚氨酯聚合物,所述聚氨酯聚合物是包含下列组分的反应产物:
(a1)多异氰酸酯,
(a2)具有异氰酸酯反应性基团的化合物,所述具有异氰酸酯反应性基团的化合物包含聚合物多元醇,所述聚合物多元醇选自下列的一种或多种:聚醚多元醇和聚烯烃多元醇,
(a3)任选的乳化剂,
(a4)任选的溶剂,和
(a5)任选的反应性稀释剂;
(b)有机抗氧化剂,所述抗氧化剂的量为0.01重量%-2.4重量%,基于所述组合物的固体组分的总重量计;
(c)螯合剂;
(d)水;
(e)任选的稳定剂;
(f)任选的交联剂;和
(g)任选的添加剂。
在本发明的一个方面中,提供了根据本发明所提供的组合物的制备方法,包含以下步骤:以任意方式混合所述聚氨酯聚合物(a)或制备所述聚氨酯聚合物的组分、有机抗氧化剂(b)、螯合剂(c)、水(d)、任选的稳定剂(e)、任选的交联剂(f)和任选的添加剂(g)。
在本发明的又一个方面中,将根据本发明所提供的组合物用于制备涂覆产品的用途。
在本发明的再一个方面中,提供了一种涂覆方法,包含以下步骤:将根据本发明所提供的组合物施加到基材表面,随后将其固化。
在本发明的还一个方面中,提供了一种涂覆产品,包含基材以及通过将根据本发明所提供的组合物施加到所述基材上形成的涂层。
在本发明的还一个方面中,提供了制造粘接产品的方法,包含以下步骤:
i. 将根据本发明的组合物施加到基材的至少一个表面;
ii. 加热并干燥施加有组合物的基材表面;和
iii. 使在步骤ii中处理过的基材表面与所述基材自身或一另外的基材的表面接触,得到所述粘接产品。
在本发明的还一个方面中,提供了一种通过根据本发明所提供的方法制造的粘接产品。
根据本发明的组合物具有良好的耐黄变性。
发明详述
本发明提供一种组合物,包含:
(a)聚氨酯聚合物,所述聚氨酯聚合物是包含下列组分的反应产物:
(a1)多异氰酸酯,
(a2)具有异氰酸酯反应性基团的化合物,所述具有异氰酸酯反应性基团的化合物包含聚合物多元醇,所述聚合物多元醇选自下列的一种或多种:聚醚多元醇和聚烯烃多元醇,
(a3)任选的乳化剂,
(a4)任选的溶剂,和
(a5)任选的反应性稀释剂;
(b)有机抗氧化剂,所述抗氧化剂的量为0.01重量%-2.4重量%,基于所述组合物的固体组分的总重量计;
(c)螯合剂;
(d)水;
(e)任选的稳定剂;
(f)任选的交联剂;和
(g)任选的添加剂。本发明还提供了该组合物的制备方法和应用,特别是在涂料和粘着剂领域中,以及使用该组合物涂覆的产品。
本文所用的术语“固化”是指液体组合物从液态到固化态的过程。
本文所用的术语“组合物”是指将在施加时固化并形成涂层的化学组分的混合物。根据本发明的组合物可以是涂料或粘着剂。
本文所用的术语“涂料”是指能够用不同的涂覆工艺施加在物体表面,形成具有一定强度的牢固且连续的固态涂层的组合物。
本文所用的术语“粘着剂”是指能够用不同的涂覆工艺施加在物体表面,在物体自身的表面上或在一物体与另一物体的表面上形成涂层,并将物体自身的表面或一物体与另一物体的表面粘合的组合物。也用作胶黏剂和/或密封剂和/或粘合剂的同义词。
聚氨酯聚合物(a)
本文所用的术语“聚氨酯聚合物”是指聚氨酯脲聚合物和/或聚氨酯聚脲聚合物和/或聚脲聚合物和/或聚硫氨酯聚合物。
所述聚氨酯聚合物优选不包含可水解基团。
本文所用的术语“可水解基团”是指聚酯基团、聚碳酸酯基团和聚酸酐基团。
多异氰酸酯(a1)
所述多异氰酸酯的官能度优选不小于2,进一步优选2-4。
所述多异氰酸酯的量优选5重量%-70重量%,进一步优选5重量%-40重量%,更优选5重量%-35重量%,最优选10重量%-30重量%,基于制备所述聚氨酯聚合物的组分的总重量计。
所述多异氰酸酯优选下列的一种或多种:脂肪族多异氰酸酯、脂环族多异氰酸酯、芳香族多异氰酸酯,以及它们的具有亚氨基噁二嗪二酮、异氰脲酸酯、脲二酮、氨基甲酸酯、脲基甲酸酯、缩二脲、脲、噁二嗪三酮、噁唑烷酮、酰基脲和/或碳二亚胺基团的衍生物。
所述脂肪族多异氰酸酯优选下列的一种或多种: 1,6-己二异氰酸酯、2,2-二甲基戊二异氰酸酯、2,2,4-三甲基己二异氰酸酯、丁烯二异氰酸酯、1,3-丁二烯-1,4-二异氰酸酯、2,4,4-三甲基-1,6-己二异氰酸酯、1,6,11-十一烷三异氰酸酯、1,3,6-六亚甲基三异氰酸酯、1,8-二异氰酸根合-4-异氰酸根合甲基辛烷、双(异氰酸根合乙基)碳酸酯、双(异氰酸根合乙基)醚、赖氨酸甲酯二异氰酸酯、赖氨酸三异氰酸酯、双(异氰酸根合甲基)硫醚、双(异氰酸根合乙基)硫醚、双(异氰酸根合丙基)硫醚、双(异氰酸根合己基)硫醚、双(异氰酸根合甲基)砜、双(异氰酸根合甲基)二硫醚、双(异氰酸根合乙基)二硫醚、双(异氰酸根合丙基)二硫醚、双(异氰酸根合甲硫基)甲烷、双(异氰酸根合乙硫基)甲烷、双(异氰酸根合甲硫基)乙烷、双(异氰酸根合乙硫基)乙烷、1,5-二异氰酸根合-2-异氰酸根合甲基-3-硫杂戊烷、1,2,3-三(异氰酸根合甲硫基)丙烷、1,2,3-三(异氰酸根合乙硫基)丙烷、3,5-二硫杂-1,2,6,7-庚烷四异氰酸酯、2,6-二异氰酸根合甲基-3,5-二硫杂-1,7-庚烷二异氰酸酯、2,5-二异氰酸根合甲基噻吩、异氰酸根合乙硫基-2,6-二硫杂-1,8-辛烷二异氰酸酯、硫代双(3-异硫氰酸根合丙烷)、硫代双(2-异硫氰酸根合乙烷)、二硫代双(2-异硫氰酸根合乙烷)、六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯,最优选下列的一种或多种:1,6-己二异氰酸酯和六亚甲基二异氰酸酯。
所述脂环族多异氰酸酯优选下列的一种或多种:2,5-双(异氰酸根合甲基)-二环[2.2.1]庚烷、2,6-双(异氰酸根合甲基)-二环[2.2.1]庚烷、双(异氰酸根合甲基)环己烷、异佛尔酮二异氰酸酯、2,5-二异氰酸根合四氢噻吩、2,5-二异氰酸根合甲基四氢噻吩、3,4-二异氰酸根合甲基四氢噻吩、2,5-二异氰酸根合-1,4-二噻烷、2,5-二异氰酸根合甲基-1,4-二噻烷、4,5-二异氰酸根合-1,3-二硫杂环戊烷、4,5-双(异氰酸根合甲基)-1,3-二硫杂环戊烷、4,5-二异氰酸根合甲基-2-甲基-1,3-二硫杂环戊烷、降冰片烷二异氰酸酯(NBDI)、苯二亚甲基二异氰酸酯(XDI)、氢化苯二亚甲基二异氰酸酯(H6XDI)、1,4-环己基二异氰酸酯 (H6PPDI)、1,5-戊二异氰酸酯(PDI)、间-四甲基苯二甲基二异氰酸酯(m-TMXDI),亚甲基双(4-环己基异氰酸酯)和环己烷二异硫氰酸酯,最优选下列的一种或多种:异佛尔酮二异氰酸酯和亚甲基双(4-环己基异氰酸酯)。
所述芳香族多异氰酸酯优选下列的一种或多种:1,2-二异氰酸根合苯、1,3-二异氰酸根合苯、1,4-二异氰酸根合苯、2,4-二异氰酸根合甲苯、乙基苯二异氰酸酯、异丙基苯二异氰酸酯、甲苯二异氰酸酯、二乙基苯二异氰酸酯、二异丙基苯二异氰酸酯、三甲基苯三异氰酸酯、苯三异氰酸酯、联苯二异氰酸酯、甲苯胺二异氰酸酯、4,4’-亚甲基双(异氰酸苯酯)、4,4’-亚甲基双(2-甲基苯基异氰酸酯)、联苄-4,4’-二异氰酸酯、双(异氰酸根合苯基)乙烯、双(异氰酸根合甲基)苯、双(异氰酸根合乙基)苯、双(异氰酸根合丙基)苯、α,α,α’,α’-四甲基苯二甲撑二异氰酸酯、双(异氰酸根合丁基)苯、双(异氰酸根合甲基)萘、双(异氰酸根合甲基苯基)醚、双(异氰酸根合乙基)邻苯二甲酸酯、2,6-二(异氰酸根合甲基)呋喃、2-异氰酸根合苯基-4-异氰酸根合苯基硫醚、双(4-异氰酸根合苯基)硫醚、双(4-异氰酸根合甲基苯基)硫醚、双(4-异氰酸根合苯基)二硫醚、双(2-甲基-5-异氰酸根合苯基)二硫醚、双(3-甲基-5-异氰酸根合苯基)二硫醚、双(3-甲基-6-异氰酸根合苯基)二硫醚、双(4-甲基-5-异氰酸根合苯基)二硫醚、双(4-甲氧基-3-异氰酸根合苯基)二硫醚、1,2-二异硫氰酸根合苯、1,3-二异硫氰酸根合苯、1,4-二异硫氰酸根合苯、2,4-二异硫氰酸根合甲苯、2,5-二异硫氰酸根合-间二甲苯、4,4’-亚甲基双(异硫氰酸苯酯)、4,4’-亚甲基双(2-甲基苯基异硫氰酸酯)、4,4’-亚甲基双(3-甲基苯基异硫氰酸酯)、4,4’-二异硫氰酸根合二苯甲酮、4,4’-二异硫氰酸根合-3,3’-二甲基二苯甲酮、双(4-异硫氰酸根合苯基)醚、1-异硫氰酸根合-4-[(2-异硫氰酸根合)磺酰基]苯、硫代双(4-异硫氰酸根合苯)、磺酰基(4-异硫氰酸根合苯)、氢化甲苯二异氰酸酯(H6TDI)、二苯甲烷二异氰酸酯和二硫代双(4-异硫氰酸根合苯),最优选下列的一种或多种:甲苯二异氰酸酯、1,2-二异氰酸根合苯、1,3-二异氰酸根合苯、1,4-二异氰酸根合苯、二苯甲烷二异氰酸酯和2,4-二异氰酸根合甲苯。
所述多异氰酸酯也可以具有异氰酸酯基团和异硫氰酸酯基团,例如1-异氰酸根合-6-异硫氰酸根合己烷、1-异氰酸根合-4-异硫氰酸根合环己烷、1-异氰酸根合-4-异硫氰酸根合苯、4-甲基-3-异氰酸根合-1-异硫氰酸根合苯、2-异氰酸根合-4,6-二异硫氰酸根合-1,3,5-三嗪、4-异氰酸根合苯基-4-异硫氰酸根合苯基硫醚和2-异氰酸根合乙基-2-异硫氰酸根合乙基二硫醚 。
所述多异氰酸酯还可以是上述多异氰酸酯的卤素取代物,例如氯取代物、溴取代物、烷基取代物、烷氧基取代物、硝基取代物或硅烷取代物如异氰酸根合丙基三乙氧基硅烷或异氰酸根合丙基三甲氧基硅烷 。
具有异氰酸酯反应性基团的化合物(a2)
本文所用的术语“异氰酸酯反应性基团”是指含Zerevitinov-活性氢的基团。Zerevitinov-活性氢定义在Rompp’s Chemical Dictionary (Rommp Chemie Lexikon),10th ed.,Georg Thieme Verlag Stuttgart,1996中。通常,含Zerevitinov-活性氢的基团在本领域中被理解为是指羟基(OH)、氨基(NHx)和硫醇基(SH)。
所述具有异氰酸酯反应性基团的化合物的量优选5重量%-95重量%,优选10重量%-90重量%,基于制备所述聚氨酯聚合物的组分的总重量计。
所述聚合物多元醇的量优选70重量%-100重量%,进一步优选75重量%-100重量%,再优选80重量%-100重量%,最优选90重量%-100重量%,基于所述具有异氰酸酯反应性基团的化合物的总重量计。
所述具有异氰酸酯反应性基团的化合物优选不包含可形成可水解基团的基团。
本文中的术语“可形成可水解基团的基团”是指酯基、碳酸酯基、酰胺基和酸酐基。
所述聚合物多元醇优选聚醚多元醇。
所述聚醚多元醇的羟基官能度优选1.5-6.0,最优选1.8-3.0。
所述聚醚多元醇的羟值优选50 mgKOH/g -700mg KOH/g,最优选50 KOH/g -600mg KOH/g。
所述聚醚多元醇的数均分子量优选400 g/mol -4000g/mol,最优选500 g/mol -3000g/mol。
所述聚醚多元醇优选下列的一种或多种:环氧烷的加聚产物、多元醇或多元醇混合物的缩合产物,和多官能醇、胺和氨基醇的烷氧基化产物,进一步优选多官能醇、胺和氨基醇的烷氧基化产物,最优选下列的一种或多种:具有400 g/mol -4000g/mol数均分子量的聚(环氧丙烷)多元醇和具有400 g/mol -4000g/mol数均分子量的聚氧化四亚甲基多元醇。
所述环氧烷的加聚产物优选下列的一种或多种:环氧乙烷、1,2-环氧丙烷、1,2-环氧丁烷、2,3-环氧丁烷、四氢呋喃、苯乙烯或表氯醇的加聚产物,以及他们的共-加聚产物和接枝产物。
所述多官能醇、胺和氨基醇的烷氧基化产物优选羟基官能起始分子例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、己二醇、二甘醇、三羟甲基丙烷、甘油、季戊四醇、山梨糖醇或它们的混合物与环氧丙烷或环氧丁烷的烷氧基化产物。
本文中的具有相应高羟基含量但特别低分子量的聚醚多元醇可以是水溶的。
然而,所述聚醚多元醇特别优选下列的一种或多种:水不可溶的具有500 g/mol -3000g/mol数均分子量的聚(环氧丙烷)多元醇和水不可溶的具有500 g/mol -3000g/mol数均分子量的聚(四亚甲基氧化物)多元醇。
本文中的“水不可溶的多元醇”是指,该多元醇在 23℃下在水中的溶解度是低于10g/ 升,优选低于 5g/ 升。换句话说,在将它在实验中分散在水中时,多元醇沉淀出来。
乳化剂(a3)
本文中的术语“乳化剂”是包含乳化基团或潜在乳化基团的化合物。
所述乳化剂的量为0.1重量% -20重量%,基于制备所述聚氨酯聚合物的组分的总重量计。
所述乳化剂优选包含至少一个异氰酸酯反应性基团和至少一个乳化基团或潜在乳化基团。
所述异氰酸酯反应性基团优选下列的一种或多种:羟基、硫醇基和氨基。
所述乳化基团或潜在乳化基团优选下列的一种或多种:磺酸基、羧酸基、叔氨基和亲水性聚醚。
所述包含磺酸基和/或羧酸基的乳化剂优选下列的一种或多种:包含磺酸基和/或羧酸基的二氨基化合物和包含磺酸基和/或羧酸基的二羟基化合物,进一步优选下列的一种或多种:N-(2-氨基乙基)-2-氨基乙磺酸的、N-(3-氨基丙基)-2-氨基乙磺酸的、N-(3-氨基丙基)-3-氨基丙磺酸基的、N-(2-氨基乙基)-3-氨基丙磺酸的、类似羧酸的、二羟甲基丙酸的或二羟甲基丁酸的钠、钾、锂和叔胺盐,最优选下列的一种或多种:N-(2-氨基乙基)-2-氨基乙磺酸盐和二羟甲基丙酸。
所述磺酸基或羧酸基可以直接以它们的盐形式使用,如磺酸盐或羧酸盐。
所述磺酸基或羧酸基也可以在聚氨酯聚合物制备过程之中或之后通过部分或完全添加中和剂成盐获得。
所述用于成盐的中和剂优选下列的一种或多种:三乙胺、二甲基环己胺、乙基二异丙基胺、氨、二乙醇胺、三乙醇胺、二甲基乙醇胺、氢氧化钠、氢氧化钾、氢氧化锂、氢氧化钙、甲基二乙醇胺和氨基甲基丙醇,最优选下列的一种或多种:三乙胺、二甲基环己胺和乙基二异丙基胺。
溶剂(a4)
所述溶剂的量为0.001重量% -20重量%,基于制备所述聚氨酯聚合物的组分的总重量计。
所述溶剂优选下列的一种或多种:丙酮、2-丁酮、四氢呋喃、二甲苯、甲苯、环己烷、乙酸丁酯、乙酸二噁烷,乙酸甲氧基丙酯、N-甲基吡咯烷酮、N-乙基吡咯烷酮、乙腈、二丙二醇二甲醚和含有醚或酯单元的溶剂,最优选下列的一种或多种:丙酮和2-丁酮。
所述溶剂可以只在制备开始时添加,或可以根据需要在制备过程中再加入一部分。
反应性稀释剂(a5)
所述反应性稀释剂的量为0.001重量% -90重量%,基于制备所述聚氨酯聚合物的组分的总重量计。
所述反应性稀释剂优选下列的一种或多种:丙烯酸和丙烯酸酯。
所述丙烯酸酯优选甲基丙烯酸酯。
外乳化剂(a6)
所述制备所述聚氨酯聚合物的组分还可以进一步包含外乳化剂(a6)。
所述外乳化剂组分的量为0.001重量%-10重量%,基于制备所述聚氨酯聚合物的组分的总重量计。
所述外乳化剂优选脂肪醇聚醚,最优选下列的一种或多种:脂肪族乙二醇聚醚和脂肪族丙二醇聚醚。
所述聚氨酯聚合物的量优选10重量%-99.5重量%,基于所述组合物的固体组分的总重量计。
所述聚氨酯聚合物的量最优选90重量%-99.5重量%,基于所述组合物的固体组分的总重量计。
所述聚氨酯聚合物可以以固体形式加入,或者可以先与组合物的水混合形成水性聚氨酯分散体后以分散体形式加入,最优选直接以分散体形式加入。
有机抗氧化剂(b)
所述有机抗氧化剂(b)的量优选0.06重量%-2.0重量%,基于所述组合物的固体组分的总重量计。
所述有机抗氧化剂优选下列的一种或多种:金属的氨基甲酸类化合物、 酚型抗氧剂、胺型抗氧剂和杂环类抗氧剂,最优选酚型抗氧剂。
所述金属优选下列的一种或多种:铜、锌、钼和锑。
所述酚型抗氧剂优选下列的一种或多种:烷基受阻酚、多环受阻酚和烷基硫代受阻酚。
所述胺型抗氧剂优选下列的一种或多种:苯二胺类抗氧剂、二苯胺类抗氧剂、苯基-α-萘胺类抗氧剂和吩噻嗪类抗氧剂。
所述杂环类抗氧剂优选下列的一种或多种:含硫化合物和含氮杂环化合物。
螯合剂(c)
本文中的术语“螯合剂”是指能够与金属离子,特别是重金属离子或过渡金属离子形成稳定复合物的化合物。
所述螯合剂的量优选0.04重量%-1.8重量%,进一步优选0.04重量-1重量%,再一步优选0.05重量%-1重量%,最优选0.1重量%-1重量%,基于所述组合物的固体组分的总重量计。
所述螯合剂优选以下列的一种或多种形式存在:螯合剂盐、螯合剂酸和螯合剂酯,进一步优选以螯合剂盐和/或螯合剂酸形式存在,最优选以螯合剂盐形式存在。
所述螯合剂盐优选螯合剂水溶性盐。
所述螯合剂水溶性盐在水中的溶解度优选不小于0.15g/100g水,最优选不小于1g/100g水,在室温20℃下测得。
所述螯合剂水溶性盐优选满足以下条件:螯合剂水溶性盐的含量为4.3*10-7mol/g的水溶液的pH值大于5,优选大于6,最优选大于9。
所述螯合剂水溶性盐优选下列的一种或多种:乙二胺四乙酸盐、酒石酸盐、柠檬酸盐、焦磷酸盐、三聚磷酸盐、六偏磷酸盐、氨基三亚甲基膦酸、乙二胺四亚甲基膦酸、二乙三胺五亚甲基膦酸和葡萄糖酸盐,进一步优选下列的一种或多种:乙二胺四乙酸盐、酒石酸盐、柠檬酸盐、焦磷酸盐、三聚磷酸盐、六偏磷酸盐和葡萄糖酸盐,最优选下列的一种或多种:乙二胺四乙酸盐和焦磷酸盐。
所述乙二胺四乙酸盐优选乙二胺四乙酸四钠。
所述焦磷酸盐优选焦磷酸钠。
所述螯合剂酸在水中可以是不溶的,或者可以是可溶的。
所述螯合剂酸的pH值优选1-6。
所述螯合剂酸优选下列的一种或多种:氨基羧酸、羟基羧酸、无机聚磷酸、羟氨基羧酸、有机多元膦酸和聚羧酸,进一步优选下列的一种或多种:乙二胺四乙酸、次氮基三乙酸、酒石酸、柠檬酸、焦磷酸、三聚磷酸、六偏磷酸和葡萄糖酸,再优选下列的一种或多种:乙二胺四乙酸、次氮基三乙酸、酒石酸、柠檬酸、焦磷酸和葡萄糖酸,最优选下列的一种或多种:乙二胺四乙酸和次氮基三乙酸。
所述氨基羧酸优选次氨基三乙酸。
稳定剂(e)
所述组合物可以进一步包含稳定剂。所述稳定剂有利地减少组合物的水解,从而延长组合物的适用期。
本文所用的术语“适用期”是指组合物的两种或更多种相互反应性组分的最初混合到所得组合物在使用合适的具有C50-1心轴的Brookfield R/S流变仪根据ASTM标准D7395-07测量时具有2500cps的在25℃下的粘度时的时间段。
所述稳定剂优选下列的一种或多种:碳二亚胺类化合物、环氧化合物、噁唑啉类化合物和氮丙啶类化合物。
所述稳定剂的含量优选0.5重量% -10重量%,最优选0.5重量%-2重量%,基于所述组合物的固体组分的总重量计。
交联剂(f)
所述组合物可以进一步包含交联剂。
所述交联剂优选下列的一种或多种:含异氰酸酯基团的化合物和含聚碳化二亚胺基团的化合物。
所述交联剂的含量优选0.1重量%-10重量%,基于所述组合物的固体组分的总重量计。
添加剂(g)
所述组合物可以进一步包含添加剂。所述添加剂优选下列的一种或多种:助粘合剂、增稠剂、粘合促进剂、润滑剂、润湿添加剂、染料、光稳定剂、老化抑制剂、颜料、流动控制剂、抗静电剂、UV吸收剂、成膜助剂、消泡剂和塑化剂。
所述添加剂的量可以是本领域的技术人员熟知的量。
不同于所述聚氨酯聚合物的聚合物(h)
所述组合物可以进一步包含不同于所述聚氨酯聚合物的聚合物。
所述不同于所述聚氨酯聚合物的聚合物优选不包含可水解基团。
所述不同于所述聚氨酯聚合物的聚合物与聚氨酯聚合物的重量比优选为1:10-10:1。
所述组合物优选是涂料或粘着剂,进一步优选粘着剂,最优选耐黄变的粘着剂。
组合物的制备方法
优选所述聚氨酯聚合物(a)和水(d)形成水性聚氨酯分散体,然后引入所述有机抗氧化剂(b)、螯合剂(c)、任选的稳定剂(e)、任选的交联剂(f)和任选的添加剂(g)得到所述组合物。
优选所述聚氨酯聚合物(a)和水(d)形成水性聚氨酯分散体,然后引入所述有机抗氧化剂(b)、螯合剂(c)、任选的稳定剂(e)、任选的交联剂(f)、任选的添加剂(g)和任选的不同于所述聚氨酯聚合物的聚合物(h)得到所述组合物。
所述组合物中的水可以在聚氨酯聚合物形成前引入,也可以在聚氨酯聚合物形成过程中引入,或者可以在聚氨酯聚合物形成后引入。所述水优选在聚氨酯聚合物形成后引入。
所述水和聚氨酯聚合物混合形成水性聚氨酯分散体。
术语“水性聚氨酯分散体”也用作水性聚氨酯脲分散体和/或水性聚氨酯聚脲分散体和/或水性聚脲分散体的同义词。
制备所述聚氨酯聚合物时可以添加催化剂,例如二月桂酸二丁基锡。
所述聚氨酯聚合物优选通过预聚物混合法、丙酮法或熔体分散法制备,最优选使用丙酮法制备。
所述聚氨酯聚合物的各组分的混合顺序可以按照常规的方式进行。
所述多异氰酸酯和具有异氰酸酯反应性基团的化合物可以一次性加入或分多次加入,可以与之前加入的是相同成分或不同成分。
存在于聚氨酯聚合物中的有机溶剂可以通过蒸馏除去。所述有机溶剂可以在聚氨酯聚合物形成过程中移除,或者可以在聚氨酯聚合物形成后移除。
所述聚氨酯聚合物中残留的有机溶剂的量优选低于1.0重量%,基于聚氨酯聚合物的总重量计。
所述螯合剂可以以固体或水溶液形式加入。优选以螯合剂的水溶液形式加入,这样将更有利于螯合剂的分散。
所述螯合剂水溶性盐可以直接加入,或者可以通过酸碱中和的形式在组合物中形成。所述酸碱中和可以是完全或部分中和,优选完全中和。
所述螯合剂可以在制备聚氨酯聚合物的扩链或中和过程中加入,或者可以在扩链后加入、或者可以在聚氨酯聚合物分散在水中的过程中或分散后加入、或者可以在聚氨酯聚合物的蒸馏过程中或蒸馏后加入。
所述酸可以是自由酸,能与碱发生中和反应形成螯合剂水溶性盐。所述自由酸优选下列的一种或多种:氨基羧酸、羟基羧酸、无机聚磷酸、羟氨基羧酸、有机多元膦酸和聚羧酸。
所述氨基羧酸优选下列的一种或多种:乙二胺四乙酸和/或氨基三乙酸。
所述羟基羧酸优选下列的一种或多种:酒石酸、柠檬酸和葡萄糖酸。
所述无机聚磷酸优选下列的一种或多种:三聚磷酸、六偏磷酸和焦磷酸。
所述羟氨基羧酸优选下列的一种或多种:羟乙基乙二胺三乙酸和/或二羟乙基甘氨酸。
所述水性聚氨酯分散体的固体含量优选 30重量% -70重量%,以所述水性聚氨酯分散体的量为100重量%计。
涂覆方法
所述基材优选下列的一种或多种:木材、塑料、金属、玻璃、纺织品、合金、织物、人造革、纸张、卡纸、EVA、橡胶、真皮、玻璃纤维、乙烯乙酸乙烯酯共聚物、聚烯烃、 热塑性聚氨酯、聚氨酯泡棉、聚合物纤维和石墨纤维,最优选下列的一种或多种:EVA、橡胶、真皮、人造革、乙烯乙酸乙烯酯共聚物、聚烯烃、 热塑性聚氨酯和聚氨酯泡棉。
所述“施加”可以是将所述粘着剂施加到所述基材的整个表面上或仅施加到所述基材的表面的一个或多个部分上。
所述“施加”可以是刷涂、浸渍、喷雾、辊涂、刮刀涂布、流涂、浇注、印刷或转印,优选刷涂、浸渍或喷雾。
制造粘接产品的方法
所述方法在步骤ii和步骤iii之间优选进一步包含步骤iv:
iv. 用光化辐射照射在步骤ii中处理过的基材表面。
所述制造粘接产品的方法,优选包含以下步骤:
i. 将根据本发明提供的粘着剂施加到基材的至少一个表面;
ii. 加热并干燥施加有粘着剂的基材表面;
iv. 用光化辐射照射在步骤ii中处理过的基材表面;和
iii. 使在步骤iv中处理过的基材表面与所述基材自身或一另外的基材的表面接触,得到所述粘接产品。
所述基材优选下列的一种或多种:木材、塑料、金属、玻璃、纺织品、合金、织物、人造革、纸张、卡纸、EVA、橡胶、真皮、玻璃纤维、乙烯乙酸乙烯酯共聚物、聚烯烃、 热塑性聚氨酯、聚氨酯泡棉、聚合物纤维和石墨纤维,最优选下列的一种或多种:EVA、橡胶、真皮、人造革、乙烯乙酸乙烯酯共聚物、聚烯烃、 热塑性聚氨酯和聚氨酯泡棉。
所述“施加”可以是将所述粘着剂施加到所述基材的整个表面上或仅施加到所述基材的表面的一个或多个部分上。
所述“施加”可以是刷涂、浸渍、喷雾、辊涂、刮刀涂布、流涂、浇注、印刷或转印,优选刷涂、浸渍或喷雾。
所述“加热并干燥施加有粘着剂的基材表面”可以是指仅加热并干燥基材表面,或者可以指加热并干燥包括施加有粘着剂的基材表面在内的部分基材或全部基材。
所述“加热并干燥”可以除去易挥发组分。所述易挥发组分可以是水。
所述“加热并干燥”优选下列的一种或多种:红外热辐射、近红外热辐射、微波和在温度升高的条件下用对流炉或喷雾干燥器。
所述加热的温度尽可能高,但不应当高于基材以不可控方式变形或遭遇其它破坏的温度界限。
所述光化辐射照射优选在所述在步骤ii中处理过的基材表面温度不低于35℃时进行,最优选在步骤ii中的处理后立即进行。
所述“光化辐射照射在步骤ii中处理过的基材表面”可以是指仅照射基材表面,或者可以指照射包括基材表面在内的部分基材或全部基材。
所述光化辐射使粘着剂结晶并固化。
所述光化辐射优选UV辐射、日光辐射、在不存在氧的情况下用惰性气体或贫氧气体进行辐射或用对辐射透明的介质覆盖需照射的部位进行辐射,最优选UV辐射或日光辐射。
所述惰性气体优选氮气或二氧化碳。所述对辐射透明的介质优选合成膜、玻璃或液体例如水。
在所述UV辐射或日光辐射中可以用中压或高压汞蒸气灯,并任选地掺杂其它元素,如镓或铁来改性汞蒸气,或者可以用激光、脉冲灯、卤素灯或准分子辐射器。
所述光化辐射最优选UV辐射。所述UV辐射中最优选使用固定安装的汞辐射。
当基材具有复杂形状的三维表面时,优选使用多个辐射装置进行辐射,合理布置辐射装置以使得表面均匀接受辐射。
所述光化辐射的波长优选200nm-750nm。
所述光化辐射的剂量优选不小于80 mJ/cm2,进一步优选是80 mJ/cm2-5000 mJ/cm2,再优选是200 mJ/cm2-2000 mJ/cm2,最优选是1250mJ/cm2-1950mJ/cm2。
在上述范围内,光化辐射的辐射剂量尽可能高,但不应当高于基材以不可控方式变形或遭遇其它破坏的辐射剂量界限。
所述接触优选是在基材表面的温度降低到粘着剂可粘合温度以下前进行,进一步优选是在基材表面温度不低于60℃前进行的。
所述在步骤iv中处理过的基材表面优选在一小时内,进一步优选30分钟内,再优选在10分钟内,最优选在5分钟内与所述基材自身或一另外的基材接触得到所述粘接产品。
所述另外的基材可以是需要粘合的任何基材。
所述另外的基材与所述基材可以相同,或者可以不相同。
所述另外的基材优选和所述基材一样经过涂布、加热和光化辐射处理。
所述另外的基材与所述基材表面接触之前优选没有用底漆、高能辐射或臭氧处理过。
所述高能辐射可以是电离辐射,特别是等离子体。
使所述在步骤ii中处理过的或在步骤iv中处理过的基材表面与所述基材自身或所述另外的基材接触后,还可以进一步进行热处理。
使所述在步骤ii中处理过的或在步骤iv中处理过的基材表面与所述基材自身或所述另外的基材接触后,还可以进一步进行冷却处理,使所述粘接产品的温度降至室温。
所述引入热的方法优选下列的一种或多种:在温度升高的条件下用对流炉或喷雾干燥器、红外热辐射、近红外热辐射、微波和与涂有本发明的粘着剂的基材接触的物体来传递热。
在步骤ii中处理过的或在步骤iv中处理过的基材表面与所述基材自身或另外的基材接触之前,优选不需要引入热至基材表面。
粘接产品
所述粘接产品优选鞋。
实施例
除非另外限定,本文所使用的所有技术和科学术语具有本发明所属领域技术人员通常理解的相同意义。当本说明书中术语的定义与本发明所属领域技术人员通常理解的意义有矛盾时,以本文中所述的定义为准。
除非另有说明,否则在说明书和权利要求书中使用的表达成分的量、反应条件等的所有数值被理解为在被术语“约”修饰。因此,除非有相反指示,否则在这里阐述的数值和参数是能够根据需要获得的所需性能来变化的近似值。
本文中所用的“和/或”是指所提及的要素之一或全部。
本文中所用“包含”、“包括”和“含有”涵盖只有所提及要素的情形以及除了所提及要素还存在其它未提及要素的情形。
本发明中所有百分比均为重量百分比,另有说明的除外。
本发明的分析和测量都在23℃的温度下进行,另有说明的除外。
除非另有说明,否则在本说明书中所用的“一”、“一种”、“一个”和“该”意在包括“至少一种”或“一种或多种”。例如,“一组分”是指一种或多种组分,因此在所述实施方案的实施中可能考虑并可能采用或使用多于一种组分。
水性聚氨酯分散体的固体含量使用Mettler Toledo的HS153水分分析仪根据DIN-EN ISO 3251进行。
异氰酸酯基团(NCO)含量根据DIN-EN ISO 11909按体积测定,测定的数据包括游离的和潜在游离的NCO含量。
异氰酸酯官能度根据GPC测定。
pH值使用德国Sartorius的PB-10pH计在23℃下测量。
数均分子量通过凝胶渗透色谱法使用四氢呋喃作为流动相,对照聚苯乙烯标样在23℃下测定。
羟值根据ASTM D4274测定。
原料和试剂
Desmophen®3600:低官能度聚醚多元醇,官能度为2,数均分子量2000g/mol,羟值56 mg KOH/g,可购自德国科思创股份有限公司。
Desmodur®T-80:甲苯二异氰酸酯混合物,可购自德国科思创股份有限公司。
乙二胺四乙酸四钠盐(EDTA4Na):其乙二胺四乙酸四钠盐的含量为4.3*10-7 mol/g的水溶液的pH值为10.35,可购自国药集团化学试剂有限公司,室温20℃时测得的其溶解度为 100g/100g。
焦磷酸钠:其焦磷酸钠的含量为4.3*10-7 mol/g的水溶液的pH值为9.89,可购自国药集团化学试剂有限公司,室温20℃时测得的其溶解度为 6.2g/100g。
次氮基三乙酸:次氮基三乙酸的含量为4.3*10-7 mol/g的水溶液的pH值为2.92,可购自国药集团化学试剂有限公司,室温20℃时测得的其溶解度为 <0.01g/100g。
2,6-二叔丁基-4-甲基苯酚:有机抗氧化剂,可购自默克化学。
发明实施例和对比实施例中的组合物的制备
水性聚氨酯分散体的制备
将380.2g Desmophen®3600在110℃和15 mbar下脱水1小时,添加7.6g 2,2-二羟甲基丙酸并在搅拌的同时冷却。在60℃下添加62.8g Desmodur®T-80,在80-90℃下搅拌直到达到2.1%的异氰酸酯含量。然后将混合物溶解在676g丙酮中并冷却到50℃得到反应溶液。将7.3g 浓度为31%的氢氧化钠的水溶液添加到反应溶液中并搅拌5分钟,随后添加6.8g 2-(2-氨基乙氧基)乙醇在41g水中的溶液。剧烈搅拌30分钟后,添加648g水将该混合物分散,随后蒸馏分离出丙酮,获得水性聚氨酯分散体,固体组分含量为40.1重量%。
组合物的制备
表1示出了发明实施例和对比实施例中的组合物的组成和性能测试结果。
按照表1中所示的量,将有机抗氧化剂、螯合剂与制备的水性聚氨酯分散体混合,并将该混合物搅拌或震荡得到均匀的组合物。
性能测试
耐黄变性测试方法
分别称取20g发明实施例与对比实施例的组合物,倒入平底的特氟龙盘中,存放在室温下得到干涂层。涂层厚度为0.74 mm ±0.08mm。将涂层均匀切成几份,其中一份放入80℃的烤箱内烘烤7小时。剩余的涂层继续存放于常温下,作为颜色变化对比的参照物。
颜色的对比基于CIELAB方法。将样品置于同一白色背景上用BYK色差仪测试L,a,b值。∆b值等于经过高温处理的样品的b值和在室温存放未经过高温处理的相同样品的b值的差值。∆b值越大,样品的黄变程度越大。
性能测试结果示于表1中。
表1:发明实施例和对比实施例中的组合物的组成和性能测试结果
n.b.:组合物絮凝,无法形成涂层。
在比较发明实施例1-5和对比实施例1-7时,可以看出,由使用根据本发明的组合物形成的涂层的∆b值比在对比组合物的情况中小得多小,说明由使用根据本发明的组合物形成的涂层的耐黄变性比在对比组合物的情况中好得多。
对于本领域技术人员显而易见的是,本发明不限于前述的具体细节,且在不脱离本发明的精神或主要特性的前提下,本发明可实施为其他特定形式。因此从所有方面来说都应将所述实施例认为是例示性而非限制性的,从而由权利要求书而非前述说明来指出本发明的范围。因此,任何改变,只要其属于权利要求等效物的含义和范围中,都应视作属于本发明。
Claims (19)
1.一种组合物,包含:
(a)聚氨酯聚合物,所述聚氨酯聚合物是包含下列组分的反应产物:
(a1)多异氰酸酯,
(a2)具有异氰酸酯反应性基团的化合物,所述具有异氰酸酯反应性基团的化合物包含聚合物多元醇,所述聚合物多元醇选自下列的一种或多种:聚醚多元醇和聚烯烃多元醇,
(a3)任选的乳化剂,
(a4)任选的溶剂,和
(a5)任选的反应性稀释剂;
(b)有机抗氧化剂,所述抗氧化剂的量为0.01重量%-2.4重量%,基于所述组合物的固体组分的总重量计;
(c)螯合剂;
(d)水;
(e)任选的稳定剂;
(f)任选的交联剂;和
(g)任选的添加剂。
2.如权利要求1所述的组合物,其特征在于,所述聚合物多元醇的量是70重量%-100重量%,基于所述具有异氰酸酯反应性基团的化合物(a2)的总重量计。
3.如权利要求1所述的组合物,其特征在于,所述有机抗氧化剂(b)的量为0.06重量%-2.0重量%,基于所述组合物的固体组分的总重量计。
4.如权利要求1所述的组合物,其特征在于,所述螯合剂(c)的量为0.04重量%-1.8重量%,优选0.04重量-1重量%,进一步优选0.05重量%-1重量%,最优选0.1重量%-1重量%,基于所述组合物的固体组分的总重量计。
5.如权利要求1所述的组合物,其特征在于,所述螯合剂(c)以下列的一种或多种形式存在:螯合剂盐和螯合剂酸。
6.如权利要求5所述的组合物,其特征在于,所述螯合剂盐是螯合剂水溶性盐,所述螯合剂水溶性盐选自下列的一种或多种:乙二胺四乙酸盐、酒石酸盐、柠檬酸盐、焦磷酸盐、三聚磷酸盐、六偏磷酸盐和葡萄糖酸盐。
7.如权利要求5所述的组合物,其特征在于,所述螯合剂酸是下列的一种或多种:乙二胺四乙酸、次氮基三乙酸、酒石酸、柠檬酸、焦磷酸和葡萄糖酸。
8.如权利要求1所述的组合物,其特征在于,所述稳定剂(e)是下列的一种或多种:碳二亚胺类化合物、环氧化合物、噁唑啉类化合物和氮丙啶类化合物,所述稳定剂的量是0.5重量%-10重量%,基于所述组合物的固体组分的总重量计。
9.如权利要求1-8任一项所述的组合物,其特征在于,所述组合物是涂料或粘着剂。
10.如权利要求1-9任一项所述的组合物的制备方法,包含以下步骤:以任意方式混合所述聚氨酯聚合物(a)或制备所述聚氨酯聚合物的组分、有机抗氧化剂(b)、螯合剂(c)、水(d)、任选的稳定剂(e)、任选的交联剂(f)和任选的添加剂(g)。
11.如权利要求10所述的制备方法,其特征在于,所述聚氨酯聚合物(a)和水(d)形成水性聚氨酯分散体,然后引入所述有机抗氧化剂(b)、螯合剂(c)、任选的稳定剂(e)、任选的交联剂(f)和任选的添加剂(g)得到所述组合物。
12.如权利要求10-11任一项所述的制备方法,其特征在于,所述螯合剂(c)以水溶液形式加入。
13.根据权利要求1-9任一项所述的组合物用于制备涂覆产品的用途。
14.一种涂覆方法,包含以下步骤:将如权利要求1-9任一项所述的组合物施加到基材表面,然后固化。
15.一种涂覆产品,包含基材以及将根据权利要求1-9任一项所述的组合物施加到所述基材上形成的涂层。
16.制造粘接产品的方法,包含以下步骤:
i. 将根据权利要求1-9任一项所述的组合物施加到基材的至少一个表面;
ii. 加热并干燥施加有组合物的基材表面;和
iii. 使在步骤ii中处理过的基材表面与所述基材自身或一另外的基材的表面接触,得到所述粘接产品。
17.如权利要求16所述的方法,其特征在于,其在步骤ii和步骤iii之间进一步包括步骤iv:
iv. 用光化辐射照射在步骤ii中处理过的基材表面。
18.如权利要求16所述的方法,其特征在于,所述基材优选下列的一种或多种:木材、塑料、金属、玻璃、纺织品、合金、织物、人造革、纸张、卡纸、EVA、橡胶、真皮、玻璃纤维、乙烯乙酸乙烯酯共聚物、聚烯烃、 热塑性聚氨酯、聚氨酯泡棉、聚合物纤维和石墨纤维。
19.一种根据权利要求16-18任一项所述的方法制造的粘接产品。
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CN201810978328.9A CN110857329A (zh) | 2018-08-24 | 2018-08-24 | 一种聚氨酯组合物及其制备方法和应用 |
CN2018109783289 | 2018-08-24 | ||
EP18201270.8A EP3640271A1 (en) | 2018-10-18 | 2018-10-18 | A polyurethane composition, preparation method and application thereof |
EP18201270.8 | 2018-10-18 | ||
PCT/EP2019/072368 WO2020078604A1 (en) | 2018-08-24 | 2019-08-21 | A polyurethane composition, preparation method and application thereof |
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