CN1224754C - 特殊硬化剂在用于涂覆柔性衬底的2组分pu体系中的应用 - Google Patents
特殊硬化剂在用于涂覆柔性衬底的2组分pu体系中的应用 Download PDFInfo
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- CN1224754C CN1224754C CN 02126515 CN02126515A CN1224754C CN 1224754 C CN1224754 C CN 1224754C CN 02126515 CN02126515 CN 02126515 CN 02126515 A CN02126515 A CN 02126515A CN 1224754 C CN1224754 C CN 1224754C
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- 125000005594 diketone group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
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- 238000005498 polishing Methods 0.000 description 1
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- 229920006254 polymer film Polymers 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
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- 238000011105 stabilization Methods 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
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- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
由粘合剂组分A)和硬化剂组分B)组成的2组分PU体系在涂覆柔性衬底,特别是皮革或织物方面的用途,其特征在于硬化剂组分B)包含式I的天冬氨酸酯:其中,R1和R2彼此独立地相同或不同,并代表C1-C4-烷基,X是下式的基团:其中,A为二价有机基团,Z为含4-18个碳原子的二价脂肪族基团,n为0或1。
Description
技术领域
本发明涉及在用于涂覆柔性衬底如皮革和织物的2组分PU体系中使用特殊硬化剂以产生具有良好动力学强度的涂层的用途。
背景技术
人们本来已知衬底具有聚氨酯的反应涂层。在反应涂层中,将粘合剂(多异氰酸酯)和硬化剂(多胺),两者均任选溶解在一种适当的溶剂中,施用在衬底上,优选使用喷射枪。
在现有技术领域中,将异氰酸酯官能团预聚体(粘合剂)与选定的多胺(硬化剂),例如惰性芳香族多胺或可逆封闭的脂肪族多胺,完全混合然后或者直接喷在待涂覆的衬底上或者优选喷在临时的支撑体上再与待涂覆的衬底,如皮革、纸、非织造布或织物进行层压,将涂覆后的原料运送至一个干燥的槽中以进行涂层的进一步反应。随后将基本上完全反应的原料从非粘性的支撑体上剥离。这种现有技术的代表包括,例如DE-A 1 570 524(US-A 3475266);DE-A 2637115(US-A4 108 842)和DE-A 2826 232。用这种方法涂覆的皮革具有杰出的性能特征;它们易于照料而且更特殊的是拥有非常好的抗挠曲性。
用于这种方法的起始原料必须具有完美的适当反应性和特性曲线。例如,反应体系在加工条件下必须呈粘性足够长的时间以便于在技术上足够长的时间跨距内使衬底被层压上。另一方面,涂层必须迅速干燥以便于使涂覆后的衬底在技术上合理的时间后能从临时非粘性的支撑体上剥离下来。
发明内容
本发明的目的是提供一种能提供具有良好抗挠曲性的涂层的聚氨酯体系,其用于柔性衬底,特别是皮革的反应性涂层。
EP-A 403921描述了一种用于产生基于多异氰酸酯组分并使用天冬氨酸酯作为硬化剂的涂层。这个参考文献主要描述了用于刚性衬底例如金属片、塑料、木材和玻璃的高度交联的涂层,但没有讨论用于柔性衬底的涂层所需的高动力学强度。
已经发现当不仅使用NCO预聚体作为粘合剂,优选其具有一定的NCO含量和限定的官能度,而且使用含有通式I的特殊天冬氨酸酯类硬化剂构成聚脲聚氨酯时,可以达到这个目标:
其中
R1和R2独立地为相同或不同的基团并代表C1-C4-烷基,
X是下面式的基团:
其中
A为二价有机基团,
Z为4-18个碳原子的二价脂族基团,优选-(CH2)6-或-CH2CH(CH3)(CH2)2-。
N为0或1。
特别令人惊讶的是使用式I的特殊天冬氨酸酯类的涂层具有良好的动力学强度(耐挠曲性)。这是一个出乎意料的发现,因为通常使用的胺硬化剂都具有伯氨基并与相应的NCO预聚体复合反应生成高弹性的聚氨酯聚脲,因此非常耐挠曲性负载。相反,根据本发明使用的天冬氨酸酯具有仲胺基;相应的聚氨酯聚脲的弹性明显更弱。相关的技术优势在于根据本发明的应用提供了更软的皮革涂层。这是所期望的,因为这导致涂覆后的皮革具有更自然的外观。
进一步还发现,在根据本发明的方法中,即使在接近于通常用于工业中的1当量比的NCO粘合剂/胺硬化剂的条件下,反应动力学参数或者可直接与已确定的体系相比,或者通过水和/或酸性化合物的催化作用而非常易于调节。
本发明也提供了在用于涂覆柔性衬底,特别是皮革或织物,特别优选皮革的2组分PU体系中含有式I的天冬氨酸酯类的硬化剂组分的应用。
在一个优选的实施方案中,根据本发明的应用的特征在于多NCO官能团的粘合剂A)具有的NCO含量为2-8%,数均分子量为700-8000g/mol并且NCO官能度为2.0-3.0,而胺硬化剂B)含有式I的天冬氨酸酯,前提条件是NCO粘合剂A)与胺组分B)的当量比为1∶1-1.33∶1。
该涂层特别优选通过一种喷射系统应用两组分A和B来施用,其中两组分在该喷射头中进行混合。
粘合剂
用于组分A)的有用的多NCO官能团粘合剂优选芳香族或脂肪族预聚体,该预聚体基于聚酯、聚醚或聚碳酸酯并且具有的NCO含量为2-8%。NCO官能度优选为2.0-3.0,特别为2.2-2.5。
该NCO预聚体A)可以通过将有机多异氰酸酯a)与NCO-反应活性化合物b)反应制备,在这种情况下有用的有机多异氰酸酯a)举例来说包括芳香族或脂肪族聚异氰酸酯。
举例来说,多异氰酸酯a)是式为Q(NCO)n的化合物,该化合物的平均分子量小于800并且其中n为2-4,Q为脂肪族C4-C12烃基、环脂族C6-C15烃基或芳香族C6-C15烃基,例如选自下列物质的二异氰酸酯:4,4’-二异氰酸根合二环己基甲烷,3-异氰酸根合甲基-3,3,5-三甲基环己基异氰酸酯(异佛尔酮二异氰酸酯=IPDI),四亚甲基二异氰酸酯、六亚甲基二异氰酸酯(HDI)、2-甲基五亚甲基二异氰酸酯,2,2,4-三甲基六亚甲基二异氰酸酯(THDI),十二亚甲基二异氰酸酯,1,4-二异氰酸根合环己烷,4,4’二异氰酸根合3,3’二甲基二环己基甲烷,4,4’-二异氰酸根合二环己基(2,2)丙烷,3-异氰酸根合甲基-1-甲基-1-异氰酸根合环己烷(IMCI),1,3-二异氰酸根合4-甲基环己烷,1,3-二异氰酸根合2-甲基环己烷和α,α,α’,α’-四甲基-m-或-p-亚二甲苯基二异氰酸酯(TMXDI)以及它们的混合物。1,3-和1,4-亚苯基二异氰酸酯,2,4-和2,6-甲苯二异氰酸酯以及这些异构体的任一所期望的混合物、位置异构的二苯基甲烷二异氰酸酯和它们的混合物、以及由苯胺-甲醛缩合物的光气化作用获得的多核多异氰酸酯。使用上述异氰酸酯的任一所期望的混合物都是可能的。
优选使用1-异氰酸根合3,3,5-三甲基-5-异氰酸根合甲基环己烷(IPDI),4,4’-二异氰酸根合二环己基甲烷,六亚甲基二异氰酸酯,甲苯二异氰酸酯异构体和二苯基甲烷二异氰酸酯和它们的异构体混合物。特别优选使用芳香族二异氰酸酯。
也可能共用多异氰酸酯,该多异氰酸酯是由脂肪族和芳香族系列的二异氰酸酯通过缩二脲作用、脲基甲酯化作用、三聚作用、二聚作用,也包括用OH官能度>2的短链多元醇进行的氨基甲酯化作用形成的。因此,多异氰酸酯e),在含有NCO基团的同时,也包含缩二脲、脲基甲酯、亚氨基噁二嗪二酮、异氰脲酸酯、脲二酮和脲烷结构单元。这些多异氰酸酯更详细的描述在“Lackarze,Chemie,Eigenschaften undAnwendungen”中,编辑D.Stoye,W.Freitag,Hanser Verlag,Munich,Vienna 1996。这些多异氰酸酯也可以以混合物形式使用。这些多异氰酸酯不仅可以在预聚合作用中共同使用,而且可以顺序加入。这里优选使用芳香族系列的氨基甲酯多异氰酸酯和基于甲苯二异氰酸酯/六亚甲基二异氰酸酯的混合三聚体;在产品为脂肪族系列的情况下,特别优选脲基甲酯、缩二脲、三聚体和三聚体与基于六亚甲基二异氰酸酯的脲二酮的混合物。
优选的NCO-反应活性化合物b)具体来说是多元醇。有用的多元醇包括高分子量以及,少量的低分子量羟基化合物。
高分子量羟基化合物包括通常用于聚氨酯化学的羟基聚脂、羟基polyactones、羟基聚醚、羟基聚硫醚、羟基聚缩醛、羟基聚碳酸酯、二聚脂肪醇和/或酯酰胺,每一种的平均分子量都为400-8000并且优选平均分子量为500-6500g/mol。
有用的低分子量多羟基化合物包括通常用于聚氨酯工业的多元醇,分子量为62-399g/mol,例如乙二醇、三甘醇、四甘醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、1,6-己二醇、1,8-辛二醇、新戊二醇、1,4-二(羟甲基)环己烷,二(羟甲基)三环-[5.2.1.02.6]癸烷或1,4-二(2-羟基乙氧基)苯、2-甲基-1,3-丙二醇、2,2,4-三甲基戊二醇、2-乙基-1,3-己二醇、双丙二醇、聚丙二醇、二丁二醇、聚丁二醇、双酚A、四溴双酚A、甘油、三羟甲基丙烷、1,2,6-己三醇、1,2,4-丁三醇、季戊四醇、对环己二醇、甘露醇、山梨糖醇、甲基糖苷和4,3,6-二酐己糖醇。
有用的聚醚多元醇包括通常用于聚氨酯工业的聚醚,例如四氢呋喃、氧化苯乙烯、环氧乙烷、环氧丙烷、环氧丁烷或表氯醇,特别是环氧乙烷和/或环氧丙烷的加成或混合加成化合物,它们是使用两到六羟基起始分子如水或上述提及的多元醇或含有1-4个NH的胺制备的。
优用的聚酯多元醇举例来说包括多羟基醇,优选二羟基醇和任选的另外的三羟基醇与多元,优选二元羧酸的反应产物。除了游离的多羧酸以外也可使用相应的多羧酸酸酐或相应的多羧酸低级醇酯或它们的混合物来制备聚酯。多羧酸可以是脂肪族、环脂族、芳香族和/或杂环类并任选被如卤素原子取代,和/或是不饱和的。它们的实例有:
己二酸、邻苯二甲酸、间苯二甲酸、丁二酸、辛二酸、壬二酸、癸二酸、偏苯三酸、邻苯二甲酸酐、四氢邻苯二甲酸酐、戊二酸酐、四氯邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、马来酸酐、马来酸、富马酸、二聚和三聚脂肪酸如油酸,任选与单体脂肪酸、对苯二甲酸二甲基酯、对苯二甲酸双乙二醇酯混合。
有用的多羟基醇包括上述提及的多元醇。
所考虑的聚碳酸酯多元醇可以通过碳酸衍生物,例如碳酸二苯酯和碳酰氯,与二醇反应获得。有用的二醇包括,举例来说,乙二醇、三甘醇、四甘醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、新戊二醇、1,4-二(羟甲基)环己烷,二(羟甲基)三环-[5.2.1.02.6]癸烷或1,4-二(2-羟基乙氧基)苯、2-甲基-1,3-丙二醇、2,2,4-三甲基戊二醇、二丙二醇、聚丙二醇、二丁二醇、聚丁二醇、双酚A、四溴双酚A或它们的混合物。优选该二醇组分含有40-100重量%的己二醇,优选1,6-己二醇,和/或己二醇衍生物,优选这些组分不但含有端羟基,还含有醚或酯基,例如通过将1mol己二醇与至少1mol,优选1-2mol的如在DE-A 1 770 245中描述的己内酰胺反应获得的产品,或己二醇与其本身的醚化反应来形成二或三己二醇获得的产品。这些衍生物的制备是已知的,例如从DE-A 1 570 540中可知。类似的,可以使用描述在DE-A 3 717 060中的聚醚型聚碳酸酯二醇。
所述羟基聚碳酸酯优选基本上是线型的。但是它们也可以任选通过引入多官能团成分,特别是低分子量多元醇而成为轻度支化的。为此目的有用的化合物举例来说有三羟甲基丙烷,1,2,6-己三醇,甘油、1,2,4-丁三醇,季戊四醇、对环己二醇、甘露醇、山梨糖醇、甲基糖苷和4,3,6-二酐己糖醇。
非常特别优选环氧丙烷型聚醚,其平均含有2-3个羟基和最高至50重量%的引入的聚环氧丙烷单元并具有200-9000g/mol的平均分子量,和/或平均分子量为200-4000g/mol的双功能团四氢呋喃聚醚,和/或总不饱和度不超过0.04mEq/g而且平均分子量(从OH含量和官能度计算)为2000-12000g/mol的环氧丙烷聚醚。低不饱和度的聚醚型多元醇原则上是已知的并且描述在下列文献中的实施例中:EP-A 283148,US-A 3 278 457,3 427 256,3 829 505,4 472 560,3 278458,3 427 334,3 941 849,4 721 818,3 278 459,3 427 335和4 355 188。制备这种低饱和度聚醚型多元醇的关键是用金属氰化物来催化。
粘合剂成分A)可以用常规的方法制备,通过所提及的多羟基化合物与过量的二异氰酸酯反应制得,优选在约40-120℃反应。选定NCO/OH的比为1.5∶1-20∶1并优选为1.7∶1-15∶1,任何过量的单体通过已知的技术方法从预聚物中进行分离,例如薄膜蒸馏或萃取。
粘合剂成分A)优选含有高达30%并优选高达25%的溶剂,并且其粘度优选为300-100 000mPas/25℃,更优选为500-15000mPas并特别优选500-5000mPas/25℃。
粘合剂成分A)也可以含有具有稳定作用的物质。该稳定剂为本身在聚合物化学中已知的稳定剂,例如如描述在H.Zweifel的“聚合材料的稳定(Stablization of Polymeric Materials)”,Springer-Verlag,柏林1997中的那些。
有用的稳定剂还包括通常用于稳定NCO官能团产品的添加剂,例如酰基卤、有机和无机质子酸。适合的酸性稳定剂的实例为:苯甲酰氯、邻苯二甲酰二氯、氯乙酸、2-氯丙酸、部分水解的磷酸酯如磷酸二丁酯、磷酸二乙酯或磷酸二(2-乙基己基)酯。
硬化剂
优选的硬化剂包含式I的化合物,其中n=0。
硬化剂成分B)包含胺类硬化剂,其含有通式I的天冬氨酸酯,其中R1和R2独立地均优选为甲基或乙基,更优选为甲基。
该天冬氨酸酯用常规的方法(参看EP-A 403 921)制备,通过式(II)的伯胺
H-X-H (II)
与通式(III)的马来酸或富马酸酯反应制备:
R1OOC-CH=CH-COOR2 (III),
其中
R1,R2和Z的定义如上。
适合的式(II)的二胺的实例为1,3-二氨基丙烷、1,4-二氨基丁烷、1,6二氨基己烷、2,2,4-三甲基-1,6-氨基己烷、2-甲基-1,5-二氨基戊烷、1,11-二氨基十一烷、1,12-二氨基十二烷、苯二甲胺、六羟基苯二甲胺、二(氨甲基)三环十二烷(TCD-胺)。二胺也可以用混合物。同样适合的是具有伯胺基团的双官能团聚醚型胺,例如由Texaco以商标为Jeffamine销售的产品。优选使用1,6-二氨基己烷和2-甲基-1,5-二氨基戊烷并且特别优选使用1,6-二氨基己烷。硬化剂组分B)优选包含高达50%特别优选高达25%的溶剂。
在一个用于制备胺类硬化剂B)具体实施方案中,将式(III)的酯与式为H-X-X的二胺II进行反应
其中
X如式(I)中的定义,并且n=1,
这样,其缺陷是就会有低于5%(基于所使用的反应组分III的量)的二胺以游离酯的形式留在反应产物中。
为了在二胺II中引入二价有机基团,这个实施方案最初用常规方法通过将线型聚醚二醇与二异氰酸酯反应制备了NCO官能度为2并且NCO含量为1-30重量%的NCO预聚体。优选NCO含量为1-10重量%并且更优选2-8重量%的脂肪族预聚体。
然后这些预聚体同样使用常规方法通过与式(IV)的二胺
H2N-Z-NH2反应转变成式(II)的二胺。因此,二价有机基团A可以含有氨基甲酯和脲结构单元,同时还有醚结构单元。
优选该制备过程通过最初在溶液中加入式(IV)的二胺并且逐滴加入预聚体来实现,优选在20-60℃下进行。如果需要,也可能通过随后加热来引发乙内酰脲的形成,例如如描述在US-A 3 549 599中的那样。
硬化剂组分B也可以是式(I)的硬化剂的混合物,其中n=0和n=1。这种混合物制备特别简单,通过预聚体与过量的式(IV)的二胺进行反应来实现。这样就生成了式(II)和(IV)的二胺的混合物。然后这种混合物与式(III)的酯的反应直接生成本发明将要使用的天冬氨酸酯混合物。
硬化剂组分B,如在现有技术领域中所描述的,也可以与少量的辅助成分或添加剂一起配制,也可以与催化活性物质一起配制。
这种添加剂的实例为硅酮类的流平添加剂、着色剂和催化活性量的水和/或有机质子酸,其可以任选在α位被卤素取代以增强它们的活性。这些添加剂通常刚好在它们使用前加入到硬化剂组分中,而平时不加入。
在根据本发明的方法中,即使在NCO粘合剂/胺硬化剂为通常用于工业中的接近于1当量比的情况下,反应动力学参数或者可与已确定的体系相比,或者通过水和/或酸性化合物的催化作用非常易于调节。例如,反应体系在加工条件下必须呈粘性足够长的时间以便在技术上足够长的时间跨距内使衬底被层压上。另一方面,涂层必须迅速干燥以便于使涂覆后的衬底在技术上合理的时间后能从临时非粘性的支撑体上剥离下来。用于层压的理想时间跨度为3-360秒并优选10-180秒;用于剥离的优选时间跨度为从喷射完成的时刻开始3-25分钟并且优选5-12分钟(当使用皮革作为衬底时,所提及的时间跨度上限与在低于100℃的温度下工作有关)。
根据本发明的方法提供:用一种简单的方法通过直接或逆向涂覆得到的涂覆后的柔性衬底特别是皮革。因此本发明也提供了涂覆后的柔性衬底如皮革或织物,其特征在于它们是通过本发明的方法制备的。相关技术优点在于根据本发明的应用提供了更软的皮革涂层。这是所期望的,因为这导致了涂覆后的皮革具有更自然的外观。
具体实施方式
下面的实例举例说明了本发明,不管怎样,都不希望成为对由权利要求所定义的本发明的限制。
实施例
硬化剂1(本发明的)
向一个配备有搅拌器、滴液漏斗、回流冷凝器和内置温度计的1L的四颈烧瓶中在氮气保护下加入116.2g(1mol)2-甲基-1,5-二氨基戊烷。在将内容物加热到45℃后,在45℃并搅拌下在1小时内加入344.4g(2mol)马来酸二乙酯。然后混合物在50℃继续搅拌48小时,再加入115.2g丁酮。这就获得了NH当量重为288g的80%溶液。
硬化剂2(本发明的)
向一个配备有搅拌器、滴液漏斗、回流冷凝器和内置温度计的1L的四颈烧瓶中在氮气保护下加入116.2g(1mol)1,6-二氨基己烷。在将内容物加热到45℃后,在45℃并搅拌下在1小时内加入344.4g(2mol)马来酸二乙酯。然后混合物在50℃继续搅拌48小时,再加入115.2g丁酮。这就获得了NH当量重为288g的80%溶液。
硬化剂3(非本发明的)根据EA-A-403921,天冬氨酸酯F
向一个配备有搅拌器、滴液漏斗、回流冷凝器和内置温度计的1L的四颈烧瓶中在氮气保护下加入210.4g(1mol)二(4-氨基环己基)甲烷。在将内容物加热到45℃后,在45℃并搅拌下在1小时内加入344.4g(2mol)马来酸二乙酯。然后混合物在50℃继续搅拌48小时,再加入138.7g丁酮。这就获得了NH当量重为347g的80%溶液。
粘合剂1(本发明的)
600g己二酸和1,6-己二醇及新戊二醇(对二醇而言摩尔比为1.65∶1)的聚酯(OH值:66,分子量:1700g)在80-90℃下减压脱水。然后加入129g甲苯二异氰酸酯(80%的2,4-异构体),混合物在搅拌下在90℃反应30分钟。然后再加入32g 3摩尔2,4-甲苯二异氰酸酯和2摩尔1,6-六亚甲基二异氰酸酯(5mol%,根据总异氰酸酯组分估算)的混合三聚物(参考DE-A 3 011 711),反应混合物在90℃反应30分钟,冷却至60℃并用190g乙酸乙酯稀释至80%。NCO含量:3.45%;粘度:2000mPa s(22℃);固含量:80%。对应于1当量NCO,产物为1217g。
粘合剂2(本发明的)
向配备有搅拌器和回流冷凝管的烧瓶中加入下列物质的混合物:188g(0.2212当量的OH)己二酸和1,6-己二醇与新戊二醇(相对于二醇的摩尔比为1.65∶1)的脱水聚酯(OH值:66,分子量:1700g),439g(0.2744当量的OH)TMP(三甲基丙烷)起始的PO-EO共聚醚(其EO含量为17.5%并且分子量Mn=4800g/mol),200g乙酸乙酯和0.5g磷酸二丁酯。该混合物与172.5g(1.38当量的NCO)二苯基甲烷二异氰酸酯异构体的混合物(NCO含量33.6%)进行混合,所有原料全部一次加入。将反应混合物加热到回流温度。在该温度下搅拌5小时后,NCO含量达到3.7%。所得产物的粘度为1100mPa s(22℃),固含量为80%。对应于1当量NCO,产物为1135g。
粘合剂3(本发明的)
向一个磺化反应烧瓶中加入500g(4当量的NCO)二苯基甲烷二异氰酸酯异构体的混合物(NCO含量33.6%),2.8g的磷酸二丁酯和0.42g4-甲基-2,6-二叔丁基苯酚。922.5g(0.5766当量的OH)TMP(三甲基丙烷)起始的PO-EO共聚醚(其EO含量为17.5%并且分子量Mn=4800g/mol)在搅拌下迅速逐滴加入,并升温至60℃。在60℃反应6小时后,NCO值达到10.1%。然后在不冷却的条件下迅速逐滴加入750g(0.75当量的OH)丙二醇起始的PO-EO共聚酯(其EO含量为50%),并温度升至70℃。在该温度下继续搅拌直至NCO值达到5.16%(3h)。产物冷却至40℃并与544g乙酸乙酯混合。
这样就提供了一种NCO含量为4.1%,粘度为750mPa s(22℃),固含量为80%的透明溶液。对应于1当量NCO,该溶液为1024g。
涂覆皮革的制备:
一个由两个抛光滚轴(其可以设定精确的间隔距离)构成的成膜器在后轴之前有一张隔离纸插入其中。纸和前轴之间的距离使用探针标尺调节。这个距离对应于所得涂层的湿膜厚度。
粘合剂与硬化剂在一个烧杯中充分混合30秒。粘合剂/硬化剂用量比根据所报道的这些组分的当量用量结合所选定的NCO(粘合剂)/胺(硬化剂)当量比进行计算。
将混合物倾倒在纸和前轴之间的辊隙上(混合物太粘而不能滴穿)。该纸立即被垂直向下拉过辊隙,在纸上形成相应的膜。当膜仍然呈粘性时,将皮革(短纤维状的铬片)放在这个膜上并使用橡胶辊在中度压力下用手层压。
然后在循环空气干燥橱中将样品在80℃下干燥5分钟。在降至室温后,将隔离纸剥离。这样获得的涂覆后的皮革片进行挠曲寿命(DIN53 351=EN 13 334)和水蒸汽透过率(DIN 53 333=EN 12 991)测试。
所有根据这个配方制备的涂覆后的皮革使用下列参数设定进行制备。
预聚体/硬化剂的当量比=1.08∶1;膜厚(湿):0.2mm。这些参数实际上与在制造条件下的那些惯例一致。
实施例1-6(本发明的)
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | |
粘合剂 | 1 | 2 | 3 | 1 | 2 | 3 | 1 |
硬化剂 | 1 | 1 | 1 | 2 | 2 | 2 | 3 |
溶剂含量 | 20% | 20% | 20% | 20% | 20% | 20% | 20% |
膜性能1) | |||||||
0值2) | 1.6 | 0.9 | 0.9 | 1.7 | 1.1 | 1.0 | 0.7 |
拉伸强度[MPa] | 13 | 2.4 | 2.2 | 14.6 | 3.0 | 2.0 | 1.0 |
断裂伸长率 | 610% | 390% | 370% | 650% | 400% | 340% | 290% |
水存储24h |
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | |
拉伸强度[MPa] | 11.4 | 1.6 | 1.5 | 10.4 | 1.7 | 2 | 0.9 |
断裂伸长率 | 620% | 300% | 240% | 610% | 340% | 300% | 270% |
皮革性能 | |||||||
干态挠曲性 | 60000/x | 100000/o | 70000/x | 100000/o | 90000/x | 100000/x | 30000/x |
湿态挠曲性 | 20000/x | 20000/o | 20000/o | 20000/o | 20000/o | 20000/o | 8000/x |
WVTR[mg/cm2h] | 0.38 | 0.81 | 1.00 | 0.45 | 0.69 | 0.85 | 0.87 |
图例说明:对于所有的挠曲性结果,斜号“/”前面的数字表示挠曲次数;斜号“/”后面的符号是对涂层破坏的评价:o=未破坏;x=非常小的破坏。所有的挠曲性测试在破坏征兆出现时停止,因此该表没有包含任何表征中度破坏或完全毁坏的结果。
1) 在表中的溶剂含量是硬化剂的溶剂含量
2) 0值时在100%伸长度时的拉伸强度[MPa]
实施例7(非本发明的)
硬化剂3与粘合剂1按上面配方化合。聚合物膜在干燥后仍然很粘并且在1小时后才能从隔离纸上剥离下来。抗挠曲性与本发明实例相比明显差得多。
实施例8(本发明的)
为了证实扩大辊隙涂层测试至工业制造规模的可行性,另外根据在DE-A 2 637 115中的实施例1在一个特征为在喷射头强行混合的2组分喷射系统上使用实施例6的结合,来生产涂覆后的皮革。调整计量比以便于使预聚体与硬化剂的当量比为1.08并且湿膜厚度为0.27mm。使用的皮革还是一个短纤维铬片。
所获得的皮革的性能总结在下表中。可以看出机器试验提供了比辊隙涂层测试更长的挠曲寿命。
挠曲试验寿命 | |
干态 | 100000/o |
湿态 | 100000/o |
冷冻态(-25℃) | 30000/o |
水解70℃/95%r.h.7天 | 30000/o |
撕裂强度(0.27mm厚度) | 7N/cm |
水蒸气通过率 | 1.26mg/cm2h |
水蒸气吸收率(20℃/65%r.h.) | 12.6mg/cm2 |
图例说明:对于所有的挠曲性结果,斜号“/”前面的数字表示挠曲次数;斜号“/”后面的符号是对涂层破坏的评价:o=未破坏;x=非常小的破坏。所有的挠曲性测试在破坏征兆出现时就停止了,因此该表没有包含任何表征中度破坏或完全毁坏的结果。
Claims (8)
1.由粘合剂组分A)和硬化剂组分B)组成的2组分PU体系在涂覆柔性衬底方面的应用,其特征在于硬化剂组分B)包含式I的天冬氨酸酯
其中
R1和R2彼此独立地相同或不同,并代表C1-C4-烷基,
X是下式的基团:
其中
A为二价有机基团,
Z为含4-18个碳原子的二价脂肪族基团
n为0或1。
2.根据权利要求1的应用,其特征在于粘合剂A)包含一种多NCO官能团化合物,该化合物的NCO含量为2-8重量%,数均分子量为700-8000g/mol并且NCO官能度为2.0-3.0,前提条件是该粘合剂A)与硬化剂B)的当量比为1∶1-1.33∶1。
3.根据权利要求1的应用,其中R1和R2各为甲基或乙基。
4.根据权利要求1的应用,其中Z是-(CH2)6-或-CH2CH(CH3)(CH2)2-。
5.根据权利要求1的应用,其用于涂覆皮革或织物。
6.根据权利要求1-5中的至少一个的应用,其中粘合剂A)基于芳香族二异氰酸酯。
7.通过权利要求1的应用生产的涂覆的皮革。
8.通过权利要求1的应用生产的涂覆的织物。
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DE10135316.2 | 2001-07-19 | ||
DE2001135316 DE10135316A1 (de) | 2001-07-19 | 2001-07-19 | Verwendung spezieller Härter in 2-Komponenten PU-Systemen zum Beschichten flexibler Substrate |
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DE102009016173A1 (de) | 2009-04-03 | 2010-10-14 | Bayer Materialscience Ag | Schutzlack |
DE102009027395A1 (de) * | 2009-07-01 | 2011-01-05 | Evonik Degussa Gmbh | Reaktive Derivate auf Basis Dianhydrohexitol basierender Isocyanate |
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CN104130390B (zh) * | 2014-07-04 | 2016-04-13 | 山东一航新材料科技有限公司 | 聚醚型聚天冬氨酸酯及其制备方法 |
CN115710828B (zh) * | 2022-11-24 | 2024-05-14 | 湖南航天三丰科工有限公司 | 一种蒙皮用聚天门冬氨酸酯涂料及其制备方法和应用 |
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CN111032718A (zh) * | 2017-08-30 | 2020-04-17 | 陶氏环球技术有限责任公司 | 溶剂型粘合剂组合物 |
CN111032718B (zh) * | 2017-08-30 | 2022-12-02 | 陶氏环球技术有限责任公司 | 溶剂型粘合剂组合物 |
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