CN109337029A - 一种高耐磨tpu/硅胶复合材料及其制备方法 - Google Patents
一种高耐磨tpu/硅胶复合材料及其制备方法 Download PDFInfo
- Publication number
- CN109337029A CN109337029A CN201811055209.2A CN201811055209A CN109337029A CN 109337029 A CN109337029 A CN 109337029A CN 201811055209 A CN201811055209 A CN 201811055209A CN 109337029 A CN109337029 A CN 109337029A
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- CN
- China
- Prior art keywords
- tpu
- melt adhesive
- layer
- hot melt
- silica gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 34
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- 239000012528 membrane Substances 0.000 claims description 30
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- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 claims description 5
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- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical compound CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
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- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- PXDRFTPXHTVDFR-UHFFFAOYSA-N propane;titanium(4+) Chemical compound [Ti+4].C[CH-]C.C[CH-]C.C[CH-]C.C[CH-]C PXDRFTPXHTVDFR-UHFFFAOYSA-N 0.000 claims 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
- 239000004254 Ammonium phosphate Substances 0.000 claims 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 235000019289 ammonium phosphates Nutrition 0.000 claims 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims 1
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- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 3
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
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- 230000005540 biological transmission Effects 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
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- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
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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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- B32B7/04—Interconnection of layers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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
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- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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Abstract
本发明涉及一种TPU/硅胶复合材料,所述TPU/硅胶复合材料包括依次叠层的基布层、第一热熔胶层、TPU层、第二热熔胶层和硅胶层;所述第一热熔胶层和第二热熔胶层均为TPU热熔胶层。本发明提供的高耐磨TPU/硅胶复合材料耐磨性好,在9kPa的压力下,磨1000转后磨损现象不明显,且光散射较硅胶材料具有明显提升,阻燃性良好。本发明通过减薄硅胶层至合适厚度,配合热熔胶层,实现与TUP层牢固粘结,且流延法避免气泡产生,使得材料能够在获得良好耐磨性的前提下,获得了良好的光散射性。
Description
技术领域
本发明属于人造革制造领域,具体涉及一种高耐磨TPU/硅胶复合材料及其制备方法。
背景技术
随着我国经济的高速发展,皮革制品的需求量越来越大,档次也越来越高。汽车内饰革已广泛地应用在乘用汽车、运输汽车的内饰件中。汽车内饰用革,最佳选择为真皮,但真皮在其自身生产过程中污染环境严重,重金属含量容易超标,在内饰件加工过程中成材率较低,其价格昂贵,难以为中低档乘用车所接受;而且人们对环境保护逐渐重视,在提倡环保节能、可持续发展的今天,人们也开始开发出仿皮面料来取代动物皮革,以避免对野生动物的伤害和对自然环境的破坏。
人造皮革也叫仿皮或胶皮,是PVC和PU等人造材料的总称。它是在纺织布基或无纺布基上,由各种不同配方的PVC和PU等发泡或覆膜加工制作而成,可以根据不同强度、耐磨度、耐寒度和色彩、光泽、花纹图案等要求加工制成,具有花色品种繁多、防水性能好、边幅整齐、利用率高和价格相对真皮便宜的特点。汽目前,汽车门板、汽车座椅面料、仪表板、车厢内壁、车顶篷、方向盘把套等部位,主要采用非织造布等与聚氯乙烯、聚氨酯等复合的材料。现有的汽车内饰耐磨性差,阻燃性好表现不佳。
本领域需要开发一种高耐磨TPU/硅胶复合材料及其制备方法,其具有耐磨,阻燃的效果。
发明内容
本发明的目的在于提供一种TPU/硅胶复合材料,
所述TPU/硅胶复合材料包括依次叠层的基布层、第一热熔胶层、TPU层、第二热熔胶层和硅胶层;所述第一热熔胶层和第二热熔胶层均为TPU热熔胶层。
本发明提供的TPU/硅胶复合材料利用硅胶层的耐磨性,和TPU层的阻燃性,将两者叠加,获得耐磨性较高,且外观较好的复合材料。而热熔胶层粘结强度大,起到提高TPU/硅胶复合材料层间粘结牢固性的作用。
优选地,所述硅胶层厚度为0.01~0.10mm,例如可以为0.02mm、0.03mm、0.05mm、0.07mm、0.09mm等。
硅胶层的设置厚度能够保证即起到耐磨效果,又不影响透光性能的作用。
优选地,所述第二热熔胶层厚度为0.02~0.05mm,例如可以为0.03mm、0.04mm等。
第二热熔胶层的厚度匹配硅胶层和TPU层的厚度,使得硅胶层能够牢固与TPU层结合,且不影响材料的透光性。
优选地,所述TPU层厚度为0.01~0.08mm,例如可以为0.02mm、0.03mm、0.04mm、0.05mm、0.06mm、0.07mm等。
TPU层的设置厚度与硅胶层和热熔胶层厚度配合,使得其具有合适的硬度,且透光性合适。
优选地,所述第一热熔胶厚度为0.11~0.20mm,例如可以为0.12mm、0.13mm、0.14mm、0.15mm、0.16mm、0.17mm、0.18mm、0.19mm等。
优选地,所述基布层的厚度为1.0~3.0mm,例如可以为1.1mm、1.2mm、1.5mm、1.8mm、2.2mm、2.5mm、2.7mm、2.9mm等。
优选地,所述第一TPU热熔胶层和第二TPU热熔胶层的制备原料按重量份数包括如下原料组分:
作为示例,本发明所述TPU热熔胶层的制备原料中,聚酯多元醇可以是36份、37份、38份、39份、40份、41份、43份或44份等;二异氰酸酯可以是32份、35份、38份、40份、42份、45份、48份或50份等;催化剂可以是0.2份、0.4份、0.6份、0.8份、1.0份、1.2份、1.5份或1.8份等;扩链剂可以是2份、3份、5份、8份、9份、10份、12份或14份等。
优选地,所述聚酯多元醇包括癸二酸系聚酯多元醇,优选分子量为1000~2000(例如1100、1200、1300、1400、1500、1600、1700、1800、1900等)的癸二酸系聚酯多元醇。
优选地,所述癸二酸系聚酯多元醇的制备方法为:将癸二酸、对苯二甲酸与乙二醇混合,然后加入锆酸异丙酯,升温至120~200℃(例如130℃、140℃、150℃、160℃、170℃、180℃、190℃等)进行缩聚反应得到癸二酸系聚酯多元醇。
优选地,所述癸二酸和对苯二甲酸的摩尔比为1:2~3(例如1:2.2、1:2.4、1:2.6、1:2.8、1:2.9等)。
优选地,所述乙二醇与癸二酸的摩尔比为3.5~4.5:1,例如3.6:1、3.7:1、3.8:1、3.9:1、4.0:1、4.1:1、4.2:1、4.3:1、4.4:1等。
优选地,所述锆酸异丙酯的加入量为3×10-3~4×10-3mol/mol癸二酸。
优选地,所述二异氰酸酯包括二苯甲烷二异氰酸酯或甲苯二异氰酸酯。
癸二酸系聚酯多元醇由癸二酸和对苯二甲酸同时发生酯化,其中含有合适比例的短链酸和芳香酸,芳香基团结构规整,结晶性好,能够提高机械性能,但是过高的结晶性导致粘结性变差,复配癸二酸后,能够提高粘结性能。
优选地,所述第一催化剂包括对甲苯磺酸、二月桂酸二丁基锡、乙二醇锑、四异丙基钛酸酯中的任意1种或至少2种的组合。典型但非限制性的第二催化剂的组合如二月桂酸二丁基锡与乙二醇锑,乙二醇锑与四异丙基钛酸酯。
优选地,所述扩链剂包括1,6-己二醇、甲基丙二醇、1,4-丁二醇中的任意1种或至少2种的组合。典型但非限制性的扩链剂的组合如1,6-己二醇与甲基丙二醇,1,6-己二醇与1,4-丁二醇。
优选地,所述TPU热熔胶层的制备原料还包括0.1~1重量份(例如0.2重量份、0.3重量份、0.4重量份、0.5重量份、0.6重量份、0.7重量份、0.8重量份、0.9重量份等)的第一抗氧剂。
优选地,所述第一抗氧剂包括抗氧剂245、抗氧剂1135、抗氧剂PUR67、抗氧剂PUR68中的任意1种或至少2种的组合。
优选地,所述TPU热熔胶层的制备原料还包括0.1~5重量份的阻燃剂,例如0.5份、1.0份、1.5份、2.0份、2.5份、3.0份、3.5份、4.0份或4.5份等。
优选地,所述阻燃剂按重量百分比包括:20~30wt%的亚磷酸二甲酯、30~40wt%的聚磷酸铵、30~40wt%的季戊四醇。
在所述阻燃剂中,所述亚磷酸二甲酯的质量百分含量可为20%、22%、24%、26%、28%或30%等,所述聚磷酸铵的质量百分含量可为30%、32%、34%、36%、38%或40%等,所述季戊四醇的质量百分含量可为30%、32%、34%、36%、38%或40%等。
优选地,所述TPU热熔胶层的制备原料还包括0.1~5重量份的增粘树脂,例如0.5份、1.0份、1.5份、2.0份、2.5份、3.0份、3.5份、4.0份或4.5份等。
优选地,所述增粘树脂包括聚乙烯-醋酸乙烯共聚物、端羟基热塑性聚酯、氢化松香树脂中的任意1种或至少2种的组合。
优选地,所述TPU层的制备原料按重量份数包括如下原料组分:
所述热塑性聚氨酯颗粒的制备原料按重量份数包括如下组分:
优选地,所述聚六亚甲基碳酸酯二醇的重均分子量为1000~2000,如重均分子量为1100、1200、1300、1400、1500、1600、1700、1800、1900或2000等。
优选地,所述爽滑剂选自油酸酰胺、芥酸酰胺或山嵛酸酰胺中的任意1种或至少2种的组合;典型但非限制性的组合如油酸酰胺和芥酸酰胺、油酸酰胺和山嵛酸酰胺等。
优选地,所述第二抗氧化剂选自二硬脂基季戊四醇亚磷酸酯、亚磷酸三苯酯、二丁基羟基甲苯BHT、N,N’-双[[3-(3,5)-二叔丁基-4-羟基苯基]丙酰基]己二胺中的任意1种或至少2种的组合;典型但非限制性的组合如二硬脂基季戊四醇亚磷酸酯和亚磷酸三苯酯、亚磷酸三苯酯和二丁基羟基甲苯等。
优选地,所述抗紫外剂选自UV-P、UV-328或UV-B83中的任意1种或至少2种的组合;典型但非限制性的组合如UV-P和UV-328、UV-P和UV-B83等。
优选地,所述第二催化剂包括对甲苯磺酸、二月桂酸二丁基锡、乙二醇锑、四异丙基钛酸酯中的任意1种或至少2种的组合。典型但非限制性的第二催化剂的组合如二月桂酸二丁基锡与乙二醇锑,乙二醇锑与四异丙基钛酸酯。
优选地,所述硅胶层为液体硅橡胶固化层。
优选地,所述液体硅橡胶包括脱醇缩合型液体硅橡胶。
优选地,所述基布层包括超细纤维非织造布,优选单位面积重量为50-400g/m2(例如可以为100g/m2、120g/m2、150g/m2、180g/m2、200g/m2、220g/m2、250g/m2、280g/m2、300g/m2、320g/m2、350g/m2、380g/m2或400g/m2等)的超细纤维非织造布。
优选地,所述热熔胶层通过将热熔胶流延得到。
流延制备热熔胶层后,将热熔胶层与基布层压合,一方面能够提高热熔胶层与基布层的结合强度,降低热熔胶层的厚度,另一方面能够降低现有技术热熔胶喷涂制备热熔胶层造成的空气污染。
本发明目的之二是提供一种目的之一所述的聚氨酯皮革的制备方法,所述制备方法包括如下步骤:
(1)TPU热熔胶膜的制备:按照TPU热熔胶层的制备原料配方混合制备原料,螺杆挤出得到TPU热熔胶颗粒,将所述TPU热熔胶颗粒通过单螺杆挤出机按照温度为180~220℃(例如185℃、190℃、195℃、200℃、205℃、210℃、215℃或220℃等),模头温度为180~210℃(例如180℃、185℃、190℃、195℃、200℃、205℃或210℃等)的条件流延得到的TPU热熔胶膜,将所述TPU热熔胶膜与基布进行对压复合,形成第一复合膜;
(2)TPU层复合阶段:按照TPU层的制备原料配方混合制备原料,螺杆挤出得到TPU膜颗粒,将所述TPU膜颗粒通过单螺杆挤出机按照温度为180~220℃(例如185℃、190℃、195℃、200℃、205℃、210℃、215℃或220℃等),模头温度为180~210℃(例如180℃、185℃、190℃、195℃、200℃、205℃或210℃等)的条件流延得到TPU层;将所述TPU层与第一复合膜对压复合,形成第二复合膜;
(3)硅胶层复合阶段:将液体硅橡胶均匀涂布在第二复合膜的TPU层表面,经60~80℃的固化,得到TPU/硅胶复合材料。
与现有技术相比,本发明具有以下有益效果:
(1)本发明提供的高耐磨TPU/硅胶复合材料耐磨性好,在9kPa的压力下,磨1000转后磨损现象不明显,且光散射较硅胶材料具有明显提升,阻燃性良好。
(2)本发明通过减薄硅胶层至合适厚度,配合热熔胶层,实现与TUP层牢固粘结,且流延法避免气泡产生,使得材料能够在获得良好耐磨性的前提下,获得了良好的光散射性。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
实施例1
一种TPU/硅胶复合材料,包括依次叠层的1.5mm厚的基布层超细纤维非织造布(单位面积重量为200g/m2)、0.15mm厚的第一热熔胶层、0.05mm厚的TPU层、0.03mm厚的第二热熔胶层和0.05mm厚的硅胶层。
所述TPU热熔胶层的制备原料按重量份数包括如下原料组分:
所述聚酯多元醇的制备方法为:将1mol癸二酸、2.5mol对苯二甲酸与4.0mol乙二醇混合,然后加入0.003mol锆酸异丙酯,升温至160℃进行缩聚反应得到癸二酸系聚酯多元醇(重均分子量1500);
所述阻燃剂按按重量百分比包括:30wt%亚磷酸二甲酯、35wt%聚磷酸铵、35wt%季戊四醇;
所述PU层的制备方法包括:将PU树脂工作液涂布在TPU层上烘干粘合;所述PU树脂工作液的配方如下:聚氨酯树脂85重量份;二甲基甲酰胺22重量份;乙酸乙酯40重量份;表面活性助剂硫酸化蓖麻油3重量份;抗菌剂十二烷基二甲基苄基溴化铵1.0重量份;色粉5重量份。
所述TPU膜层通过将入选原料混合后流延得到,所述原料组分按重量份数包括:热塑性聚氨酯颗粒93重量份;爽滑剂山嵛酸酰胺0.05重量份;抗氧化剂二丁基羟基甲苯0.5重量份;抗紫外线剂UV-B83 0.5重量份;所述热塑性聚氨酯颗粒按重量份数包括如下原料组分:重均分子量为1500的聚六亚甲基碳酸酯二醇35份;1,5-奈二异氰酸酯15份;苯亚甲基二异氰酸酯25份;1、4-丁二醇18份;催化剂0.5份。
制备方法包括如下步骤:
(1)TPU热熔胶膜阶段:将TPU热熔胶原料流延得到的TPU热熔胶膜与基布进行对压复合,形成第一复合膜;
(2)TPU膜层复合阶段:将热塑性聚氨酯颗粒和助剂通过单螺杆挤出机,按照螺杆温度为200℃,模头温度为190℃的条件流延成TPU膜,与第一复合膜对压复合,形成第二复合膜;
(3)硅胶层复合阶段:将液体硅橡胶(道康宁HV1510/40)均匀涂布在第二复合膜的TPU层表面,经60~80℃的固化,得到TPU/硅胶复合材料。
实施例2
一种TPU/硅胶复合材料,包括依次叠层的3.0mm厚的基布层超细纤维非织造布(单位面积重量为400g/m2)、0.11mm厚的第一热熔胶层、0.01mm厚的TPU层、0.02mm厚的第二热熔胶层和0.01mm厚的硅胶层。
所述TPU热熔胶层的制备原料按重量份数包括如下原料组分:
所述聚酯多元醇的制备方法为:将1mol癸二酸、2.5mol对苯二甲酸与4.0mol乙二醇混合,然后加入0.003mol锆酸异丙酯,升温至200℃进行缩聚反应得到癸二酸系聚酯多元醇(重均分子量2000);
所述阻燃剂按按重量百分比包括:20wt%亚磷酸二甲酯、40wt%聚磷酸铵、40wt%季戊四醇;
所述PU层的制备方法包括:将PU树脂工作液涂布在TPU层上烘干粘合;所述PU树脂工作液的配方如下:聚氨酯树脂90重量份;二甲基甲酰胺25重量份;乙酸乙酯50重量份;表面活性助剂硫酸化蓖麻油5重量份;抗菌剂十二烷基二甲基苄基溴化铵2重量份;色粉10重量份。
所述TPU膜层通过将入选原料混合后流延得到,所述原料组分按重量份数包括:热塑性聚氨酯颗粒95重量份;爽滑剂芥酸酰胺1.0重量份;抗氧化剂亚磷酸三苯酯1.0重量份;抗紫外线剂UV-328 1.0重量份;所述热塑性聚氨酯颗粒按重量份数包括如下原料组分:重均分子量为2000的聚六亚甲基碳酸酯二醇40份;1,5-奈二异氰酸酯20份;苯亚甲基二异氰酸酯30份;1、4-丁二醇25份;催化剂1.0份。
制备方法包括如下步骤:
(1)TPU热熔胶膜阶段:将TPU热熔胶原料流延得到的TPU热熔胶膜与基布进行对压复合,形成第一复合膜;
(2)TPU膜层复合阶段:将热塑性聚氨酯颗粒和助剂通过单螺杆挤出机,按照螺杆温度为200℃,模头温度为190℃的条件流延成TPU膜,与第一复合膜对压复合,形成第二复合膜;
(3)硅胶层复合阶段:将液体硅橡胶(道康宁HV1510/40)均匀涂布在第二复合膜的TPU层表面,经60~80℃的固化,得到TPU/硅胶复合材料。
实施例3
一种TPU/硅胶复合材料,包括依次叠层的0.1mm厚的基布层超细纤维非织造布(单位面积重量为200g/m2)、0.20mm厚的第一热熔胶层、0.08mm厚的TPU层、0.05mm厚的第二热熔胶层和0.10mm厚的硅胶层。
所述TPU热熔胶层的制备原料按重量份数包括如下原料组分:
所述聚酯多元醇的制备方法为:将1mol癸二酸、2.5mol对苯二甲酸与4.0mol乙二醇混合,然后加入0.003mol锆酸异丙酯,升温至160℃进行缩聚反应得到癸二酸系聚酯多元醇(重均分子量1500);
所述阻燃剂按按重量百分比包括:25wt%亚磷酸二甲酯、35wt%聚磷酸铵、35wt%季戊四醇;
所述PU层的制备方法包括:将PU树脂工作液涂布在TPU层上烘干粘合;所述PU树脂工作液的配方如下:聚氨酯树脂85重量份;二甲基甲酰胺22重量份;乙酸乙酯40重量份;表面活性助剂硫酸化蓖麻油3重量份;抗菌剂十二烷基二甲基苄基溴化铵1重量份;色粉5重量份。
所述TPU膜层通过将入选原料混合后流延得到,所述原料组分按重量份数包括:热塑性聚氨酯颗粒93重量份;爽滑剂山嵛酸酰胺0.05重量份;抗氧化剂二丁基羟基甲苯0.5重量份;抗紫外线剂UV-B83 0.5重量份;所述热塑性聚氨酯颗粒按重量份数包括如下原料组分:重均分子量为1500的聚六亚甲基碳酸酯二醇35份;1,5-奈二异氰酸酯15份;苯亚甲基二异氰酸酯25份;1、4-丁二醇18份;催化剂0.5份。
制备方法包括如下步骤:
(1)TPU热熔胶膜阶段:将TPU热熔胶原料流延得到的TPU热熔胶膜与基布进行对压复合,形成第一复合膜;
(2)TPU膜层复合阶段:将热塑性聚氨酯颗粒和助剂通过单螺杆挤出机,按照螺杆温度为200℃,模头温度为190℃的条件流延成TPU膜,与第一复合膜对压复合,形成第二复合膜;
(3)硅胶层复合阶段:将液体硅橡胶(道康宁HV1510/40)均匀涂布在第二复合膜的TPU层表面,经60~80℃的固化,得到TPU/硅胶复合材料。
实施例4
与实施例1的区别在于,所述汽车用仿真皮纹理聚氨酯皮革,包括依次叠层的1.5mm厚的基布层超细纤维非织造布(单位面积重量为200g/m2)、0.25mm厚的第一热熔胶层、0.10mm厚的TPU层、0.07mm厚的第二热熔胶层和0.13mm厚的硅胶层。
实施例5
与实施例2的区别在于,所述汽车用仿真皮纹理聚氨酯皮革,包括依次叠层的0.01mm厚的基布层超细纤维非织造布(单位面积重量为200g/m2)、0.10mm厚的第一热熔胶层、0.01mm厚的TPU层、0.01mm厚的第二热熔胶层和0.01mm厚的硅胶层。
性能测试:
将实施例得到的TPU/硅胶复合材料进行如下性能测试:
(1)磨耗强度:在9KPa的压力下,磨1000转后观察磨损现象,实施例1~3均无磨损现象,实施例4~5有少量磨损现象;
(2)阻燃性:实施例1~5均为UL94V-0。
申请人声明,本发明通过上述实施例来说明本发明的工艺方法,但本发明并不局限于上述工艺步骤,即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (8)
1.一种TPU/硅胶复合材料,其特征在于,所述TPU/硅胶复合材料包括依次叠层的基布层、第一热熔胶层、TPU层、第二热熔胶层和硅胶层;
所述第一热熔胶层和第二热熔胶层均为TPU热熔胶层。
2.如权利要求1所述的TPU/硅胶复合材料,其特征在于,所述硅胶层厚度为0.01~0.10mm;
优选地,所述第二热熔胶层厚度为0.02~0.05mm;
优选地,所述TPU层厚度为0.01~0.08mm;
优选地,所述第一热熔胶厚度为0.11~0.20mm;
优选地,所述基布层的厚度为1.0~3.0mm。
3.如权利要求1所述的TPU/硅胶复合材料,其特征在于,所述第一TPU热熔胶层和第二TPU热熔胶层的制备原料按重量份数包括如下原料组分:
所述聚酯多元醇包括癸二酸系聚酯多元醇,优选分子量为500~800的癸二酸系聚酯多元醇;
优选地,所述癸二酸系聚酯多元醇的制备方法为:将癸二酸、对苯二甲酸与乙二醇混合,然后加入锆酸异丙酯,升温至120~200℃进行缩聚反应得到癸二酸系聚酯多元醇;
优选地,所述癸二酸和对苯二甲酸的摩尔比为1:2~3;
优选地,所述乙二醇与癸二酸的摩尔比为3.5~4.5:1;
优选地,所述锆酸异丙酯的加入量为3×10-3~4×10-3mol/mol癸二酸。
4.如权利要求3所述的TPU/硅胶复合材料,其特征在于,所述二异氰酸酯包括二苯甲烷二异氰酸酯或甲苯二异氰酸酯;
优选地,所述第一催化剂包括对甲苯磺酸、二月桂酸二丁基锡、乙二醇锑、四异丙基钛酸酯中的任意1种或至少2种的组合;
优选地,所述扩链剂包括1,6-己二醇、甲基丙二醇、1,4-丁二醇中的任意1种或至少2种的组合。
5.如权利要求3或4所述的TPU/硅胶复合材料,其特征在于,所述TPU热熔胶层的制备原料还包括0.1~1重量份的第一抗氧剂;
优选地,所述第一抗氧剂包括抗氧剂245、抗氧剂1135、抗氧剂PUR67、抗氧剂PUR68中的任意1种或至少2种的组合;
优选地,所述TPU热熔胶层的制备原料还包括0.1~5重量份的阻燃剂;
优选地,所述阻燃剂按重量百分比包括:20~30wt%的亚磷酸二甲酯、30~40wt%的聚磷酸铵、30~40wt%的季戊四醇;
优选地,所述TPU热熔胶层的制备原料还包括0.1~5重量份的增粘树脂;
优选地,所述增粘树脂包括聚乙烯-醋酸乙烯共聚物、端羟基热塑性聚酯、氢化松香树脂中的任意1种或至少2种的组合。
6.如权利要求1~5之一所述的TPU/硅胶复合材料,其特征在于,所述TPU层的制备原料按重量份数包括如下原料组分:
所述热塑性聚氨酯颗粒的制备原料按重量份数包括如下组分:
优选地,所述聚六亚甲基碳酸酯二醇的重均分子量为1000~2000;
优选地,所述爽滑剂选自油酸酰胺、芥酸酰胺或山嵛酸酰胺中的任意1种或至少2种的组合;
优选地,所述第二抗氧化剂选自二硬脂基季戊四醇亚磷酸酯、亚磷酸三苯酯、二丁基羟基甲苯BHT、N,N’-双[[3-(3,5)-二叔丁基-4-羟基苯基]丙酰基]己二胺中的任意1种或至少2种的组合;
优选地,所述抗紫外剂选自UV-P、UV-328或UV-B83中的任意1种或至少2种的组合。
优选地,所述第二催化剂包括对甲苯磺酸、二月桂酸二丁基锡、乙二醇锑、四异丙基钛酸酯中的任意1种或至少2种的组合。
7.如权利要求1~6之一所述的TPU/硅胶复合材料,其特征在于,所述硅胶层为液体硅橡胶固化层;
优选地,所述液体硅橡胶包括脱醇缩合型液体硅橡胶;
优选地,所述基布层包括超细纤维非织造布,优选单位面积重量为50-400g/m2的超细纤维非织造布;
优选地,所述热熔胶层通过将热熔胶流延得到。
8.根据权利要求1~7之一所述的TPU/硅胶复合材料的制备方法,其特征在于,所述制备方法包括如下步骤:
(1)TPU热熔胶膜的制备:按照TPU热熔胶层的制备原料配方混合制备原料,螺杆挤出得到TPU热熔胶颗粒,将所述TPU热熔胶颗粒通过单螺杆挤出机按照温度为180~220℃,模头温度为180~210℃的条件流延得到的TPU热熔胶膜,将所述TPU热熔胶膜与基布进行对压复合,形成第一复合膜;
(2)TPU层复合阶段:按照TPU层的制备原料配方混合制备原料,螺杆挤出得到TPU膜颗粒,将所述TPU膜颗粒通过单螺杆挤出机按照温度为180~220℃,模头温度为180~210℃的条件流延得到TPU层;将所述TPU层与第一复合膜对压复合,形成第二复合膜;
(3)硅胶层复合阶段:将液体硅橡胶均匀涂布在第二复合膜的TPU层表面,经60~80℃的固化,得到TPU/硅胶复合材料。
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CN113386413B (zh) * | 2021-07-09 | 2023-02-03 | 昆山联滔电子有限公司 | 一种皮革和硅胶复合物及其制备方法和应用 |
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Denomination of invention: A high wear-resistant TPU/silicone composite material and its preparation method Granted publication date: 20211214 Pledgee: Agricultural Bank of China Limited Dongguan Daojiao Branch Pledgor: DONGGUAN XIONGLIN NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2024980017876 |