CN110431373A - 三维成型制品 - Google Patents

三维成型制品 Download PDF

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Publication number
CN110431373A
CN110431373A CN201880019087.3A CN201880019087A CN110431373A CN 110431373 A CN110431373 A CN 110431373A CN 201880019087 A CN201880019087 A CN 201880019087A CN 110431373 A CN110431373 A CN 110431373A
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CN
China
Prior art keywords
product
fabric
fiber
dimensionally shaped
acrylic
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Pending
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CN201880019087.3A
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English (en)
Inventor
厄齐曼·穆拉特
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Dsm Protective Materials Co ltd
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DSM IP Assets BV
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Publication of CN110431373A publication Critical patent/CN110431373A/zh
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • F41H1/00—Personal protection gear
    • F41H1/04—Protection helmets
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/083—Combinations of continuous fibres or fibrous profiled structures oriented in one direction and reinforcements forming a two dimensional structure, e.g. mats
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

本发明涉及一种具有外表面和内表面的三维成型制品，该外表面包含至少一种拉伸强度为至少1.5GPa的聚乙烯纤维的织物(100)，该织物浸渍有丙烯酸基热塑性材料。该三维成型制品还可包含具有单向排列纤维的单层。该三维成型制品具有改进的表面外观，因此需要很少或不需要后处理并且对涂料和漆料具有良好的粘附性。

Description

三维成型制品
本发明涉及一种具有外表面和内表面的三维成型制品。本发明还涉及一种制造三维成型制品的方法，以及具有丙烯酸基热塑性材料的聚乙烯纤维的织物作为外表面用于制造三维成型制品的用途，优选用于制造三维成型的抗冲击制品，更优选用于制造三维成型的防弹制品。
WO2007107359描述了一种三维成型制品，其由单向聚乙烯纤维和聚氨酯基质材料构成，所述三维成型制品在一种方法中制造，由此施加控制构件以降低产品的可变性。
尽管现有技术的三维成型制品具有低可变性，但仍需要进一步改进，特别是在表面外观方面。
本发明的一个目的是提供一种具有改进的表面外观的三维成型制品。
该目的通过具有外表面(“1”)和内表面(“2”)的三维成型制品实现，所述外表面包含至少一种织物('100')，所述织物包含拉伸强度为至少1.5GPa的聚乙烯纤维，所述织物浸渍有丙烯酸基热塑性材料。
根据本发明的三维成型制品具有改善的表面外观。根据本发明的三维成型制品的另一个优点是改善了涂料层和漆料的粘附性。这增加了经涂布的三维成型制品的耐久性，并且因此不太可能发生涂料层或漆料从制品上剥离或磨损。
根据本发明的三维成型制品具有外表面(1)和内表面(2)，通常在至少两个方向上具有曲率，并且可以是例如小穹顶(cupola)、圆顶(dome)、半圆顶、半球、头盔和顶篷。
用于本发明的至少一种织物(100)优选是纺织织物，其具有例如平纹、方平纹、缎纹和破斜纹(crow feet)编织式样，但它也可以是针织网络，或是以各种常规技术中的任何一种形成织物的网络。所述至少一个织物(100)的替代实施例也可以是毡。
用于本发明的至少一种织物(100)包含拉伸强度为至少1.5GPa、优选至少2.5GPa的聚乙烯纤维。更优选地，织物中的纤维具有至少3.5GPa的强度，这导致更好的结构刚性。甚至更优选地，织物中的纤维具有至少4GPa的强度以获得具有更好冲击性能的产品，并且最优选至少4.5GPa，从而得到具有非常好的防弹性能的三维成型制品。
用于本发明的聚乙烯纤维可以合适地基于线性聚乙烯(PE)。线性聚乙烯在本文中应理解为是指每100个C原子具有少于1个侧链的聚乙烯，并且优选每300个C原子具有少于1个侧链；侧链或支链通常含有至多10个C原子。线性聚乙烯可以进一步含有至多5mol％的一种或多种可与其共聚的其它烯烃，例如丙烯、丁烯、戊烯、4-甲基戊烯、辛烯。优选地，线性聚乙烯是超高分子量聚乙烯，其特性粘度(IV，在135℃的十氢化萘溶液中测定)为至少为4dl/g；更优选至少8dl/g。
由聚乙烯长丝组成的高性能聚乙烯(HPPE)纤维优选用于织物或单层中，所述聚乙烯长丝通过凝胶纺丝法制备，例如在GB 2042414 A或WO 01/73173中所述。凝胶纺丝工艺主要由以下组成：制备具有高特性粘度的线性聚乙烯溶液，在高于溶解温度的温度下将溶液纺丝成长丝，将长丝冷却至低于胶凝温度，从而发生胶凝，并在除去溶剂之前、期间或之后拉伸长丝。这种拉伸导致拉伸纤维具有至少1.5GPa的强度。如果这些聚乙烯纤维是高度拉伸的，它们的强度为至少3.0GPa。
用于本发明的至少一种织物(100)优选用丙烯酸基热塑性材料浸渍。在一个特定的实施方式中，丙烯酸基热塑性材料丙烯酸类树脂或丙烯酸类聚合物的玻璃化转变温度Tg为至少25℃。基于丙烯酸类树脂的热塑性材料本身是本领域公知的。用于本发明的丙烯酸类树脂的Tg优选为至少25℃，更优选至少35℃，甚至更优选至少45℃，最优选至少55℃。通常，聚合物的Tg在25至120℃的范围内，更通常在30至90℃的范围内。在一个具体的实施方式中，用于本发明的热塑性丙烯酸类树脂的Tg为25℃-53℃，并以水分散体形式施用。
Tg为至少25℃的热塑性丙烯酸类树脂优选包含丙烯酸类聚合物，其包括甲基丙烯酸甲酯、丙烯酸乙酯和/或丙烯酸丁酯。丙烯酸类聚合物可以基于包含酸基团的前体，其含量为0-10wt％，优选0.1-8wt％，更优选0.5-7wt％，甚至更优选0.5-6wt％，最优选0.5-4wt％，并且还可以基于-OH官能的单体，其量为0-30wt％，优选0-20wt％，更优选0-15wt％，甚至更优选0-10wt％，最优选1-10wt％。丙烯酸类聚合物的数均分子量通常为至少1000g/mol，更通常为至少2000g/mol。上限通常不超过2000000g/mol。通常，数均分子量在5000g/mol至800000g/mol的范围内，优选在10000g/mol至500000g/mol的范围内，更优选在100000g/mol至500000g/mol的范围内。在另一个实施方式中，丙烯酸类聚合物的重均分子量通常为至少10000g/mol，更通常为至少20000g/mol。上限通常不超过4000000g/mol。通常，重均分子量在15000g/mol至2500000g/mol的范围内，优选在20000g/mol至2000000g/mol的范围内，更优选在50000g/mol至1500000g/mol的范围内。
用于浸渍织物(100)的丙烯酸类聚合物或丙烯酸类聚合物可以是包含20-600nm、更优选30-400nm、最优选50-300nm的聚合物粒度的乳液。该乳液的pH通常为2-11，优选3-10，更优选4-9。固体含量通常为10-60wt％，优选20-55wt％，最优选30-50wt％。下面更详细地描述本文所提到的丙烯酸类。所述丙烯酸类树脂或丙烯酸类聚合物包括乙烯基聚合物，并且优选包含(甲基)丙烯酸酯和任选的(甲基)丙烯酸类，包括甲基丙烯酸甲酯、丙烯酸乙酯和/或丙烯酸丁酯，和苯乙烯-(甲基)丙烯酸酯或苯乙烯-(甲基)丙烯酸类。
乙烯基聚合物在本文中通常是指衍生自至少一种烯属不饱和单体的加成聚合(通常通过自由基方法)的聚合物。因此，乙烯基单体在本文中是指能够进行自由基聚合的烯属不饱和单体。乙烯基聚合物优选由0至10wt％的至少一种含有酸官能团的乙烯基单体(单体(i))和90至100wt％的不是(i)所含的另一种乙烯基单体(单体(ii))组成。这种乙烯基单体(ii)的实例包括共轭二烯，任选取代的二烯；苯乙烯和取代的苯乙烯；烯烃如乙烯或丙烯；乙烯基卤化物；乙烯基酯如乙酸乙烯酯、丙酸乙烯酯、月桂酸乙烯酯和新癸酸(versaticacid)的乙烯基酯如VeoVaTM 9和VeoVaTM 10(VeoVa是Shell的商标)；杂环乙烯基化合物，单烯属不饱和二羧酸的二烷基酯(如马来酸二正丁酯和富马酸二正丁酯；乙烯基醚；特别是下式的丙烯酸和甲基丙烯酸的酯：
CH2＝CR1CO2R2，其中
R1是H或甲基，并且
R2是任选取代的1-20个碳原子、优选1-8个碳原子的烷基，或5-12个环碳原子的环烷基。
此类单体的其他具体例子包括：烷基酯和(氯)烷基酯例如α-氯丙烯酸甲酯，α-氯丙烯酸正丙酯，α-氯丙烯酸正丁酯，丙烯酸β-氯乙基酯，丙烯酸β-氯丁基酯，(甲基)丙烯酸甲酯，(甲基)丙烯酸乙酯，(甲基)丙烯酸丙酯(所有异构体)，(甲基)丙烯酸丁酯(所有异构体)，(甲基)丙烯酸异冰片酯，(甲基)丙烯酸环己酯，(甲基)丙烯酸2-乙基己酯，(甲基)丙烯酸辛酯，(甲基)丙烯酸月桂酯，(甲基)丙烯酸三氟乙酯，马来酸二乙酯，富马酸二乙酯；乙烯基酯例如乙酸烯丙酯，氯乙酸烯丙酯，乙酸甲代烯丙酯(methallyl acetate)，乙酸乙烯酯，乙酸异丙烯酯；卤乙烯例如氯乙烯，偏二氯乙烯，烯丙基氯，1,2-二氯丙烯-2，甲代烯丙基氯和三氯乙烯；腈类例如丙烯腈和甲基丙烯腈；乙烯基芳基类例如苯乙烯，α-甲基苯乙烯，邻甲基苯乙烯，间甲基苯乙烯，对甲基苯乙烯，五氯苯乙烯，邻氯苯乙烯，间氯苯乙烯，对氯苯乙烯和对氰基苯乙烯；共轭二烯或氯二烯例如丁二烯和氯丁二烯；以及乙烯基取代的杂环亚胺例如2-乙烯基-吡啶和乙烯基咔唑。也可用于形成乙烯基聚合物的其它乙烯基单体是带有官能团(并且上文未提及)的那些乙烯基单体。它们可以包括例如羟基官能单体例如丙烯酸羟乙酯(HEA)和甲基丙烯酸羟乙酯(HEMA)，以及烯属不饱和酰胺例如丙烯酰胺和甲基丙烯酰胺。基于用于形成所述乙烯基聚合物的总单体组合物，作为(iii)的一部分并入的此类官能单体的量为0-20重量％，优选0-7重量％，更优选0-2重量％，最优选0.1至2重量％。然而，在大多数情况下，不使用所述官能单体。也可用于形成乙烯基聚合物的其它乙烯基单体是带有可交联基团(并且上文未提及)的那些。可交联基团在与交联剂组合时或者通过彼此反应而赋予可交联性。携带可交联基团的乙烯基单体包括例如烯丙基、缩水甘油基或乙酰乙酰氧基酯、乙酰乙酰氧基酰胺、酮和醛官能乙烯基单体、含酮酰胺例如双丙酮丙烯酰胺、以及硅烷官能(甲基)丙烯酸单体。带有可交联基团的优选乙烯基单体是甲基丙烯酸乙酰乙酰氧基乙酯(AAEM)、双丙酮丙烯酰胺(DAAM)和硅烷官能(甲基)丙烯酸单体，最优选DAAM。特别优选的乙烯基单体(ii)选自甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸2-乙基己酯、苯乙烯和丙烯腈中的一种或更多种。
含有酸官能团的乙烯基单体(i)优选为烯属不饱和单羧酸或二羧酸，其例子包括丙烯酸、甲基丙烯酸、丙烯酸2-羧乙酯、富马酸、马来酸、衣康酸、和二羧酸的单-取代的C1-C20烷基酯。单羧酸是优选的，特别优选的用于(i)的单体是甲基丙烯酸和丙烯酸中的一种或两种。
可以通过本领域已知的任何自由基聚合方法(例如乳液聚合或悬浮聚合)制备乙烯基聚合物。乳液聚合是优选的。可以使用本领域已知的各种聚合方法制备聚合物，例如单批顺序梯度聚合，也通常称为自动进料(power feed)聚合。如果期望的话，可以使用预先形成的或原位形成的种子。
单体组合物聚合形成乙烯基聚合物通常需要使用产生自由基的引发剂来引发聚合。合适的产生自由基的引发剂包括无机过氧化物，例如过硫酸钾、过硫酸钠或过硫酸铵，过氧化氢或过碳酸盐；有机过氧化物，例如酰基过氧化物(包括例如过氧化苯甲酰)，烷基氢过氧化物例如叔丁基氢过氧化物和枯烯氢过氧化物；二烷基过氧化物例如二叔丁基过氧化物；过氧酯例如过苯甲酸叔丁酯等；也可以使用混合物。EDTA(EDTA：乙二胺四乙酸)也可被有用地用作氧化还原引发剂体系的一部分。可以使用表面活性剂以帮助聚合单体和产生的乙烯基聚合物A在水中的分散或乳化。合适的表面活性剂包括但不限于常规的阴离子、阳离子和/或非离子表面活性剂及其混合物，例如二烷基磺基琥珀酸酯的Na、K和NH4盐，硫酸化油的Na、K和NH4盐，烷基磺酸的Na、K和NH4盐，烷基硫酸酯的Na、K和NH4盐，磺酸的碱金属盐；脂肪醇，乙氧基化脂肪酸和/或脂肪酰胺，以及脂肪酸的Na、K和NH4盐例如硬脂酸钠和油酸钠。其它阴离子表面活性剂包括连接至磺酸基、硫酸半酯基团(其又连接到聚乙二醇醚基团)、膦酸基团、磷酸类似物和磷酸酯或羧酸基团的烷基或(烷)芳基。阳离子表面活性剂包括连接至季铵盐基团的烷基或(烷)芳基。非离子表面活性剂包括聚乙二醇醚类化合物，优选聚环氧乙烷类化合物。通过在聚合过程中使用链转移剂(CTA)例如3-巯基丙酸或正月桂基硫醇，可以降低乙烯基聚合物的分子量Mw。使用特定Co螯合物催化剂作为CTA的催化链转移聚合也可用于降低Mw。
本发明中的丙烯酸基热塑性材料优选是基于丙烯酸类树脂或丙烯酸类聚合物的热塑性基质材料，其优选具有至少25℃的玻璃化转变温度。基质材料的替代实施方案可包括玻璃化转变温度为至少25℃的基于丙烯酸类树脂或丙烯酸类聚合物的热固性等价物。根据本发明的三维成型制品证明具有改善的表面外观。以这种方式，可以涂布制品，由此需要涂覆较少的底漆或表面涂饰，或者在涂覆涂层之前甚至不需要对表面进行处理以使缺陷和折痕均匀。
在上述织物(100)中，丙烯酸基热塑性材料的存在量为至多70wt％，优选至多60wt％，更优选至多50wt％。该织物包含至少10％、优选至少15wt％、更优选至少20wt％的丙烯酸基热塑性材料。通常，丙烯酸基热塑性材料在织物中的存在量为10-60wt％，优选20-50wt％，更优选30-40wt％。
织物(100)的重量通常为70g/m2至400g/m2，优选为100g/m2至400g/m2，更优选为150g/m2至300g/m2。
根据本发明的三维制品可包括两层或更多层织物(100)。这两个或更多个层(100)可以彼此直接连接，或者可以交替连接并连接到其它基于纤维的片材。合适的三维成形制品可以由若干层织物(100)组成，其中这种制品的总重量为75至750g/m2，优选100至500g/m2。除了织物层(100)之外，根据本发明的制品还可包含其它基于纤维的片材或层。这些层可包括织造的单向纤维层或非织造纤维层。这些层可适当地基于纤维，所述纤维包括聚烯烃纤维、超高分子量聚乙烯纤维、超高分子量聚丙烯纤维、芳族聚酰胺纤维、超高分子量聚乙烯醇纤维、来自液晶聚合物的纤维、或它们的混合物。合适的聚烯烃特别是乙烯和丙烯的均聚物和共聚物，其也可含有少量的一种或多种其它聚合物，特别是其它烯烃-1-聚合物。优选地，纤维网络包括超高分子量聚乙烯纤维。
在一个优选的实施方式中，所述制品还包含至少一层、优选至少2层具有单向排列的超高分子量聚乙烯纤维。具有嵌入塑料(塑性)基质材料中的单向排列纤维的层在下文中称为“单层”。术语“塑料基质材料”是指将纤维保持在一起并且优选完全或至少部分地包封纤维的材料。这种单层(本领域技术人员也称为预浸料)和获得这种单层的方法公开在例如EP 191306和WO 95/00318 A1中。单层可以通过下述方法获得：例如通过从纤维线轴经过梳齿抽拔若干纤维或者纱线，以共面和平行的方式在一个平面中对多根纤维进行取向，并且在取向之前、期间或之后以公知的方法，用塑料基质材料浸渍所述纤维。在这种方法中，可以使用预先已经用不同于所述塑性基质材料的聚合物涂布的纤维，以便例如在处理过程中保护纤维，或者以便得到更好的纤维到单层的塑料上的粘附性。优选地，使用未经涂布的纤维。纤维可以在用塑料基质材料涂布或接触纤维之前进行处理。这种处理包括等离子体处理或电晕处理。
单层的重量通常为20g/m2至200g/m2，优选为30g/m2至100g/m2，优选为40g/m2至75g/m2。
通常堆叠单层，使得堆叠中两个连续单层中纤维的方向通常相差角度α。虽然可以在宽范围内选择角度α，但角度α优选在45-135度之间，更优选在65-115度之间，最优选在80-100度之间。在后面的优选范围内，特别优选的角度α为约90度。堆叠的单层通常是商业上可获得的，具有例如，2、4或6个单层，并且在本领域中被称为交叉层(cross ply)。
在交叉层中，纤维网络占据片材总体积的不同比例。然而，优选地，纤维网络占复合材料的至少约50体积％、更优选约70体积％、最优选至少约75体积％，基质任选地占据剩余体积。
术语“纤维”不仅包括单丝，而且还包括复丝纱线或扁平带材。扁平带材的宽度优选在2mm和100mm之间，更优选在5mm和60mm之间，最优选在10mm和40mm之间。扁平带材的厚度优选在10μm和200μm之间，更优选在25μm和100μm之间。扁平带材可以由一种材料的单一构件组成，但也可以包含单向取向的纤维和任选的基质材料。带材也可以通过凝胶纺丝工艺制造，但也可以通过固态工艺获得，由此压缩和拉伸聚合物粉末以获得具有所期望强度的带材。
在任选的单层中使用的纤维可以与织物(100)中的纤维相同，或者可以在物理或化学方面上不同，并且具有至少1.5GPa、优选至少2.5GPa的强度。更优选地，单层中使用的纤维具有至少3.5GPa的强度，这导致高冲击性能和具有增加的刚性的最终产品的良好组合。甚至更优选地，用于本发明网络的纤维具有至少4GPa的强度，以获得具有良好防弹性能的产品，最优选至少4.5GPa。
用塑料基质材料浸渍单向排列的纤维可以例如通过以下方式来实现：将一个或更多个塑料膜施加到纤维平面的顶部、底部或两侧，然后使它们与纤维一起穿过加热的压力辊。然而，优选地，纤维在一个平面内以平行方式取向后，向其涂布一定量的含有单层的塑料基质材料的液体物质。这么做的优点是能够更迅速且更好地浸渍纤维。所述液体物质可以是例如塑料的溶液、分散体或熔体。如果使用塑料基质材料的溶液或分散体来制造单层，则该方法还包括蒸发溶剂或分散剂，优选随后在升高的温度下压缩。这样的温度和压力容易通过常规实验来确定，并且通常在70℃和纤维的熔化温度之间，优选75-135℃之间，和1-100巴之间，优选5-80巴之间，更优选10-60巴之间。
为了制造单层，优选使用热塑性基质材料的水分散体，其中在涂覆至HPPE纤维之后，水至少部分、优选至少90重量％、更优选至少99重量％被蒸发。
本发明的一个特殊实施方式涉及三维成型制品，其包含至少一种HPPE纤维的织物(100)，所述HPPE纤维浸渍有Tg至少为25℃的热塑性丙烯酸类树脂，该制品还包含至少两个单向排列的具有基质的HPPE纤维的单层。优选地，织物中的HPPE纤维或单向排列的纤维是聚乙烯纤维，其强度至少为3.5GPa。在一个特定的实施方式中，聚氨酯或聚醚氨酯基于脂族二异氰酸酯，因为这进一步改善了产品性能，包括其颜色稳定性。用于单向排列纤维的这些塑料基质材料的100％模量至少为3MPa。优选地，100％模量为至少5MPa。100％模量通常低于500MPa。
在另一个优选的实施方式中，用于单向排列纤维的合适的替代型基质材料是其由水分散体施用。聚合物包含苯乙烯-异戊二烯-苯乙烯(SIS)三嵌段共聚物组合物，其100％模量为1.4MPa，并且取决于这种三嵌段共聚物的类型，甚至可以小于1.4MPa。
另一个优选的实施方式涉及用于浸渍织物(100)的合适材料，其作为乙烯和/或丙烯的官能化均聚物或共聚物(也称为聚乙烯、聚丙烯或其共聚物)的水悬浮液施用。它可包括各种形式的聚乙烯，乙烯-丙烯共聚物，具有共聚单体(诸如1-丁烯、异丁烯)以及具有含杂原子的单体(诸如丙烯酸、甲基丙烯酸、乙酸乙烯酯、马来酸酐、丙烯酸乙酯、丙烯酸甲酯)的其它乙烯共聚物；通常α-烯烃和环烯烃均聚物和共聚物，或它们的共混物。优选地，它是乙烯或丙烯的共聚物，其可含有一种或多种具有2至12个C原子的烯烃作为共聚单体，特别是乙烯、丙烯、异丁烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯、丙烯酸、甲基丙烯酸和乙酸乙烯酯。在聚合物树脂中不存在共聚单体的情况下，可以使用多种聚乙烯或聚丙烯，例如线性低密度聚乙烯(LLDPE)、极低密度聚乙烯(VLDPE)、低密度聚乙烯(LDPE)、全同立构聚丙烯、无规立构聚丙烯、间同立构聚丙烯或其共混物。官能化是指聚合物是通过共聚或接枝而官能化。“接枝”是指主要用含有杂原子的烯属不饱和单体对聚合物主链的化学改性，而“官能共聚物”是指乙烯或丙烯与烯属不饱和单体的共聚合。优选地，烯属不饱和单体包含氧和/或氮原子。最优选地，烯属不饱和单体包含羧酸基团或其衍生物，得到酰化聚合物，特别是乙酰化聚乙烯或聚丙烯。优选地，羧酸类反应物选自丙烯酸类、甲基丙烯酸类、肉桂酸类、巴豆酸类和马来酸类、富马酸类和衣康酸类反应物。所述官能化聚合物通常包含1-10wt％的羧酸类反应物或更多。这种官能化在树脂中的存在可以大幅增强树脂的分散性和/或允许减少为此目的存在的其它添加剂，例如表面活性剂。
本发明还涉及制造具有外表面和内表面的三维成型制品的方法，包括以下步骤：
(a)提供至少一种拉伸强度为至少1.5GPa的聚乙烯纤维的织物，所述织物浸渍有丙烯酸基热塑性材料，由此所述至少一种织物形成所述制品的外层；和
(b)将来自(a)的产品与至少一个任选的单向排列纤维的单层堆叠在一起；
(c)提供用于成型三维制品的模具；
(d)任选地用脱模剂涂布模具表面；
(e)将步骤(b)的叠层定位在所述模具中；然后
(f)在90至145℃的温度下，优选在100至135℃的温度下，在1至35MPa的压力下，在2至60分钟的时间内压缩所述叠层；然后
(g)冷却至低于80℃的温度，并从所述模具中释放如此获得的制品。
已经证明，使用具有丙烯酸基热塑性材料的聚乙烯纤维的织物作为外表面用于制造三维成型制品包括是非常有益的。不仅能够使模制产品的表面光滑，而且还能够实现良好的漆料粘附性。
进一步证明了脱模剂有利于产品的表面外观。另一种替代性选择是经涂布的模具用于制造根据本发明的三维制品。
受益于本发明的合适的三维成型制品包括小穹顶、圆顶、半圆顶、半球、帽、建筑头盔、运动头盔、摩托车头盔、防弹头盔和顶篷。
在附图中，图1表示具有外表面(1)和内表面(2)的三维成型制品的横截面图，该外表面包含至少一个含有聚乙烯纤维的织物(100)。
测试程序
丙烯酸热塑性材料的聚合物数均分子量是在40℃下根据DIN 55672通过凝胶渗透色谱法测定的，其中使用四氢呋喃作为溶剂，苯乙烯/二乙烯基苯作为包装材料，并使用聚苯乙烯Mp 160-10000000(聚合物标准服务(PSS)DIN认证的标准品)进行校正。
实施例中聚合物的玻璃化转变温度采用以差示扫描量热法DSC(10℃/分钟)实验确定的以℃计的值，取导数曲线的峰值作为Tg。
根据ISO 527测定基质材料的模量。在长度为100mm(夹子之间的自由长度)且宽度为24mm的膜条上测定100％模量。100％模量是在0％和100％的应变之间测量的割线模量。
拉伸强度(或强度)是根据ASTM D885M中规定在复丝纱线上限定和测定的，使用500mm的纤维的名义标定长度，50％/min的十字头速度，在25℃下测量。在测得的应力-应变曲线的基础上，随着0.3和1％应变之间的梯度来测定模量。为了计算模量和强度，将测得的拉伸应力除以纤度，纤度通过称重10米的纤维测定；假定聚乙烯的密度为0.97g/cm3，计算以GPa计的值。
聚乙烯的特性粘度(IV)是根据ASTM D1601在135℃下在十氢化萘中测定的，溶解时间为16小时，采用用量为2g/l溶液的DBPC作为抗氧化剂，并且将在不同浓度下测量的粘度外推得到零浓度下的粘度。
根据ISO 2409，使用'Gitterschnitt'测试进行粘附性测试。以1mm的刮擦距离以规则图案刮擦测试样品，其中划痕必须在涂层中而不是在基材中。将3M粘合带(ScotchTM)施加在划痕图案上并随后拉出。良好的粘附性意味着涂层不会脱落。粘附性差将导致涂层与基材分离。
视觉量化分离的量。
现在将通过以下对比实验和实施例进一步阐明本发明，但不限于此。
实施例
材料：
织物：采用强度为3.5GPa的UHMWPE纤维和30wt％的(甲基丙烯酸甲酯丙烯酸类共聚物)的平纹织物；片材的总重量为245g/m2
CF：在一个方向上的聚乙烯纤维和在相反方向上的碳纤维的平纹编织结构，具有31wt％的聚乙烯；片材的总重量为235g/m2
UD：由18wt％的基于聚醚二醇和脂族二异氰酸酯的聚氨酯树脂和强度为3.5GPa的UHMWPE纤维的交叉单层的层组成的一个片材；片材的总重量为145g/m2
对比实验A：
通过堆叠43片UD并在175巴的压力和130℃的温度下将它们在模具中压制25分钟，然后在压力下冷却至至少80℃，然后从模具中取出，来制备头盔。在将叠层放入模具中之前，用脱模剂喷涂模具。
在从头盔的边沿切割碎片之后，由于切割边沿的外表面处的一些长丝的分层而发生一些表面缺陷。此外，由于模塑过程，在外表面层中出现一些折痕。头盔上涂有标准的绿色漆料，目测检查表面外观。可以看出，漆料不能减轻表面缺陷，外表面仍然可以看到缺陷。
通过Gitterschnitt测试漆料粘附性，并且由于漆料的剥落而证明是差的。
对比实验B：
与对比实验A相同地制造头盔，其中压制42片UD和一片CF外层。
在头盔的外表面层中没有出现折痕；然而，由于头盔的更垂直部分中的高剪切力，CF中的碳纤维发生纤维断裂。在涂漆之后，由于CF外层中仍然可见的断裂纤维，头盔的表面外观是有缺陷的。
通过Gitterschnitt的漆料粘附性证明是良好的，没有发生漆料剥落。
实施例1：
与对比实验A相同地制造头盔，其中压制42片UD和一层织物外层。
压制后头盔外表面层无折痕；没有发生纤维断裂，且表面光滑。涂漆后表面外观光滑无缺陷。
通过Gitterschnitt的漆料粘附性证明是良好的，没有漆料剥落。
如实施例1中举例说明的那样，只有根据本发明的制品显示出良好的表面外观，这可以通过在涂漆之前和之后基本没有折痕的光滑表面来判断，以及显示出良好的漆料粘附性。

Claims (15)

1.具有外表面和内表面的三维成型制品，所述外表面包含至少一种拉伸强度为至少1.5GPa的聚乙烯纤维的织物(100)，所述织物浸渍有丙烯酸基热塑性材料。
2.根据权利要求1所述的制品，其中所述丙烯酸基热塑性材料的玻璃化转变温度为至少25℃。
3.根据权利要求1或2所述的制品，其中丙烯酸基热塑性材料的量为4-35重量％。
4.根据权利要求1-3所述的制品，其中所述纤维是UHMWPE纤维。
5.根据权利要求1-4所述的制品，其中所述织物是平纹织物。
6.根据权利要求1-5所述的制品，其还包含至少一个单向纤维的单层。
7.根据权利要求1-6所述的制品，其还包含至少两层单向排列的聚乙烯纤维。
8.根据权利要求1-7所述的制品，其中具有单向排列纤维的单层包含100％模量为至少3MPa的基质材料。
9.根据权利要求8所述的制品，其中所述基质材料是热塑性聚氨酯。
10.根据权利要求1-9所述的制品，其中所述制品的面重量为75-1250克/平方米。
11.根据权利要求1-10所述的制品，其中所述制品的面重量为125-1000克/平方米。
12.如前述权利要求中任一项所述的制品，其中所述制品是头盔。
13.如前述权利要求中任一项所述的制品，其中所述制品是天线罩。
14.制造具有外表面和内表面的三维成型制品的方法，包括以下步骤：
(a)提供至少一种拉伸强度为至少1.5GPa的聚乙烯纤维的织物，所述织物浸渍有丙烯酸基热塑性材料，由此所述至少一种织物形成所述制品的外层；和
(b)将来自(a)的产品与至少一个任选的单向排列纤维的单层堆叠在一起；
(c)提供用于成型三维制品的模具；
(d)任选地用脱模剂涂布模具表面；
(e)将步骤(b)的叠层定位在所述模具中；然后
(f)在90至135℃的温度下，在1至35MPa的压力下，在2至60分钟的时间内压缩所述叠层；然后
(g)冷却至低于80℃的温度，并从所述模具中释放如此获得的制品。
15.具有丙烯酸基热塑性材料的聚乙烯纤维的织物作为外表面用于制造包括头盔的三维成型制品的用途。
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IL269231B2 (en) 2024-08-01
BR112019019404A2 (pt) 2020-04-14
EP3601931B1 (en) 2022-05-04
IL269231B1 (en) 2024-04-01
BR112019019404B1 (pt) 2023-04-11
WO2018172304A1 (en) 2018-09-27
AU2018240334A1 (en) 2019-10-03
AU2018240334B2 (en) 2024-03-21
EP3601931A1 (en) 2020-02-05
US20200009827A1 (en) 2020-01-09
KR20190128209A (ko) 2019-11-15
KR102514352B1 (ko) 2023-03-24
TWI818905B (zh) 2023-10-21

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