CN107406598A - 粉末状乙烯基酯预浸料 - Google Patents
粉末状乙烯基酯预浸料 Download PDFInfo
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- CN107406598A CN107406598A CN201580067887.9A CN201580067887A CN107406598A CN 107406598 A CN107406598 A CN 107406598A CN 201580067887 A CN201580067887 A CN 201580067887A CN 107406598 A CN107406598 A CN 107406598A
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- powder
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- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical group C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
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- 239000008187 granular material Substances 0.000 description 1
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- 231100000616 occupational exposure limit Toxicity 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- B29B11/00—Making preforms
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- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/14—Peroxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2363/10—Epoxy resins modified by unsaturated compounds
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Reinforced Plastic Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
本发明提供包括具有在‑5到+30℃范围内的Tg和在2‑75dPa.s范围内的100℃的熔体粘度的乙烯基酯树脂作为唯一树脂的粉末预浸料，其可用于在低至80℃的温度下制造复合材料。
Description
技术领域
本发明涉及涂覆有树脂的增强纤维。
背景技术
结构复合材料(复合制品，composites)的体积(主体)部分由用玻璃纤维增强的不饱和聚酯树脂(UPR)主导，并且通常称为GRP(玻璃纤维增强的聚酯)。该树脂的反应性稀释剂一成不变地为苯乙烯，其正遭受更严格的管制措施、特别是在工作场所中较低的职业接触极限(occupational exposure limits)。这已经导致树脂供应商和加工者(processor)寻求苯乙烯的替代方案。第一途径一直涉及使用替代性的乙烯基芳族单体例如乙烯基甲苯和二乙烯基苯。然而，这些物质的管制状况(status)未显著地有别于苯乙烯的管制状况。第二途径一直是使用甲基丙烯酸酯单体(典型地为二甲基丙烯酸丁二醇酯、二甲基丙烯酸三甘醇酯和甲基丙烯酸羟基丙基酯)。这些甲基丙烯酸酯的较低的蒸气压意味着进入到工作场所气氛中的排放物(emission)比苯乙烯的那些低得多。然而，该优势由于这些物质的潜在的皮肤敏感性而抵消。
存在很多种不同的用于制造结构复合材料部件的转化方法。所选择的方法取决于多种因素例如：待制造的部件的数量、部件的尺寸、结构要求和期望的生产率。高的生产率可通过热压成型实现，其中首先将树脂转化成‘预浸料’：树脂预浸渍的增强材料。在所述技术中，预浸料为“预浸渍的”复合材料纤维的术语。对于热压成型，这些预浸料的典型例子为Dough Moulding Compound(DMC)和Sheet Moulding Compound(SMC)。
WO9222603(DSM)公开了由纤维材料和实质上粉末化的热固性树脂组成的半成品，该热固性树脂具有高于35℃的玻璃化转变温度、比所述玻璃化转变温度高至少40℃的固化温度和在所述玻璃化转变温度和所述固化温度之间的温度下的小于5000Pa.s的粘度，树脂粒子是部分融合的并且与所述纤维材料部分接触。所有实例依赖于基于不饱和聚酯的单一组合物，然而，它们要求使用至少一种稀释剂即氰尿酸三烯丙基酯(高沸点的可共聚单体)；在150℃下进行固化。
因此，存在对于可在低至80℃的温度固化的不含单体的组合物的需求。
本发明的主题是使用粉末树脂的新颖的预浸料理念(concept)，由此显著减少具有潜在担忧和潜在皮肤敏感问题的物质的挥发性工作场所排放。另外，本发明具有明显的加工和生产率益处。
发明内容
本发明的基础是固体热固性树脂，其为乙烯基酯(通过环氧树脂和不饱和一元羧酸的开环而制造的树脂)。本文使用的乙烯基酯包括纯的乙烯基酯和多种乙烯基酯(其通过它们的分子量、酸和/或环氧物的化学类型进行区分)的共混物。每种乙烯基酯必须具有Tg和熔体粘度的适当平衡。所述树脂在常规设备中通过常规工艺制造。然而，所述树脂不稀释(let-down)于苯乙烯或任何其它稀释剂中。
然后，将固体树脂以仔细受控的方式进行机械研磨或微粉化以制造具有取决于期望应用的粒度和粒度分布的粉末。典型地，所述粉末具有80％体积的20-100um的粒子、和99％的0.5-100um的粒子。
此刻，可通过共混方式、优选地通过干式(干法)共混掺杂固化引发剂和任何期望的添加剂。待干式共混的粒子的尺寸和分布应该基本相同。添加剂包括填料、表面改性剂、颜料和可能的阻燃剂或泡沸添加剂。
然后，使用所述粉末浸渍纤维增强材料，其可为松散纤维形式、或者非织造或纺织(织造)材料形式。所述浸渍可为通过简单浇铸(casting)工艺的方式、通过喷雾或通过静电工艺进行。
然后，必须将所述粉末树脂通过短的加热过程例如在烘箱中放置或辐射暴露而原位固定。使加热步骤的温度和持续时间最小化以确保粒子在未过度交联的情况下附着到纤维。
现在加工者可存储、输送或使用由此获得的预浸料以制造结构组件。在固定步骤期间存在最小量的不可避免的交联，其可具有提高刚好足以容许在室温下存储所述预浸料的Tg的优点。
应用
所述理念，即在用在敞模成型工艺例如手工铺展和喷射成型中的液体UPR的替代物方面首先想到用原始(origin)作为粉末的树脂涂覆增强纤维，。显而易见的优点在于除去了苯乙烯在工作场所中的排放。可制造的部件在尺寸、形状和厚度上可变化。设想到的领域(sector)为船舶(marine)、建筑和工业。
结构复合材料部件通常为‘凝胶涂覆的(Gel Coated)’。凝胶涂层为提供该部件的装饰和保护层的组件。凝胶涂覆工艺可为高的苯乙烯排放源。可使用粉末预浸料理念代替所述凝胶涂层。在这样的情况中，玻璃罩纱(遮蔽物，veil)或薄纱(tissue)用粉末树脂、引发剂、颜料和任选的填料进行浸渍。将浸渍的罩纱放置到加热模具中以促进固化，并且然后复合材料部件可通过放置粉末预浸料层或常规树脂和增强材料而构建。据认为，该理念特别适用于例如在冷冻运输中作为绝缘面板的薄而平的复合材料结构体。
在建筑和运输领域中的很多复合材料应用要求阻燃性。常规上，这已经通过在所述树脂制剂中包含卤素化合物或通过添加氢氧化铝填料而实现。第一途径具有在失火事件时高的烟雾排放的不利方面；另外，这些卤素化合物的很多正面临REACH(REACH是欧盟关于化学品的注册、评估、授权和限制的规章)的监督。第二途径的问题在于，高水平(含量)的填料使得液体树脂难以加工。然而，我们已经证明，使用树脂与泡沸添加剂和填料的粉末共混物的粉末预浸料理念制造了高度有效的泡沸复合材料。感觉其对于轨道机动车辆(railrolling-stock)应用是特别合适的。
以上引入片材成型化合物的理念。本化合物使用基于苯乙烯的液体树脂，尽管使用甲基丙烯酸酯稀释剂的一些产品已经现于市场。粉末预浸料理念容许除去苯乙烯和任何其它稀释剂、具有较高的纤维内容物和因此具有较大的结构强度。
通常对于高的结构要求，预浸料还与环氧树脂并存。在它们使用上的约束包括高成本、短的保存期限以及对于相对长的固化周期和高的加工温度的需要。本发明提供了在这些参数的每一个上的显著改进。设想到，产品将普遍地适用于工业和日常(leisure)应用。
描述
本发明的基础为作为乙烯基酯的固体热固性树脂。所述树脂在常规设备中通过常规加工制造。然而，所述树脂不稀释于苯乙烯或任何其它稀释剂中。制剂的范围和类型对于本领域技术人员是熟知的。
乙烯基酯为通过环氧树脂和不饱和一元羧酸的开环制造的树脂。其为热固性树脂。
典型地，所述环氧树脂基于双酚A(当量180-500)，并且所述一元羧酸为甲基丙烯酸。也可使用丙烯酸及衍生物。还可使用酚醛清漆(Novolac)环氧树脂以及酚醛清漆和双酚A环氧树脂的共混物。
典型地，所述成分以1当量的环氧树脂对1摩尔的酸的比率进行反应。
乙烯基酯的实例为通过使双酚A环氧树脂和甲基丙烯酸进行反应而获得的双酚A缩水甘油基甲基丙烯酸酯。
实质上在本申请中关键之处在于平衡Tg和熔体粘度。所述树脂的Tg应该在-5到+30’C、优选地在+5到+25’C、最优选地在+10到+20℃的范围内。100’C的熔体粘度应该在2-75dPa.s、优选地在10-25dPa.s的范围内。
必须将所述树脂转化为粉末。这可通过机械研磨机或空气驱动的粉碎机例如在低于Tg的温度下操作的喷磨机完成。优选的粒度范围可通过加工中的分级或加工后的处理例如筛分实现。平均粒度(d50)的宽范围将为10-30um。典型地，所述粉末将具有80％体积的20-100um的粒子和99％的0.5-100um的粒子。
必须将所述粉末在低于其Tg的温度下存储。
此刻，添加剂通过共混或涂覆工艺(仍然在低于Tg的温度下)进行掺杂，并且将包括固化引发剂(或引发剂)和其它期望的添加剂例如填料、表面改性剂、颜料以及可能的阻燃剂和泡沸添加剂。固化引发剂或催化剂对于本领域技术人员是熟知的，并且典型地为有机过氧化物；1小时半衰期温度优选地低于100℃、更优选地低于85℃、最优选地低于70℃。所述引发剂可与一种或多种加速剂或促进剂、典型地钴化合物和胺化合物组合；作为拇指规则(定律)，这些可使所述固化温度降低10-20℃。所述填料可用来所述树脂组合物增量(extend)，例如碳酸钙，或者用来赋予性能优点，例如氢氧化铝(阻燃性)。表面改性剂可例举金属硬脂酸盐；它们对于保存所述树脂粒子在存储期间的完整性是有用的。
然后，使用粉末共混物浸渍可为松散纤维形式、或者非织造或纺织材料形式的纤维增强材料。所述纤维需要与所述乙烯基酯树脂相容，并且因此优选为玻璃纤维、更优选地选自E-玻璃和S-玻璃。所述浸渍可通过简单浇铸工艺的方式、通过喷雾或优选地通过静电工艺进行。选择的工艺取决于预期应用。例如，已知所述静电工艺提供特别高效且均匀的树脂粒子的分布，并且因此对于高结构要求是十分合适的。这样的高效静电工艺的实例在EP1 998 953 B1中提供。
然后，必须通过短的加热过程例如在烘箱中放置、辐射暴露或压延(calendaring)将粉末树脂共混物原位固定。其目的不是使所述树脂组合物固化，而是将所述树脂粒子固定到所述纤维。所述加工将典型地在70-100℃、优选地70-95℃、最优选地70-90℃进行典型地3-7分钟、优选地约5分钟的时期。
现在，加工者可存储、输送或使用粉末预浸料以在包括将根据本发明的预浸料放置到模具中和加热所述预浸料的过程中制造结构或半结构组件，其中加热步骤包括在70-120℃、优选地75-100℃、更优选地80-90℃范围内的温度下进行加热。
实施例
玻璃化转变温度Tg通过根据ISO 11357-2:2013的方法测定。
熔体粘度使用标准的锥板(cone and plate)粘度计测定。
粒度分布通过基于Mie散射理论的激光衍射法测定。它是由l'ISO13320(2009)涵盖(收录)的确立的技术。
实施例1A：双酚A乙烯基酯的合成
将146g双酚A环氧树脂(当量182-192)和653g双酚A环氧树脂(当量450-500)加入到装备有搅拌器的2升Quickfit烧瓶、回流、冷却、氮气和空气鼓泡。向其添加0.3g鹿蹄草素(toluhydroquinone,甲基氢醌)和3g 2,4,6-三(二甲基氨基甲基)苯酚催化剂(AncamineK54)。当在维持所述温度低于115℃这样的速率下加入200g甲基丙烯酸时，将混合物缓慢地加热到110℃。然后，将所述混合物保持在115℃下直至达到低于8mg KOH/g的酸值。将所述混合物倒入到铝制托盘中并且容许其冷却和凝固。
实施例1B：环氧酚醛清漆乙烯基酯的合成
将175g双酚A环氧树脂(当量182-192)和480g环氧酚醛清漆树脂(当量170-180)加入到装备有搅拌器的2升Quickfit烧瓶、回流、冷却、氮气和空气鼓泡。向其添加0.2g鹿蹄草素和3.5g 2,4,6-三(二甲基氨基甲基)苯酚催化剂(Ancamine K54)。当在维持所述温度低于110℃这样的速率下加入330g甲基丙烯酸时，将所述混合物缓慢地加热到100℃。然后将所述混合物保持在115℃下直至实现低于13mg KOH/g的酸值。将所述混合物倒入到铝制托盘中以进行冷却并且然后转移到深度冷冻器。
实施例2A：双酚A乙烯基酯粉末
将实施例1A中的固体机械地粗磨成2-5mm直径的颗粒。在控制到15℃的实验室气候下进行以下操作。将所述颗粒在Waring共混机中转化成粉末。通过将干冰引入到共混机腔室中而进一步降低温度。对所得的粉末进行筛分以制造1,000g的<100um的混合物。在低剪切共混过程中向其加入20g硬脂酸钙。
特性：Tg＝17℃，80℃的熔体粘度>100dPa.s，100℃的熔体粘度＝49dPa.s，粒度分布：
| d10 | d50 | d90 | d100 |
| 3um | 14um | 42um | 96um |
然后，在低剪切共混过程中向所述粉末添加10g热解法二氧化硅和15g Perkadox16引发剂(二(4-叔丁基环己基)过氧二碳酸酯，64℃的1小时半衰期温度)。将所述粉末在低于Tg下存储。
实施例3A：双酚A乙烯基酯粉末
在用Perkadox L DFG(过氧化二苯甲酰，91℃的1小时半衰期温度)代替Perkadox16的情况下，重复实施例2A。将所述粉末在低于所述Tg下存储。实施例2B：环氧酚醛清漆乙烯基酯粉末
使用实施例1B的固体并且在控制到-15℃的实验室橱柜中重复实施例2A。
特性(在添加引发剂之前)：Tg＝-4℃，80℃的熔体粘度为6dPa.s，100’C的熔体粘度为2dPa.s。粒度分布：未测定(Tg太低)。
实施例4A：粉末预浸料
将包括800g/m2的双轴向的(45/45°)衣物(weight)和200g/m2的短切原丝毡的玻璃增强毡切割成片段(section)15x 15cm。将片段放置在如EP 1 998953B1中描述的D-Preg静电浸渍机的腔室中。将实施例3A中描述的且从所述深度冷冻器直接取出的粉末量(30g)施加到所述毡，然后进行浸渍，如EP 1 998 953 B1中描述的。将所述粉末通过在90’C的烘箱中放置5分钟而原位固定，从而制造15x 15cm预浸料层片(ply)。
实施例4B：粉末预浸料
包括800g/m2的双轴向(45/45°)纺织层和200g/m2的短切原丝层的玻璃增强材料组合毡切割成15x 15cm的片段。将片段放置在如EP 1 998 953 B1中描述的D-Preg静电浸渍机的腔室中。将实施例2B中描述的且从所述深度冷冻器直接取出的粉末量(30g)施加到所述毡，其然后进行浸渍，如EP 1 998 953 B1中描述的。将所述粉末通过在70℃的烘箱中放置5分钟而原为固定，从而制造15x 15cm预浸料层片。
实施例5A：粉末预浸料模制品(Mouldings)
在金属模具中将两片实施例4A中制造的预浸料以相同取向放置在彼此之上，并且在120℃施加一巴压力。将所述部件在10分钟之后脱模，并且发现其具有215MPa的抗弯强度和10.2GPa的模量。
实施例5B：粉末预浸料模制品
在金属模具中将两片实施例4B中制造的预浸料以相同的取向放置在彼此之上，并且在80℃施加一巴压力。在10分钟之后将所述部件脱模。
实施例6：泡沸的乙烯基酯粉末
将以下粉末进行共混：
100g 3A中制造的粉末
100g多磷酸铵(FR cros 484ex-Budenheim)
50g三聚氰胺(Melafine ex-OCI)
50g季戊四醇(Charmor PM40ex-Perstorp)
粒度分布：d50＝25um，d90＝100um
实施例7：泡沸的预浸料
将包括800g/m2双轴向(45/45°)纺织层和200g/m2的短切原丝层的玻璃增强材料组合毡切割成15x 15cm的片段。将片段放置到如EP 1 998 953 B1中描述的D-Preg静电浸渍机的腔室中。将实施例6中描述且从所述深度冷冻器直接取出的所述粉末量(90g)施加到所述毡，随后进行浸渍，如在EP 1 998 953 B1中描述的。将所述粉末通过在90℃的烘箱中放置5分钟而原位固定，从而制造15x 15cm预浸料层片。
实施例8：泡沸的模制品
在金属模子中将两片实施例7中制造的预浸料以相同的取向放置在彼此之上，并且在120℃施加100巴(10MPa)的压力。在14分钟之后将所述部件脱模。在Epiradiateur试验(NFP 92-501)的模拟中，面板显示显著(卓越)的泡沸效果。
以上实施例在所述粉末或其衍生物中均不包含苯乙烯或任何其它可共聚的单体。这与其中在每个实施例中存在氰尿酸三烯丙基酯的WO9222603形成对比。该单体被分类为对于环境是有害和危险的。
以上实施例中制造的模制品的加工温度在80-120℃的范围内。这与在WO9222603中给出的实施例的150℃形成对比。使用较低的加工温度的能力代表了对于加工者的显著益处。
Claims (10)
1.粉末预浸料，其包含乙烯基酯树脂作为唯一树脂，其中所述树脂具有在-5到+30℃范围内的Tg和在2-75dPa.s范围内的100℃的熔体粘度。
2.根据权利要求1的粉末预浸料，其中所述乙烯基酯树脂具有在+5到+25℃、优选地在+10到+20℃范围内的Tg。
3.根据权利要求1或2的粉末预浸料，其中所述乙烯基酯树脂具有在10-25dPa.s范围内的100℃的熔体粘度。
4.根据前述权利要求任一项的粉末预浸料，其包含一种或多种固化引发剂，所述固化引发剂优选地选自有机过氧化物，具有优选地低于100℃、更优选地低于85℃、最优选地低于70℃的1小时半衰期温度的。
5.根据前述权利要求任一项的粉末预浸料，其包含选自填料、表面改性剂、颜料、阻燃剂、泡沸添加剂、及其混合物中的一种或多种添加剂。
6.根据前述权利要求任一项的粉末预浸料，其中所述树脂为不含反应性稀释剂和单体的乙烯基酯。
7.根据前述权利要求任一项的粉末预浸料，其包括选自松散纤维、非织造织物和纺织织物的纤维。
8.根据前述权利要求任一项的粉末预浸料的制备方法，其包括固定步骤，该固定步骤包括在70-100℃、优选地70-95℃、最优选地70-90℃范围内的温度下加热优选地3-7分钟的时期、更优选地约5分钟的时期。
9.根据权利要求8的粉末预浸料的制备方法，其中所使用的粉末将具有80％体积的20-100um的粒子和99％的0.5-100um的粒子。
10.由根据权利要求1-7任一项的粉末预浸料制备复合材料的方法，其包括将所述预浸料放置到模具中和加热所述预浸料，其中加热步骤包括在70-120℃、优选地75-100℃、更优选地80-90℃范围内的温度下进行加热。
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| EP14290355.8A EP3026076B1 (en) | 2014-11-27 | 2014-11-27 | Vinyl ester powder pre-preg |
| PCT/IB2015/002401 WO2016083896A1 (en) | 2014-11-27 | 2015-11-30 | Vinyl ester powder pre-preg |
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| JP (1) | JP6755500B2 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107778782A (zh) * | 2017-12-05 | 2018-03-09 | 镇江海威新材料科技有限公司 | 一种快速固化、高性能低成本的环氧乙烯基酯树脂预浸料及其制备方法 |
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| CN107428970B (zh) * | 2015-03-26 | 2021-09-10 | 日铁化学材料株式会社 | 纤维增强塑料成型用材料、其制造方法和成型物 |
| EP3696864A1 (en) * | 2019-02-13 | 2020-08-19 | TIGER Coatings GmbH & Co. KG | Housing material |
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| Publication number | Publication date |
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| WO2016083896A1 (en) | 2016-06-02 |
| JP6755500B2 (ja) | 2020-09-16 |
| KR20180080125A (ko) | 2018-07-11 |
| EP3026076B1 (en) | 2018-10-17 |
| DK3026076T3 (en) | 2019-01-28 |
| AU2015352117A1 (en) | 2017-06-15 |
| US20200354535A1 (en) | 2020-11-12 |
| US20170327656A1 (en) | 2017-11-16 |
| BR112017011186A2 (pt) | 2019-01-08 |
| MX2017006981A (es) | 2018-06-06 |
| JP2018530625A (ja) | 2018-10-18 |
| BR112017011186B1 (pt) | 2022-02-22 |
| CA2968934A1 (en) | 2016-06-02 |
| US11434338B2 (en) | 2022-09-06 |
| MY183119A (en) | 2021-02-15 |
| NZ732298A (en) | 2023-09-29 |
| US10752743B2 (en) | 2020-08-25 |
| ES2705038T3 (es) | 2019-03-21 |
| CN107406598B (zh) | 2021-08-20 |
| AU2015352117B2 (en) | 2020-02-27 |
| SA517381603B1 (ar) | 2021-03-01 |
| EP3026076A1 (en) | 2016-06-01 |
| KR102401893B1 (ko) | 2022-05-24 |
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