CN109311290B - 包含具有改善的机械性质的丙烯酸类聚合物片材的航空玻璃 - Google Patents

包含具有改善的机械性质的丙烯酸类聚合物片材的航空玻璃 Download PDF

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CN109311290B
CN109311290B CN201780038179.1A CN201780038179A CN109311290B CN 109311290 B CN109311290 B CN 109311290B CN 201780038179 A CN201780038179 A CN 201780038179A CN 109311290 B CN109311290 B CN 109311290B
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sheet
glazing
aircraft
acrylic polymer
modified acrylic
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CN109311290A (zh
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M.鲁比
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Saint Gobain Glass France SAS
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Saint Gobain Glass France SAS
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Abstract

本发明涉及：‑航空窗玻璃，其包含至少一个改性丙烯酸树脂片材，其特征在于该片材在此与至少一个其它改性丙烯酸树脂片材和/或至少一个通过流延产生的聚丙烯酸甲酯(PMMA)片材，和/或至少一个其它透明聚合物如聚碳酸酯(PC)的片材，和/或至少一个特别地化学增韧的玻璃片材结合，形成层压和/或多层窗玻璃；‑其用于空中飞行器的用途。

Description

包含具有改善的机械性质的丙烯酸类聚合物片材的航空玻璃
本发明涉及航空窗玻璃，其使用特别苛刻：鸟撞击，外部和内部之间的压力差，暴露于外部侧非常低的温度。对于这些窗玻璃，必须保证持久保持的高水平的机械强度，透明度和光学质量。
已知通过拉伸，例如沿着在片材平面中的两个垂直方向(双轴拉伸)，物理地改性聚合物材料片材，如丙烯酸类聚合物，特别是聚(甲基丙烯酸甲酯)(PMMA)，以便为它带来对通过微裂纹化产生的应力松弛的抵抗性，也就是说，在暴露于寒冷，机械磨损和化学化合物，空气中的水分时具有耐久性的高光学质量，以及必要的穿孔能力(在将窗玻璃螺栓固定到交通工具的车身或车厢，框架或安装结构的情况下)，以及机械强度(鸟击等)的改进。
然而，拉伸工艺是棘手的，漫长且昂贵(材料损失，材料价格等)。如此拉伸的材料具有当其经受高于约100℃的温度时回复的缺点，限制并使热成型方法复杂化：热成型并且必须重新拉伸，通过吹制或其它方法施加应力。因此，拉伸的材料在意外暴露的情况下具有失去尺寸的风险。
本发明的目的是使用透明聚合物，特别是丙烯酸类聚合物，在其聚合物链中包含纳米结构化的嵌段和/或添加有限制裂纹蔓延的微米填料或纳米填料，用于呈平面或弯曲的，层压和/或多层窗玻璃形式具有增强机械性质的复杂的运输窗玻璃的应用。这些改性聚合物不需要繁缛的拉伸工艺，并且通过热成型使成型更具容易性(尺寸稳定性)；它们不是预应力的，并且在暴露于热量的情况下(例如飞机舷窗)具有提高的安全性。
因此，本发明的一个主题是一种航空窗玻璃，其包含至少一个改性丙烯酸类片材(feuille d'acrylique modifié)，其特征在于该片材在此与至少一个其它改性丙烯酸类片材和/或至少一个通过流延产生的聚丙烯酸甲酯(PMMA)片材，和/或至少一个其它透明聚合物如聚碳酸酯(PC)的片材，和/或至少一个玻璃片材，特别地化学增强的玻璃片材结合，形成层压和/或多层窗玻璃。
在本发明的意义上，“改性丙烯酸类”应理解为意指经化学改性以改善其机械性质的透明丙烯酸类聚合物，其具有以下特征：
-密度＜1.2；
-弯曲模量＞2000，优选2300MPa；
-无缺口夏比冲击强度＞35，优选40kJ/m2；
-透光率(可见光谱的波长)＞90％；
-雾度＜1；
-热膨胀系数≤70ppm/°K；
-耐化学性：根据美国军用标准MIL-P-25690，与甲苯/乙酸异丁酯糊剂接触时的抗微裂纹性＞17MPa。
已知通过流延产生的PMMA相对于挤出的PMMA提供更佳的透明光学质量。
层压窗玻璃包括多个通过下面详细描述的层间粘合剂层彼此连接的无机(玻璃)和/或有机(聚合物材料)透明刚性片材。
多层窗玻璃具有多个通过干燥气体或空气腔彼此分开的无机和/或有机，单片和/或层压的透明刚性片材。
所有这些片材都是平面的或弯曲的。
优选地，改性丙烯酸类是具有改善的机械性质的丙烯酸类聚合物，在其聚合物链中包含纳米结构化嵌段和/或补充有限制裂纹蔓延的微米填料或纳米填料。
在本发明的一个优选但非强制性的实施方案中，对通过流延产生的聚(甲基丙烯酸甲酯)(PMMA)进行物理改性对抗通过微裂纹化产生的应力松弛(pour résister à larelaxation de contrainte par microfendillement)。物理改性尤其包括双轴拉伸(bi-étirage)；其是有利的：它允许刺穿PMMA或者当该PMMA在经受低温或机械磨损的窗玻璃的外部面上时，而不在PMMA片材中形成微裂纹。
根据本发明的航空窗玻璃的其它优选特征：
-将改性丙烯酸类片材粘合到另一个改性丙烯酸类片材或通过流延产生的聚(甲基丙烯酸甲酯)(PMMA)片材上，或通过不含与丙烯酸类反应的增塑剂的聚乙烯醇缩丁醛(PVB)或热塑性聚氨酯(TPU)粘合到玻璃片材上；
-通过热塑性聚氨酯(TPU)将改性丙烯酸类片材粘合到聚碳酸酯(PC)片材上；
-在粘合到另一片材上之前，对改性丙烯酸类片材或通过流延产生的聚(甲基丙烯酸甲酯)(PMMA)片材的表面进行涂底漆处理；涂底漆具有提高粘合质量和耐久性的作用；当它与另一片材粘合时，玻璃，特别是化学强化-增韧的玻璃，也可以涂底漆，与从未进行涂底漆的聚碳酸酯片材相反，因为聚碳酸酯片材特别地被许多化合物降解；
-至少一个改性丙烯酸类片材超出由其它材料形成的窗玻璃片材的边缘，特别是当利用这种材料的高机械品质以刺穿超出边缘的部分以通过螺栓连接等装配窗玻璃时，或者以通过夹持装配窗玻璃时；
-它是弯曲的。
本发明的另一主题是如上所述的航空窗玻璃作为用于空中飞行器，特别是直升机或飞机(无论它是运输飞行器，战斗飞行器还是战斗机)的窗玻璃的应用。
根据附图1至12将更好地理解本发明，所有附图均示意性地表示根据本发明的航空窗玻璃的不同实施方案。
以下用相同术语表示的所有材料是相同的。
参考图1，根据本发明的航空双层窗玻璃有以下组成：
-改性丙烯酸类片材1，具有至少等于1mm，优选1.5mm，最多等于25mm，优选12mm的厚度，由Arkema公司以注册商标Altuglas® Shield Up销售，
-空气腔10，和
-通过流延产生的PMMA片材2，任选地进行物理改性，例如通过拉伸，其厚度至少等于0.5mm，优选3mm，至多等于25mm，优选8mm，由Evonik®公司以参考号GS 249销售的航空级丙烯酸类聚合物。
改性丙烯酸类片材1优选构成窗玻璃的外部面，即，暴露于外部大气的外部面，但不排除它相反地构成内部面，并且在这种情况下，航空级丙烯酸聚合物片材构成窗玻璃的外部面。
图2中所示的航空窗玻璃与图1所示的航空窗玻璃的不同之处在于，它由两个改性丙烯酸类片材1和1'组成，并且构成窗玻璃外部面的片材1在此具有至少等于0.5mm，优选3mm，至多等于25mm，优选8mm的厚度，片材1'与图1中的片材1相同。
图3表示由具有三个组件1, 3, 2的层压窗玻璃，空气腔10和通过流延产生的PMMA片材2'组成的双层航空窗玻璃。
改性丙烯酸类片材1与图1中的片材1相同。两个通过流延产生的PMMA片材2, 2'的厚度至少等于0.8mm，优选1.5mm，最多等于80mm，优选12mm。
改性丙烯酸类片材1和通过流延产生的PMMA片材2通过层间粘合剂3进行粘合，所述层间粘合剂3具有至少等于0.1mm，优选0.38mm，至多等于20mm，优选2.5mm，特别是等于1.25mm的厚度。
根据第一种变型，层间粘合剂3由Huntsman公司以注册商标Crystalflex® PE399或499销售的热塑性聚氨酯(TPU)构成，并且改性丙烯酸类片材1和通过流延产生的PMMA片材2的在组装成层压体之前经受用基于甲基丙烯酸甲酯和1-丙胺,3-(三乙氧基甲硅烷基)有机硅烷和1,2-乙二胺,N-[3-(三甲氧基甲硅烷基)-丙基]-1有机硅烷(以分别的名称DOW CORNING® Z6011 SILANE和DOW CORNING Z-6020® SILANE进行销售)的组合物的涂底漆。
根据第二种变型，层间粘合剂3由聚乙烯醇缩丁醛组成，所述聚乙烯醇缩丁醛具有不与丙烯酸类反应的增塑剂，由Eastman Solutia公司以名称PVB DB 31或PVB DS 31销售，并且使改性丙烯酸类片材1和通过流延产生的PMMA 2在组装成层压体之前通过基于甲基丙烯酸甲酯的组合物进行涂底漆。
改性丙烯酸酯片材1构成在空中飞行器外侧的窗玻璃的面。
在图4中表示的是对称的层压航空窗玻璃，其中两个厚度至少等于0.1mm，优选0.55mm，最多等于20mm，优选为8mm的化学增韧玻璃片材4,4'通过层间粘合剂层3,3'与图1中的改性丙烯酸类片材相同的改性丙烯酸类片材的两侧粘接，所述层间粘合剂层3,3'与图3中的由热塑性聚氨酯制成的粘合剂层相同。
图5中的航空窗玻璃与图4中的航空窗玻璃的不同之处仅在于改性丙烯酸类片材1边缘突出的。该片材的边缘突出部分可以被刺穿以便通过螺栓连接装配窗玻璃，或者该窗玻璃使用夹持特别地夹持该边缘突出部分进行装配。
图6中的航空窗玻璃是不对称的，并与图5中的航空窗玻璃不同之处在于，除去在改性丙烯酸类片材1的单一侧上的玻璃片材及其连接的层间粘合剂层。改性丙烯酸类片材1能够构成窗玻璃的外部面和内部面。
图7中的航空窗玻璃与图6中的航空窗玻璃的不同，图8中的航空窗玻璃与图5中的不同分别仅在于在分别玻璃片材4，4'的层压体的内部面上添加功能性薄层20而不同。功能层20是例如加热层，如由掺杂锡的氧化铟(ITO，氧化铟锡)制成，具有除冰和/或除雾功能，或者热控制层，如防日光层(反射太阳辐射)。
图9与图8的不同之处仅在于两个玻璃片材4,4'而不仅仅在其内部面上带有功能层20,21。
图10表示具有多个改性丙烯酸类片材1，1'，1''的层压航空窗玻璃，所述片材在经过涂底漆处理后，以上述方式通过层间粘合剂层3,3'彼此粘合。在这里所示的所有窗玻璃中，每个改性丙烯酸类片材1,1',1''可以用类似于图10中的层压体进行代替，就像每个玻璃片材4,4'可以用通过PVB或等效物的层间粘合剂层彼此粘合的多个玻璃片材的层压体进行代替一样。
在图11中，层压航空窗玻璃由两个改性丙烯酸类片材1,1'构成，所述改性丙烯酸类片材，在该两个改性丙烯酸片材1,1'根据上述第一种变型进行涂底漆后，通过热塑性聚氨酯(TPU)的层间粘合剂层3,3'(不包含能够侵蚀聚碳酸酯的增塑剂)粘合到聚碳酸酯片材5的任一侧，聚碳酸酯片材的厚度至少等于1mm，优选2.5mm，最多等于12mm。
本发明还延伸到包含从图11的结构获得的结构的层压体，通过从其中除去改性丙烯酸类片材1'和TPU层3'，并通过用硬质抗划痕涂层或清漆(特别是聚硅氧烷类)涂覆聚碳酸酯片材5的如此释放的表面来实现。作为在一面上涂有抗划痕涂层的聚碳酸酯片材的例子，可以提及由Sabic Innovative Plastics公司以注册商标Lexan® Margards® HLGA3销售的片材。涂覆有硬质抗划痕涂层的聚碳酸酯的面构成层压窗玻璃的外部面，优选用于暴露于空中交通工具的客舱的内部大气。
图12中所示的航空窗玻璃与图11中所示的航空窗玻璃的不同之处在于，改性丙烯酸类片材1,1'相对于聚碳酸酯片材5是边缘突出的。后者是易碎的，并且不能被刺穿。在聚碳酸酯片材5周边的空闲空间通过补偿垫块30,31堵塞，所述补偿垫块30,31由例如热固性聚酯-甲基丙烯酸甲酯，环氧树脂-玻璃纤维等复合材料形成，所述复合材料适于在机械上和化学上保护聚碳酸酯片材的边缘。
为了将窗玻璃固定在其安装环境中，两个改性丙烯酸类片材1,1'的边缘突出部分以及补偿垫块30,31被刺穿并且使用合适的固定装置，例如螺栓，螺母等拧紧。将未示出的承载应力的衬套(douilles de reprise d'effort)***在补偿垫块30,31中刺穿的孔中，以避免使改性丙烯酸类片材1,1'破碎。
根据本发明的航空窗玻璃非常适用于航空应用，甚至适用于所有运输交通工具(陆地，水上或空中)，甚至适用于具有安全，防盗或防入侵要求的建筑物。特别地，它们形成优异的具有各种尺寸的飞机或直升机的窗玻璃，它们被夹持，螺栓固定和/或是除雾和/或除冰的。

Claims (13)

1.一种航空窗玻璃，其包含至少一个改性丙烯酸类聚合物片材，其特征在于该改性丙烯酸类聚合物片材与至少一个其它改性丙烯酸类聚合物片材和/或至少一个通过流延产生的聚甲基丙烯酸甲酯(PMMA)片材，和/或至少一个其它透明聚合物的片材，和/或至少一个玻璃片材组合，形成层压和/或多层窗玻璃，其中改性丙烯酸类聚合物是具有改进机械性质的丙烯酸类聚合物，该丙烯酸类聚合物在其聚合物链中包含纳米结构化的嵌段。
2.如权利要求1所述的航空窗玻璃，其特征在于，该丙烯酸类聚合物添加有限制裂纹蔓延的微米填料或纳米填料。
3.如权利要求1所述的航空窗玻璃，其特征在于，所述玻璃片材是化学增强的玻璃片材。
4.根据权利要求1-3中任一项所述的航空窗玻璃，其特征在于，所述通过流延产生的聚甲基丙烯酸甲酯(PMMA)经过物理改性以抵抗通过微裂纹化产生的应力松弛。
5.根据权利要求1-3中任一项所述的航空窗玻璃，其特征在于，使改性丙烯酸类聚合物片材粘合到另一个改性丙烯酸类聚合物片材或通过流延产生的聚甲基丙烯酸甲酯(PMMA)片材上，或者通过不含与丙烯酸类反应的增塑剂的聚乙烯醇缩丁醛(PVB)或热塑性聚氨酯(TPU)粘合到玻璃片材上。
6.根据权利要求1-3中任一项所述的航空窗玻璃，其特征在于，通过热塑性聚氨酯(TPU)将改性丙烯酸类聚合物片材粘合到聚碳酸酯(PC)片材上。
7.如权利要求5所述的航空窗玻璃，其特征在于，在粘合到另一个片材上之前，使改性丙烯酸类聚合物片材或通过流延产生的聚甲基丙烯酸甲酯(PMMA)片材的表面经受涂底漆处理。
8.根据权利要求1-3中任一项所述的航空窗玻璃，其特征在于，至少一个改性丙烯酸类聚合物片材相对于由另一种材料构成的窗玻璃片材是边缘突出的。
9.根据权利要求1-3任一项所述的航空窗玻璃，其特征在于，航空窗玻璃是弯曲的。
10.根据权利要求1-3任一项所述的航空窗玻璃，其特征在于，所述其它透明聚合物的片材是聚碳酸酯(PC)的片材。
11.根据前述权利要求任一项所述的航空窗玻璃作为用于空中飞行器的窗玻璃的用途。
12.根据权利要求11所述的用途，特征在于所述空中飞行器是直升机。
13.根据权利要求11所述的用途，特征在于所述空中飞行器是飞机。
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KR102359698B1 (ko) 2022-02-10
BR112018075787A2 (pt) 2019-03-26
FR3053277B1 (fr) 2020-11-06
US11052986B2 (en) 2021-07-06
FR3053277A1 (fr) 2018-01-05
BR112018075787B1 (pt) 2022-08-16
US20190233078A1 (en) 2019-08-01
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CA3027874A1 (fr) 2018-01-04
KR20190025563A (ko) 2019-03-11

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