CN102862348B - 一种高透明度及高强度层合玻璃及其制作方法 - Google Patents

一种高透明度及高强度层合玻璃及其制作方法 Download PDF

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CN102862348B
CN102862348B CN201210387558.0A CN201210387558A CN102862348B CN 102862348 B CN102862348 B CN 102862348B CN 201210387558 A CN201210387558 A CN 201210387558A CN 102862348 B CN102862348 B CN 102862348B
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李喜宝
卢金山
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Nanchang Hangkong University
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    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082Properties of the bulk of a glass sheet
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    • B32LAYERED PRODUCTS
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    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2333/00Polymers of unsaturated acids or derivatives thereof
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Abstract

本发明公开了一种高透明度及高强度层合玻璃及其制作方法,它以锂铝硅酸盐无机玻璃作为外层,以聚氨酯作为中间层,以有机玻璃作为内层。其中无机玻璃经适当条件的氢氟酸择优腐蚀处理,聚氨酯及有机玻璃经适当条件的冷等离子体处理,三层经温压成型形成层合玻璃风挡。该层合玻璃的可见光透过率大于85%,层间剪切强度大于5 MPa,在温度为80℃、湿度为85%的条件下湿热老化30天后层间剪切强度下降幅度小于2%。本发明制备工序简单,工艺广泛应用于工业界,工艺成本低,有良好的产业化前景。所制得的层合玻璃透明度及强度高,耐湿热老化性能优良。

Description

一种高透明度及高强度层合玻璃及其制作方法
技术领域
       本发明涉及一种层合玻璃的制作方法,尤其涉及一种高透明度及高强度层合玻璃及其制作方法。
技术背景
       层合玻璃广泛应用于汽车、飞机等的风挡部件,作为汽车、飞机上的重要组成部分,要求其具有优良的光学性能、足够的结构强度和刚度以及较长的使用寿命。目前还没有一种材料同时具备这样多种性能。将高硬度的无机玻璃与韧性较好的有机玻璃两种材料结合起来,即用有机玻璃作主承力层、用无机玻璃作防护层、中间用胶片粘结形成一种非对称的无机-有机层合玻璃结构,有利于提高风挡的力学性能。
但是,由于无机玻璃与有机材料间的不匹配性及低的化学兼容性,无机-有机层合玻璃易发生层间剪切失效,特别是无机玻璃与中间层易产生分层。为了解决这一问题,有文献报道采用粘结促进剂(如树脂)或者涂层来粘结无机玻璃和中间层。然而,由于粘结促进剂和涂层可导致可见光透过率减小及耐湿热老化性能降低,对风挡的实际应用带来一些限制。
发明内容
       本发明的目的是提供一种高透明度、高层间剪切强度及耐湿热老化性能优良的层合玻璃及其制作方法。
       为实现上述目的,本发明采取以下技术方案:采用5-20%(体积比)的氢氟酸择优腐蚀处理外层锂铝硅酸盐无机玻璃,腐蚀时间为10-60分钟;对聚氨酯中间层及有机玻璃层进行冷等离子体处理,冷等离子体处理的功率为100-300 w,真空度为5-10 Pa,时间为1-3 min;将处理后的聚氨酯夹在锂铝硅酸盐无机玻璃和有机玻璃之间,在热压机上温压成型得到高透明度和高强度的层合玻璃。
       本发明上述层合玻璃的制作方法,包括步骤:
(1) 将锂铝硅酸盐无机玻璃在5-20%(体积比)的氢氟酸中择优腐蚀处理20-60分钟,经洗涤后烘干;
(2) 将聚氨酯中间层及有机玻璃层在功率为100-300 w,真空度为5-10 Pa的条件下冷等离子体处理1-3 min;
(3) 将切割、磨边后的无机玻璃、聚氨酯和有机玻璃进行超声清洗,之后使用脱脂棉沾95%的无水乙醇擦拭其表面,烘干备用;
(4) 将聚氨酯夹在无机玻璃和有机玻璃之间,放入热压机中在温度为80-200 ℃,压力为2-10 MPa的条件下保压10-30 min。
一种高透明度及高强度层合玻璃,它包括外层锂铝硅酸盐无机玻璃、聚氨酯(PU)中间层和内层有机玻璃(PMMA);所述外层玻璃经氢氟酸择优腐蚀处理;所述外层玻璃与所述内层玻璃之间设所述聚氨酯中间层,聚氨酯中间层及有机玻璃层经冷等离子体处理;所述外层玻璃、中间层和内层玻璃经切割、磨边及洗涤干燥后温压成型形成所述高透明度及高强度层合玻璃。
外层锂铝硅酸盐无机玻璃经过体积比为5-20%的氢氟酸择优腐蚀处理20-60分钟。
聚氨酯中间层及有机玻璃层经冷等离子体处理,冷等离子体处理的功率为100-300 w,真空度为5-10 Pa,时间为1-3 min。
所述的层合玻璃的可见光透过率大于85%。
所述的层合玻璃的层间剪切强度大于5 MPa;在温度为80℃、湿度为85%的条件下湿热老化30天后层间剪切强度下降幅度小于2%。
本发明通过对无机玻璃进行择优腐蚀,得到高比表面积及绒面结构的无机玻璃表面,此表面不仅有较高的物理化学活性,而且可以减少光线反射;另外通过对聚氨酯及有机玻璃进行冷等离子体处理不仅提高了其透明度,而且在聚氨酯表面引入了大量的自由基及官能团,从而在层合时得到高可见光透过率和高层间剪切强度的层合玻璃。
本发明的发明效果为:可见光透过率大于85%;层间剪切强度大于5 MPa;在温度为80℃、湿度为85%的条件下湿热老化30天后层间剪切强度下降幅度小于2%。
本发明创新:
1、首次采用择优腐蚀处理结合冷等离子体处理相结合的方法,利用择优腐蚀及冷等离子体处理对基体表面的物理化学作用,不仅使层合玻璃的可见光透过率提高,而且使层合玻璃的层间剪切强度和耐湿热老化性能得以显著提高;
2、经过择优腐蚀处理后的无机玻璃和经过冷等离子体处理后的聚氨酯及有机玻璃只是其表面发生了物理化学变化,而基体本身没有受到任何影响。温压成型后得到高可见光透过率和高层间剪切强度的层合玻璃,可广泛应用于汽车、飞机的风挡及防弹玻璃。
附图说明
       图1为经过择优腐蚀和冷等离子体处理及没有经过任何处理的层合玻璃的紫外-可见吸收光谱,显示经过处理后层合玻璃的可见光透过率得以提高;
图2为经过冷等离子体处理及没有经过处理的聚氨酯的红外吸收光谱,显示经过冷等离子体处理后的聚氨酯表面产生大量新的自由基及官能团;
图3为经过择优腐蚀处理后的无机玻璃表面的显微结构,显示经过择优腐蚀处理后的无机玻璃表面形成绒面结构;
图4为在不同湿热老化时间下经过酸腐蚀和冷等离子体处理及没有经过任何处理的层合玻璃的层间剪切强度,显示经过处理后层合玻璃的层间剪切强度大为提高,且耐湿热老化性能得以显著提升。
具体实施方式
下面结合附图和实施例对本发明进行详细的描述。
首先将锂铝硅酸盐无机玻璃在5-20%(体积比)的氢氟酸中择优腐蚀处理20-60分钟,经洗涤后烘干备用;接着对聚氨酯及有机玻璃进行冷等离子体处理,冷等离子体处理的功率为100-300 w,真空度为5-10 Pa,时间为1-3分钟;对经过处理的无机玻璃、聚氨酯及有机玻璃进行切割、磨边,再进行超声清洗,之后使用脱脂棉沾95%的无水乙醇擦拭其表面,烘干备用;最后将聚氨酯夹在无机玻璃和有机玻璃之间,放入热压机中在温度为80-200 ℃,压力为2-10 MPa的条件下保压10-30分钟,从而得到层合玻璃风挡。
对于制造的层合玻璃板,使用天津市拓普仪器有限公司制造的WFZ-26A型分光光度计测量200-1000 nm波长范围内的透射率;使用美国热电尼高力公司制造的Nicolet 6700型红外光谱仪测量聚氨酯表面的红外吸收光谱;使用日本JEOL公司制造的JSM-5610LV型扫描电镜观察腐蚀处理后无机玻璃表面的显微结构;通过按ASTM D905中所述的方法测定层合玻璃的层间剪切强度。图1为经过择优腐蚀和冷等离子体处理及没有经过任何处理的层合玻璃的紫外-可见吸收光谱,显示经过处理后层合玻璃的可见光透过率得以提高,可见光透过率大于85%。图2为经过冷等离子体处理及没有经过处理的聚氨酯的红外吸收光谱,显示经过冷等离子体处理后的聚氨酯表面产生大量新的–NH2,-COOH及–OH,这些官能团易与无机玻璃表面的羟基形成氢键及化学键,大大提高了无机玻璃与聚氨酯间的层间剪切强度;图3为经过择优腐蚀处理后的无机玻璃表面的显微结构,显示经过择优腐蚀处理后的无机玻璃表面形成绒面结构,这不仅有利于无机玻璃减少光反射从而提高透过率,而且有利于与聚氨酯的嵌合从而进一步提高层间剪切强度;图4为在不同湿热老化时间下经过择优腐蚀和冷等离子体处理及没有经过处理的层合玻璃的层间剪切强度,显示经过处理后层合玻璃的层间剪切强度提高了近400%,且湿热老化30天后层间剪切强度保持率大于98%。

Claims (5)

1.一种高透明度及高强度层合玻璃,其特征在于:它包括外层锂铝硅酸盐无机玻璃、聚氨酯(PU)中间层和内层有机玻璃(PMMA);所述外层玻璃经氢氟酸择优腐蚀处理;所述外层玻璃与所述内层玻璃之间设所述聚氨酯中间层,聚氨酯中间层及有机玻璃层经冷等离子体处理;所述外层玻璃、中间层和内层玻璃经切割、磨边及洗涤干燥后温压成型形成所述高透明度及高强度层合玻璃;
所述外层锂铝硅酸盐无机玻璃经过体积比为5-20%的氢氟酸择优腐蚀处理20-60分钟,通过择优腐蚀使无机玻璃表面形成高低起伏的绒面层;
所述聚氨酯中间层及有机玻璃层经冷等离子体处理,冷等离子体处理的功率为100-300 w,真空度为5-10 Pa,时间为1-3 min。
2.根据权利要求1所述的一种高透明度及高强度层合玻璃,其特征在于,所述的层合玻璃的可见光透过率大于85%。
3.根据权利要求1所述的一种高透明度及高强度层合玻璃,其特征在于,所述的层合玻璃的层间剪切强度大于5 MPa;在温度为80℃、湿度为85%的条件下湿热老化30天后层间剪切强度下降幅度小于2%。
4.一种如权利要求1-5所述的一种高透明度及高强度层合玻璃的制作方法,其制作步骤如下:
(1) 将锂铝硅酸盐无机玻璃经氢氟酸择优腐蚀处理,经洗涤后烘干;
(2) 将聚氨酯及有机玻璃经冷等离子体处理;
(3) 将切割、磨边后的无机玻璃、聚氨酯和有机玻璃进行超声清洗,之后使用脱脂棉沾质量分数为95%的无水乙醇擦拭其表面,烘干备用;
(4) 将聚氨酯夹在无机玻璃和有机玻璃之间,放入热压机中温压成型得到层合玻璃。
5.根据权利要求6所述的一种高透明度及高强度层合玻璃的制作方法,其特征是:层合玻璃温压成型的温度为80-200 ℃,压力为2-10 MPa,保压时间为10-30 min,温压后聚氨酯与无机玻璃的绒面层发生嵌合,形成机械互锁结构。
CN201210387558.0A 2012-10-15 2012-10-15 一种高透明度及高强度层合玻璃及其制作方法 Expired - Fee Related CN102862348B (zh)

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