CN110944835A - 包含具有着色框的夹层膜层的层压玻璃 - Google Patents
包含具有着色框的夹层膜层的层压玻璃 Download PDFInfo
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- CN110944835A CN110944835A CN201880055155.1A CN201880055155A CN110944835A CN 110944835 A CN110944835 A CN 110944835A CN 201880055155 A CN201880055155 A CN 201880055155A CN 110944835 A CN110944835 A CN 110944835A
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- Prior art keywords
- film
- laminated glass
- plasticizer
- glass
- glass according
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Images
Classifications
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- B32B17/06—Layered 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
- B32B17/10—Layered 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
- B32B17/10005—Layered 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
- B32B17/1055—Layered 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
- B32B17/10651—Layered 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 comprising colorants, e.g. dyes or pigments
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- B32B17/06—Layered 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
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- B32B17/10005—Layered 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
- B32B17/10009—Layered 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
- B32B17/10036—Layered 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 two outer glass sheets
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- B32B17/06—Layered 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
- B32B17/10—Layered 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
- B32B17/10005—Layered 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
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
- B32B17/10256—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
- B32B17/10275—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques on interlayer
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Abstract
本发明涉及层压玻璃,其通过在两块玻璃片之间层压至少一层包含聚乙烯醇缩醛PA和任选的至少一种增塑剂WA的膜A和至少一层包含聚乙烯醇缩醛PB和至少一种增塑剂WB的膜B而得到,所述层压玻璃的特征在于,在层压之前,膜A中增塑剂WA的量小于22%重量;膜B中增塑剂WB的量为至少22%重量,且膜A至少在一个表面上包含不透明区域。
Description
技术领域
本发明涉及层压玻璃,尤其是风挡,其包含由粘着夹层膜组合的两块玻璃片,所述夹层膜至少在层压玻璃的一个边缘区域上提供有着色带。
在大多数用于汽车的风挡中,内部玻璃片提供有不透明、大多为黑色的框,以保护使风挡与底架机械连接的密封或粘着免受UV辐射。一种常见的技术是在玻璃表面上丝网印刷低熔点的黑色玻璃料(glass frit),然后在超过600℃的温度烧结该玻璃料,以固化印上的混合物。通常,烧结在玻璃形成步骤(即,最初的平片玻璃在高于600℃的温度下弯曲)期间实现。如今,在汽车工业中有用较薄玻璃片来最小化玻璃部件重量的强烈趋势。
现已发现,上述丝网印刷步骤可导致薄玻璃片的破损率增加,这与非常轻质的玻璃片的振动所造成的印刷模糊有关。在弯曲步骤中还会出现另外的问题,因为着色的黑色区域有更强的吸热,这将导致玻璃部件中的温度不均匀性,从而使均匀弯曲复杂化。
发明目的
因此,有利的是给风挡提供着色的边缘区域,而无需在一个玻璃表面上应用烧结釉。作为这个问题的解决方案,可想到不向玻璃而是向夹层膜提供着色的边缘区域。原则上,着色的边缘区域已被称为阴影带,位于夹层/风挡上部,以保护驾驶员免受阳光照射。然而,由于夹层膜通常通过挤出来制造,因此,在技术上不可能生产在所有边缘上分别具有典型细节(例如印花、点状梯度等)的阴影带的夹层膜。
从不同的技术领域,已知提供具有低或无增塑剂含量的具有涂层或导电结构的薄PVB膜,它可与普通的增塑PVB膜组合以产生功能化的层压玻璃制品(EP3074221A1)。
已发现,具有低或无增塑剂含量的薄PVB膜只能在边缘区域内涂覆或印刷颜料。与增塑PVB膜组合使用时,此类夹层膜提供对UV辐射的着色保护带,而无需将釉颜料烧结到玻璃表面。
因此,本发明的目的是一种层压玻璃,所述层压玻璃通过在两块玻璃片之间层压至少一层包含聚乙烯醇缩醛PA和任选的至少一种增塑剂WA的膜A和至少一层包含聚乙烯醇缩醛PB和至少一种增塑剂WB的膜B而获得,其中在层压之前,
- 膜A中增塑剂WA的量小于22%重量;
- 膜B中增塑剂WB的量为至少22%重量,并且
- 膜A至少在一个表面上包含不透明区域。
附图简述
图1示出本发明的层压玻璃结构的一个实施方案。
图2示出本发明的层压玻璃结构的另一个实施方案。
优选实施方案详述
在下文中,术语“在层压之前”是指膜A和B在有任何彼此接触之前的状态。例如,该术语是指分别形成各膜的组合物并分别缠绕到单独的辊上。术语“在层压之前”指在层压玻璃的层压过程中、或在由用于层压的层构建堆叠体之前,层或膜在组合之前的状态。
术语“不透明区域”是指在可见光谱中具有小于5%的透光率的膜的任何区域。在一种变体中,“不透明区域”可朝着透明渐淡。在这样的变体中,膜的“不透明区域”的至少一部分在可见光谱中具有小于5%的透光率。
本发明尤其有利于包含薄玻璃片的层压体,因为在薄玻璃上烧结釉甚至更易于产生破裂或不合格的弯曲片。在本发明的一个优选实施方案中,至少一块玻璃片的厚度小于1.8mm,例如小于1.6,小于1.4,小于1.0,或小于0.9mm。
膜A
本发明的层压体可包括一层或多层膜A,但至少一层薄膜A与本发明的层压玻璃的玻璃表面相邻地取向。也可将膜A施加到两个玻璃表面上,以提供具有玻璃/膜A/膜B/膜A/玻璃的层序的层压玻璃层压体。
如图1中所示,不透明区域优选覆盖膜A(1)的至少一个边缘,更优选覆盖膜A的二(2)、三(3)或所有四(4)个边缘(见图1)。
着色带的宽度可以为0.5至30cm,优选0.5至5cm。在不同位置的总宽度可以不同。本发明的层压体可用于汽车或飞机中,例如用于风挡或侧窗或天窗。尤其是在风挡的上部(图1(1)),印刷的带可过渡到较大的不透明或半透明区域,以隐藏驾驶员辅助摄像场或镜架。
不透明区域(以下称为“着色带”)可以为完全不透明和/或部分中断,和/或具有从完全不透明边缘到非印刷透明区域的过渡区域。中断的印刷可以点状图案的形式实现。着色带可从透明到不透明黑色或灰色连续渐显(没有反复出现到易看到的点)。图2以示例的方式显示点状涂层。
印刷带的形状可以为长方形,或者遵循成品层压玻璃的轮廓。
术语“颜料”或“着色”涉及无机或有机的有色材料,其不应溶于聚合物基质,并因此抵抗从膜A迁移到B。作为颜料,优选用炭黑、氧化铁或尖晶石颜料。颜料可以分散于载液如水、醇(alcohol)或醇与水的混合物中。另外,可加入粘合剂如聚乙烯醇、聚乙烯醇缩丁醛、聚乙烯吡咯烷酮、聚氨酯或聚苯乙烯-丙烯酸酯。以下将此类印刷组合物称为“印刷油墨”或简单称为“油墨”。
与基于有机溶剂的印刷油墨相比,水基印刷油墨是优选的,因为它们不溶胀或溶解膜A和/或导致膜缺陷。如果涂层薄和/或干燥步骤快,以致于溶剂不迁移入PVB膜,则可使用基于有机溶剂的印刷油墨。用低分子量PVB作为印刷油墨的粘合剂是有益的,因为它确保了与PVB膜A和B的良好相容性。
可通过印刷工业中通常已知的技术施加印刷油墨,例如胶版印刷、轮转凹版印刷、柔版印刷和丝网印刷,接着通常是干燥步骤。
为了避免由于干燥步骤中过度加热而引起膜A的起皱和/或变形,至关重要的是,膜A不应暴露于高于其玻璃化转变温度的温度,玻璃化转变温度通过DSC方法可测量为Tg。因此,优选使干燥步骤期间膜A的温度保持低于膜的Tg至少3℃或至少5℃或至少10℃或至少15℃或最优选或至少20℃。
根据印刷技术和所需的不透明度,印刷部分的干燥膜厚度在1-50μm之间。通常,干燥膜厚度在10-30μm之间。
优选在膜A上的印上着色层将面对膜B而不是玻璃表面地取向,以避免由于着色层的组分导致的在玻璃表面上膜A的透明中心和印上边缘部分之间的粘着力差异。
另外,在起始状态具有低增塑剂含量或甚至没有增塑剂含量的膜A可在插入玻璃/膜夹层结构之前穿孔,使其可具有任何几何图案的开口,例如通道、孔或狭缝。
因此,膜A可具有至少一个开口,使得膜B通过这个开口与至少一个玻璃表面直接接触。在粘着结合以形成成品层压玻璃后,在起始状态具有较高增塑剂含量的膜B在这些点粘着性结合到玻璃片,而不中断。因此,具体地讲,可在层压玻璃的点处获得开口,否则在这些点后,感测元件、光学元件和/或天线元件的功能可通过任选的隔热层或由膜A携带的着色层阻碍。
或者,可用膜A的厚度来补偿没有提供在膜B的完整表面上的另一层膜的厚度。在这类情况下,可由于夹层膜的厚度差异而引起光学变形。本发明的膜A可均衡另一层膜的厚度,例如通过用膜A的框或开口包围另一膜层,即,将另一膜层提供到膜A的开口。在这种情况下,膜A的厚度可与另一膜层的厚度相差小于50%,优选小于30%,甚至更优选小于15%。膜A最好具有基本与另一层膜相同的厚度。可组合数层膜A来达到所需的总厚度。另一层膜可例如配有IR反射涂层、光反射或引导结构如半透明镜面或全息层或导电结构,和/或提供另外的抗穿透性,如PET膜。
在本发明的方法中,在层压之前处于起始状态的膜A的厚度不大于膜B(一层或多层)的厚度的20%,优选15%,优选不大于10%。
在层压之前处于起始状态的膜A的厚度为10-250μm,优选20-160μm,优选30-120μm,优选40-100μm,最优选50-80μm。这个厚度范围不包括膜上的附加涂层。在层压玻璃中,该膜的厚度可通过从膜B转移增塑剂来增加。
膜A与膜B分开制备(例如挤出或溶剂流延),并且根本没有增塑剂,或有足够小比例的增塑剂,因此不会不利地影响后续的功能化和加工。
由于膜A将优选与层压玻璃的内表面之一直接接触,因此希望将其粘着力控制到中间水平,以达到机动车的不同玻璃位置强制性的令人满意的抗穿透性,如在不同的安全玻璃标准如ECE 43R中所规定。为此,膜A可包含碱金属离子和/或碱土金属离子,以调节它们对玻璃的粘着水平(所谓的抗粘着添加剂)。
优选钾或钠或锂作为碱金属离子。碱金属离子浓度的优选范围在锂的情况下为7-210ppm,优选14-140ppm,更优选21-140ppm,在钠的情况下为23-690ppm,优选46-460ppm,更优选69-460ppm,在钾的情况下为39-1170ppm,优选78-780ppm,更优选117-780ppm。另外,优选以具有1至10个碳原子的羧酸的盐形式加入碱金属离子。尤其优选乙酸钾作为粘着控制剂。
基于薄膜A的重量,碱金属盐的总量可低至0.005%重量。碱金属盐的优选范围为0.01%-0.1%,0.02-0.08%,0.03-0.06%,各重量%基于膜A的重量。
用于本发明的层压体的膜A可另外包含碱土金属离子,但由于它们对粘着的作用有限,因此,与碱金属离子比较,只应使用少量。在本发明的第一个实施方案中,膜A包含0至20ppm碱土金属离子,优选0至5ppm。
然而,已知在增塑PVB膜面对具有不同表面化学的两块玻璃片时,碱土金属离子具有粘着力的平衡作用。因此,在本发明的第二个实施方案中,膜A包含5-20ppm的碱土金属离子。碱土金属离子可以具有1至10个碳原子的羧酸的盐形式加入。尤其优选乙酸镁作为第二粘着控制剂。在这个实施方案中,膜A中以ppm计的碱金属离子与碱土金属离子之比优选至少(高)于1,尤其高于5,更优选高于10。
作为碱金属和碱土金属离子的量的替代,可用膜A和B的碱滴定度来表征膜中抗粘着剂(即碱金属和碱土金属盐)的量。膜A的碱滴定度可高于10,高于20,高于40,高于50,高于80,高于90,优选高于100,在各情况下最大值为500。与膜A大不相同,膜B的碱滴定度优选较低,更具体地讲,碱滴定度(膜A)-碱滴定度(膜B)之差大于2、6,优选大于10AT单位。
为了避免混浊,可减少膜A中氯离子和/或硝酸根离子和/或硫酸根离子的量。
因此,膜A的氯根含量可小于150ppm,优选小于100ppm,特别小于50ppm。在理想情况下,膜A的氯根含量小于10ppm或甚至0ppm。
膜A的硝酸根含量可任选小于150ppm,优选小于100ppm,特别小于50ppm。在理想情况下,膜A的硝酸根含量小于10ppm或甚至0ppm。
同样,膜A的硫酸根含量可任选小于150ppm,优选小于100ppm,特别小于50ppm。在理想情况下,膜A的硫酸根含量小于10ppm或甚至0ppm。
膜B
膜B可以为在本领域已知的任何增塑PVB膜。在层压之前的起始状态和/或在准备用于在玻璃片之间层压的堆叠体中,膜A和B可包含单一增塑剂以及不同和相同组成的增塑剂的混合物。术语“不同的组成”涉及增塑剂的类型及其在混合物中的比例二者。层压之后,即在成品层压玻璃中,膜A和膜B优选具有相同的增塑剂WA和WB。然而,在优选的变体中,膜A在其起始状态不包含任何增塑剂,而在层压后包含平衡量的增塑剂WB。
根据本发明使用的包含增塑剂的膜B在层压之前的起始状态包含至少22%重量增塑剂,例如22.0-45.0%重量,优选25.0-32.0%重量,特别是26.0-30.0%重量。
根据本发明使用的膜A在层压之前的起始状态可包含小于22%重量(例如21.9%重量)、小于18%重量、小于16%重量、小于12%重量、小于8%重量、小于4%重量、小于2%重量、小于1%重量或甚至无(0.0%重量)增塑剂。在本发明的一个优选实施方案中,具有低增塑剂含量的膜A优选包含0.0-8%重量增塑剂,最优选0-4%重量。
膜A或B优选包含聚乙烯醇缩醛,该聚乙烯醇缩醛具有一定比例的聚乙酸乙烯酯基团,相同或不同,为0.1至20%mol,优选0.5至3%mol,或5至8%mol。
在起始状态膜B的厚度为450-2500μm,优选600-1000μm,优选700-900μm。在本发明中可使用多层膜B,它们彼此堆叠或由膜A分开。
如果膜B在制备夹层结构之前拉伸和/或另外以弯曲的方式适应遮挡(例如,风挡)的形状,则在层压时指定厚度可再减小高达20%。
聚乙烯醇缩醛
根据本发明使用的膜A和B包含聚乙烯醇缩醛,其通过聚乙烯醇或乙烯-乙烯醇共聚物的缩醛化制备。
膜可包含聚乙烯醇缩醛,它们各自具有不同的聚乙烯醇含量、缩醛化度、残余乙酸酯(盐)含量、乙烯比例、分子量和/或缩醛基团的醛的不同的链长。
具体地讲,用于制备聚乙烯醇缩醛的醛或酮(keto)化合物可以为包含2至10个碳原子的直链或支链(即“正”或“异”型),这产生相应的直链或支链缩醛基团。这种聚乙烯醇缩醛相应被称为“聚乙烯醇(异)缩醛”或“聚乙烯醇(正)缩醛”。
根据本发明使用的聚乙烯醇缩醛具体由至少一种聚乙烯醇与一种或多种包含2至10个碳原子的脂族直链酮化合物反应来产生。为此,优选使用正丁醛。
用于制备膜A或B中的聚乙烯醇缩醛的聚乙烯醇或乙烯-乙烯醇共聚物可以为相同或不同的纯聚乙烯醇或乙烯-乙烯醇共聚物或其混合物,具有不同聚合度或水解度。
膜A或B中聚乙烯醇缩醛的聚乙酸乙烯酯含量可通过用皂化至适合程度的聚乙烯醇或乙烯-乙烯醇共聚物来设置。聚乙酸乙烯酯含量影响聚乙烯醇缩醛的极性,由此也改变各层的增塑剂相容性和机械强度。也可进行聚乙烯醇或乙烯-乙烯醇共聚物与多种醛或酮化合物的混合物的缩醛化。
膜A或B优选包含聚乙烯醇缩醛,该聚乙烯醇缩醛具有一定比例的聚乙酸乙烯酯基团,相同或不同,为0.1至20%mol,优选0.5至3%mol,或5至8%mol。
在膜A中使用的聚乙烯醇缩醛PA的聚乙烯醇含量可在6-26%重量、8-24%重量、10-22%重量、12-21%重量、14-20%重量、16-19%重量且优选16和21%或10-16%重量之间。
独立于膜A,用于膜B的聚乙烯醇缩醛PB的聚乙烯醇含量可在14-26%重量、16-24%重量、17-23%重量且优选18和21%重量之间。
在本发明的一个优选的实施方案中,膜A包含具有6至26%重量比例的乙烯醇基团的聚乙烯醇缩醛PA,膜B包含具有14至26%重量比例的乙烯醇基团的聚乙烯醇缩醛B。
膜A或B优选包含未交联的聚乙烯醇缩醛。也可使用交联的聚乙烯醇缩醛。使聚乙烯醇缩醛交联的方法描述于例如EP 1527107 B1和WO 2004/063231 A1(含有羧基的聚乙烯醇缩醛的热自交联)、EP 1606325 A1(与聚醛交联的聚乙烯醇缩醛)和WO 03/020776 A1(与乙醛酸交联的聚乙烯醇缩醛)。
增塑剂
根据本发明使用的膜A和/或B可包含一种或多种选自下列组的化合物作为增塑剂:
-多元脂族或芳族酸的酯,例如己二酸二烷基酯,例如己二酸二己酯、己二酸二辛酯、己二酸己基环己酯、己二酸庚酯和己二酸壬酯的混合物、己二酸二异壬酯、己二酸庚基壬酯、己二酸与脂环族酯醇或包含酯醇的醚化合物的酯;癸二酸二烷基酯,例如癸二酸二丁酯、和癸二酸与脂环族酯醇或包含酯醇的醚化合物的酯;邻苯二甲酸的酯,例如邻苯二甲酸丁基苄酯或邻苯二甲酸双-2-丁氧基乙酯
-具有一个或多个直链或支链脂族或芳族取代基的多元脂族或芳族醇或低聚醚二醇的酯或醚,例如甘油、一缩二乙二醇、二缩三乙二醇或三缩四乙二醇与直链或支链脂族或脂环族羧酸的酯;后一组的实例包括一缩二乙二醇双(2-乙基己酸酯)、二缩三乙二醇双(2-乙基己酸酯)、二缩三乙二醇双(2-乙基丁酸酯)、三缩四乙二醇双正庚酸酯、二缩三乙二醇双正庚酸酯、二缩三乙二醇双正己酸酯、三缩四乙二醇二甲醚和/或一缩二丙二醇苯甲酸酯
-与脂族或芳族酯醇的磷酸酯,例如磷酸三(2-乙基己基)酯(TOF)、磷酸三乙酯、磷酸二苯基-2-乙基己酯和/或磷酸三甲苯酯
-柠檬酸、琥珀酸和/或富马酸的酯。
根据定义,增塑剂为具有高沸点的有机液体。因此,沸点高于120℃的其它类型的有机液体也可用作增塑剂。
在起始状态增塑剂WA存在于膜A中的变体的膜A以及膜B特别优选包含1,2-环己烷二甲酸二异壬酯(DINCH)或二缩三乙二醇双-2-乙基己酸酯(3GO或3G8)作为增塑剂。
膜B可由至少两个具有不同增塑剂含量的子膜B'和B''组成。
另外,膜A和B可包含其它添加剂,例如残余量的水、UV吸收剂、抗氧化剂、粘着调节剂、荧光增白剂或荧光添加剂、稳定剂、着色剂、加工助剂、无机或有机纳米颗粒、热解硅酸和/或表面活性物质。
具体地讲,膜B可包含0.001至0.1%重量的羧酸的碱金属盐和/或碱土金属盐作为粘着控制剂。膜B优选包含至少10ppm量的镁离子,优选20ppm,最优选30ppm。
层压方法
本发明还涉及一种用于制造所述抗穿透玻璃层压体的方法,其中将膜A置于玻璃片上,然后由至少一层膜B覆盖,然后施加第二块玻璃片。
或者,可使膜B置于玻璃片上,然后用至少一层膜A覆盖,并施加第二块玻璃片。
本发明还涉及一种用于制造层压玻璃的方法,其中提供包括至少一层膜A和至少一层膜B的堆叠体,将堆叠体置于第一块玻璃片上,然后施加第二块玻璃片。
根据本发明,可首先使膜A在玻璃片上在整个区域或局部通过升高温度而熔融,然后用膜B覆盖它。或者,可将膜A和B共同置于两块玻璃片之间,并在升高的温度下熔融。
优选进行用于制造层压玻璃的层压步骤,使得膜A和B置于两块玻璃片之间,且由此制备的层状体在高压或低压和升高的温度下挤压,以形成层压体。
为了层压层状体,可使用本领域的技术人员熟悉的方法,利用或不利用预层压体的预先制备。
所谓的“高压釜(autoclave)过程”在约2小时期间在约10至15巴的高压和100至150℃的温度下进行。真空袋法或真空环法,例如根据EP 1 235 683 B1,在约200mbar和130至145℃操作。
也可使用真空层压机。这些由可加热和抽空的室组成,其中层压玻璃制品可在30-60分钟内层压。0.01至300mbar的低压和100至200℃的温度,具体地讲,130至160℃,已在实践中证明了其价值。
在最简单的情况下,为了制造层压玻璃层压体,将膜A或B放在玻璃片上,并且同步或随后放置另一片膜B或A。然后施加第二块玻璃片,并制造玻璃膜层压体。然后可通过本领域的技术人员已知的任何预层压方法去除过量的空气。在此,这些层也已首先轻微地彼此及与玻璃粘着性结合。
然后可使玻璃膜层压体经历高压釜过程。膜A优选放在第一块玻璃片上,并在施加第二块玻璃片之前由较厚的膜B覆盖。该方法可以很多可想到且原则上可行的变体来实施。例如,膜A容易地从合适宽度的卷取下,膜B则已预先裁切成要制造的层压玻璃的尺寸。特别在风挡和其它汽车玻璃部件的情况下,这是有利的。在这种情况下,特别有利的是,较厚的膜B在裁切之前还另外拉伸。这使得能够更经济地使用膜,或者对于膜B具有色调的情况,允许其曲率适应上部片边缘。
在汽车领域,特别是为了生产风挡,膜A和/或B可在膜的上部区域提供有着色区域,象油墨带一样。为此,可使膜B的任一上部与适当着色的聚合物熔体共挤出。
因此,根据本发明,膜B可具有色调,该色调特别已通过上述成形过程在先前的过程步骤中适应成风挡的几何形状。
膜B也可具有楔形厚度轮廓。即使具有膜A的平面平行厚度轮廓,本发明的层压玻璃层压体也获得楔形厚度轮廓,并且可用于机动车风挡中用于HUD显示。
在最简单的情况下,膜B为具有或不具有油墨带、且具有或不具有楔状厚度轮廓的可购得的PVB膜。其中分散有用于IR防护的纳米颗粒的膜B也可用作着色膜。当然,膜B也可以为具有声学功能的膜,使得通过与膜A组合而获得进一步改善的隔音性能。当然,膜B也可已组合了多种所提到的功能。
薄膜A通常通过用流延膜生产线挤出或以吹塑膜的形式生产。在此,也可通过受控熔体破裂或利用流延膜法另外通过用结构化冷却辊和/或结构背辊来产生表面粗糙度。或者,在功能化和用于所述抗穿透玻璃层压体之前,可用溶剂流延法来制造膜A。根据本发明使用的膜优选具有单面表面结构,其粗糙度Rz为0至25μm,优选Rz为1至20μm,特别优选Rz为3至15μm,Rz特别为4至12μm。如果膜A与玻璃片接触的一面的表面粗糙度Rz不大于其厚度的20%,则特别优选。
如果膜A的表面提供有隔热涂层,则优选在施加涂层之前有特别低的表面粗糙度。具体地讲,这里的粗糙度参数Ra小于3μm,Rz小于5μm。
实施例
将PVB树脂粉末(Kuraray Europe GmbH的商业级Mowital B60H)送到同向旋转双螺杆型实验室挤出机的入口漏斗中。同时将相对于聚合物树脂为0.525%重量的乙酸钾和四水乙酸镁的水溶液投料入挤出机入口区,经计算以得到在经脱气的熔体中分别有350ppm乙酸钾和175ppm四水乙酸镁。将熔体从34cm宽的缝模挤出到经冷却的冷却辊上成形,随后以30cm宽度与约50μm厚度缠绕无增塑剂薄膜(用ACA作为膜A利用和评估)。
给膜印有不透明的黑色条,与膜一样长,5cm宽。
在分析测定水分含量(卡尔-费休法)和金属含量(离子色谱法)之前,将卷存储在23℃/28%RH恒定气候的经调节区域中。
在生产试验层压体之前,在相同的气候下调节具有降低的粘着力的商用汽车级PVB膜(来自Kuraray Europe GmbH的TROSIFOL® VG R10 0.76=膜B的实例)。
按以下铺叠顺序,将在平玻璃洗涤机上用<5μS去离子水清洁的分别为标准厚度和超薄的透明玻璃(2 x Planiclear® 2.1 mm和Planiclear® 2.1mm分别+0.7mm透明玻璃)与膜A和B组合,由此得到尺寸30 x 30 cm的试验层压体。
对于粘着试验和抗穿透性,与汽车级PVB组合使用:底玻璃(空气侧)-膜A-VG R10-(锡侧)顶玻璃。
使夹层结构通过商业平玻璃层压钳线(nipper-line),以生产预层压体。用高压釜在标准条件下(90min,包括在140℃和12bar下30min的保持时间)完成层压。
在进一步机械评估之前,将层压体在23℃环境条件放置1星期。
根据ECE 43R(在23℃使用2.26kg钢球,在-20℃和+ 40℃使用226g钢球)测试层压体结构的抗穿透性。两种层压体结构(2 x 2.1mm和2.1mm+ 0.7mm)均安全地通过了ECE R43关于风挡玻璃制品规定的要求。
实施例1
使用可购得的喷墨油墨,例如 SentryGlas® Expressions™(基于醇溶剂),通过数字喷墨印刷实现印刷。为了防止油墨侵蚀Mowital LP BF 6-050,选择单个印刷步骤的色强度,以便获得半透明膜。通过罩印已印刷的部分,随后在22℃干燥膜之后施加下一层印刷油墨,得到必要的不透明度。
实施例2
通过使用适合柔版印刷的水基印刷油墨来实现印刷,该印刷油墨基于聚氨酯作为粘合剂、炭黑作为颜料。这样的印刷油墨可购得,例如,来自Siegwerk Druckfarben AG&Co.KGaA, Siegburg。由于水基油墨不侵蚀Mowital LP BF 6-050,因此,在一个印刷步骤中达到所需的不透明度。干燥后,测得印刷区域中膜A的水含量为2%。
用具有降低的粘着力的商业汽车级PVB膜(TROSIFOL® VG R10 0.76,来自Kuraray Europe GmbH)作为膜B。
如所述获得的包含经印刷膜A的层压体在透明部分和不透明黑色部分之间显示出精细限定的边缘。未能观察到印刷区域的模糊或变形。不透明度测得为明显低于5%可见光透射率。
另外,在7天期间使层压体经历100℃下的热浸泡试验。印刷部分和非印刷部分均未显示任何气泡或其它可见缺陷。
实施例3和4
使用一块2.1mm厚度的绿色玻璃片和一块0.7mm厚度的轻质透明玻璃片,重复以上公开的实施例。类似于用2×2.1mm玻璃得到的结果,如此获得的层压玻璃显示没有着色区域的模糊,并且总体外观与在内部玻璃表面之一上使用釉印黑框得到的层压玻璃接近。
Claims (14)
1.层压玻璃,其通过在两块玻璃片之间层压至少一层包含聚乙烯醇缩醛PA和任选的至少一种增塑剂WA的膜A和至少一层包含聚乙烯醇缩醛PB和至少一种增塑剂WB的膜B而获得,所述层压玻璃的特征在于,在层压之前,
- 膜A中增塑剂WA的量小于22%重量;
- 膜B中增塑剂WB的量为至少22%重量,并且
- 膜A至少在一个表面上包含不透明区域。
2.根据权利要求1所述的层压玻璃,其特征在于,不透明区域位于膜A上从所述层压玻璃的至少一个边缘起0.5至20cm的宽度的带中。
3.根据权利要求1或2所述的层压玻璃,其特征在于,不透明区域由选自炭黑、氧化铁和尖晶石颜料的颜料或染料提供。
4.根据权利要求1至3中任一项所述的层压玻璃,其特征在于,不透明区域以框形状提供到层压玻璃的所有边缘区域。
5.根据权利要求1至4中任一项所述的层压玻璃,其特征在于,膜A包含0-20ppm的碱金属离子。
6.根据权利要求1至5中任一项所述的层压玻璃,其特征在于,膜A包含0-20ppm的碱土金属离子。
7.根据权利要求1至6中任一项所述的层压玻璃,其特征在于,膜A中以ppm计的碱金属离子:碱土金属离子之比为至少1。
8.根据权利要求1至7中任一项所述的层压玻璃,其特征在于,膜A包含聚乙烯醇缩醛PA,其中乙烯醇基团的比例为6至26%重量。
9.根据权利要求1至8中任一项所述的层压玻璃,其特征在于,膜B包含聚乙烯醇缩醛B,其中乙烯醇基团的比例为14至26%重量。
10.根据权利要求1至9中任一项所述的层压玻璃,其特征在于,膜B具有楔形厚度轮廓。
11.根据权利要求1至10中任一项所述的层压玻璃,其特征在于,至少一块玻璃片的厚度小于1.8mm。
12.一种制造权利要求1至11中任一项所述的层压玻璃的方法,其特征在于,给膜A在至少一个表面上提供不透明区域,然后将膜A置于第一块玻璃片上,由至少一层膜B覆盖,并由第二块玻璃片覆盖,然后在超过100℃的温度下层压。
13.根据权利要求12所述的制造层压玻璃的方法,其特征在于,通过在膜A的表面上涂覆选自炭黑、氧化铁和尖晶石颜料的颜料或染料在载液中的悬浮液,来提供不透明区域。
14.根据权利要求12或13所述的制造层压玻璃的方法,其特征在于,通过经历低于膜A的Tg至少3℃的温度,使不透明区域固定在膜A的表面上。
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