CN108859364B - 具有遮阳带的夹层膜 - Google Patents

具有遮阳带的夹层膜 Download PDF

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CN108859364B
CN108859364B CN201810436821.8A CN201810436821A CN108859364B CN 108859364 B CN108859364 B CN 108859364B CN 201810436821 A CN201810436821 A CN 201810436821A CN 108859364 B CN108859364 B CN 108859364B
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film
mixture
transparent
embossing
plasticizer
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CN108859364A (zh
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六车慎一
H.安田
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Kuraray Europe GmbH
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  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
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Abstract

本发明公开了具有遮阳带的夹层膜。本发明涉及具有透明区域和非透明区域的夹层膜，其中非透明区域由两个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第一混合物的外层和一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第二混合物的内层来提供，并且透明区域由一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第三混合物的层来提供，其特征在于第一混合物和第三混合物对于波长为380至780 nm的光具有至少85%的透射率，并且第二混合物对于波长为380至780 nm的光具有低于80%的透射率，并且其中至少非透明区域设置有根据EN ISO 4287测得的Rz/Rv比为1.6至2.5的表面粗糙度。

Description

具有遮阳带的夹层膜
技术领域
本发明涉及具有至少三个层的基于增塑的聚乙烯醇缩醛的夹层膜，其中内层具有降低的透明度。
背景技术
层压安全玻璃通常由两块玻璃嵌板（glass panes）和一个粘合膜组成，所述粘合膜使玻璃嵌板结合在一起并且基于增塑的聚乙烯醇缩醛，优选聚乙烯醇缩丁醛（PVB）。层压安全玻璃特别用作机动车辆中的挡风玻璃。
挡风玻璃常常设置有在该挡风玻璃上部的所谓的遮阳带（shade band），其保护驾驶员免受阳光直射。
挡风玻璃的遮阳带由夹层膜的有色或着色区域提供。这又通过挤出在两层透明材料之间的有色或着色材料的小层而提供给夹层。如图1中所示，有色或着色区域A通常具有大约5至30厘米的宽度，如从膜的边缘看到的那样，其中颜色强度朝向挡风玻璃的下部降低。
在大量不同的技术和挤出装置中，具有有色或着色区域（即遮阳带）的基于增塑的聚乙烯醇缩醛的夹层膜的生产是已知的。通常，通过以下过程来产生有色或着色区域：在两个透明层之间并入或多或少楔形的中间层，导致在挡风玻璃下部方向上的颜色减少（或导致透明度增加）。图2和图3示意性显示了在两个透明层之间的有色中间层，其中颜色减少。
用于汽车应用的夹层膜通常通过压花来产生以提供表现出良好的通气行为的规则的（非随机的）表面结构（特别是在通过真空袋法生产玻璃层压件的方法中）。夹层膜的压花例如描述在WO2016030284A1中。
但是，如图2和图3中所描绘的遮阳带膜在有色或着色区域表现出在层处的两个内部界面。这样的膜例如公开在EP 3070063A1中。由于透明材料和有色材料具有不同的组成，它们具有不同的机械性质。即使在膜仅包含透明材料的剩余部分（即一个层）没有光学畸变的情况下，这样的不同机械性质也可能在压花过程中导致产生在内部界面处的光学畸变。
因此，本发明的目的是提供通过压花产生的具有遮阳带的夹层膜，其不具有在遮阳带区域的内部界面处的光学畸变。
已经发现，当通过压花产生的表面结构具有特定性质时，可以避免通过压花遮阳带区域所产生的光学畸变。
发明内容
本发明的目的是具有透明区域和非透明区域的夹层膜，其中非透明区域由两个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第一混合物的外层和一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第二混合物的内层来提供，并且透明区域由一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第三混合物的层来提供，其中第一混合物和第三混合物对于波长为380至780 nm的光具有至少85%的透射率，并且第二混合物对于波长为380至780 nm的光具有低于80%的透射率，并且其中至少非透明区域设置有根据EN ISO 4287测得的Rz/Rv比为1.6至2.5的表面粗糙度。
优选地，至少非透明区域设置有Rz/Rv比为1.6至2.3、或1.7至2.3的表面粗糙度；更优选的是Rz/Rv比为1.9至2.1。如果Rz/Rv比大于2.5，则发生不良的脱气和不良的光学畸变。另一方面，如果Rz/Rv比小于1.6，则沟槽太深并且将导致不良的边缘密封。
膜的表面粗糙度可以进一步压花有多个深度Rz为20至100 µm的沟槽。
Rz和Rv如EN ISO 4287中所定义的那样用于本申请中。Rz代表表面结构的平均粗糙度深度，且Rv代表取样长度内表面粗糙度的最深轮廓谷的深度。根据DIN EN ISO 4287测量具有粗糙度值Rz和最大轮廓谷深度Rv的膜的表面粗糙度。用于测量表面粗糙度的测量装置必须满足EN ISO 3274。所用的轮廓滤波器必须符合DIN EN ISO 11562。
膜的非透明区域的表面粗糙度可以与膜的透明区域的表面粗糙度相同，并可以通过首先在熔体破裂条件下挤出膜并随后进行压花步骤来提供。
因此，本发明的另一目的是制造具有透明区域和非透明区域的夹层膜的方法，其中非透明区域由两个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第一混合物的外层和一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第二混合物的内层来提供，并且透明区域由一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第三混合物的层来提供，其中第一混合物和第三混合物对于波长为380至780 nm的光具有至少85%的透射率，并且第二混合物对于波长为380至780 nm的光具有低于80%的透射率，其中通过在熔体破裂条件下挤出膜并随后进行压花步骤来使得至少非透明区域设置有Rz/Rv比为1.6至2.5的表面粗糙度。
在本发明的优选实施方案中，内层对于波长为380至780 nm的光的透射率为3-75%、更优选8-70%、尤其是15-60%。
嵌在外层之间的内层可以具有夹层膜总面积的5-40%、优选5-25%的面积。
通常，用于汽车用途的浮法玻璃和/或层压窗玻璃（laminated glazing）对于波长为380至780 nm的光具有至少88%的透射率。
为了着色，可以在没有特殊限制的情况下使用着色剂、颜料和染料。
颜料的实例包括有机颜料，如偶氮型、酞菁型、喹吖啶酮型、苝型、二噁嗪型、蒽醌型、异吲哚啉代（isoindolino）型等等，氧化物、氢氧化物、硫化物、铬酸、碳酸盐、硅酸盐，无机颜料，如砷酸盐、亚铁氰化物、碳、金属粉末等等。
染料的实例包括诸如偶氮、蒽醌、酞菁、喹吖啶酮、苝、二噁嗪、蒽醌、吲哚啉酮、异吲哚啉代、醌亚胺、三苯甲烷、噻唑、硝基和亚硝基染料的染料。其中，偶氮型和蒽醌型优选用作几乎不阻挡具有近红外光波长（750至1000 nm）的光线的染料。
遮阳带PVB膜（即具有非透明区域和透明区域的包含增塑的聚乙烯醇缩醛的膜）例如可以根据WO2005090054A1中公开的方法挤出。非透明区域的外层在遮阳带外部（即在透明区域中）结合成单一层。优选地，外层具有相同的组成。除了颜色之外，内层可以具有与外层相同的组成。
在沟槽之间的隆起上的随机表面图案在膜的挤出过程中产生，并且在压花过程中应基本保持为挤出过程中获得的原样。
优选地，在压花后获得的沟槽之间的隆起的表面粗糙度比挤出后获得的表面粗糙度低至多20%、更优选至多10%。在挤出和压花后获得的沟槽之间的隆起的表面粗糙度最好是相同的。这可以通过不与隆起区域中的膜接触或不与之充分接触的压花工具来实现。
包含增塑的聚乙烯醇缩醛的熔体的挤出优选在熔体破裂条件下使用具有可以调节温度的模唇（lips）的挤出模头来进行。这样的挤出工艺是本领域技术人员例如由EP 0185 863 B1已知的。
在沟槽之间的隆起上的随机表面图案可以与膜表面上的相同或不同。在熔体破裂挤出过程中可以通过改变放料间隙（discharge gap）的宽度和直接在模头出口上的模唇温度来产生不同的表面图案或粗糙度水平。
优选的是实施挤出工艺以获得具有Rz = 10至70 µm的表面的随机粗糙度的膜，更优选获得具有Rz = 25至60 µm的表面的随机粗糙度的膜。
在本发明的第一变体中，在熔体破裂条件下用具有100-270℃、优选100-240℃的模唇温度的挤出模头来实施挤出。
在本发明的第二变体中，以500-3500 kg/h的熔体流量实施熔体破裂条件下的挤出。
在挤出后，在步骤b）中对膜在一侧或两侧上在各个情况下独立地以Rz = 20至100µm、优选Rz = 20至80 µm、特别是Rz = 25 µm至70 µm的表面结构和粗糙度深度施以压花。
膜的最终表面结构可以在单一步骤中或优选在两个不同的压花步骤中压花。在单一步骤压花中，使用两个压花辊，而在多步骤压花中，使用压花辊和压辊（pressureroller）。压辊（pressing roller）优选具有肖氏A硬度为20-80的橡胶表面。
可以以使得结构化膜的两侧具有不同的粗糙度深度Rz的方式进行根据本发明的压花步骤。这可以例如通过不同的压花工具或压花工具和/或压辊的温度来实现。
膜的两个表面上的沟槽可以彼此共享70至90°或5-45°的角度。在另一方面，在膜的至少一个表面上的沟槽相对于挤出方向具有5-45°、优选35-45°的角度。
沟槽的间距在膜的表面上可以相同或不同，其中表面之间5%的偏差被视为是相同的。沟槽的间距可以为100-1500 µm、优选200-1000 µm。
在压花工艺之前和/或之后，可以将膜冷却到-10至+40℃，从而以这种方式固定膜的表面结构。冷却优选经由相应调节温度的冷却辊来进行。
优选地，压花辊由金属或陶瓷制成，并且具备具有随后呈现在膜表面上的结构的阴轮廓图案（negative profile pattern）的表面。压花辊的沟槽的深度高于膜的预期粗糙度是优选的，以便在压花后保持熔体破裂表面。
压花辊的温度为80至200℃、尤其是80至170℃、优选100至160℃、特别是110至155℃。特别优选地，压花辊具有（例如用聚合物或陶瓷）涂覆的钢表面以减少膜的粘附。
在第一实施方案中，挤出的膜在具有相同或不同的表面压纹的两个压花辊之间压花。
在本发明的另一实施方案中，在反向旋转的压花辊和压辊之间引导膜。优选地，膜在压花辊之间和/或压花辊与压辊之间暴露于10至400 N/mm、尤其是10至150 N/mm、优选30至130 N/mm和特别是40至110 N/mm的线压力（line pressure）。如果进行若干个工艺步骤b）的话，线压力可以相同或不同。线压力是指基于膜宽度的对辊（roller pair）的压紧力。
压辊优选具有0至50℃、优选5至30℃的温度，即它们相对于压花辊被主动冷却。压辊的温度在工艺步骤b）中可以相同或不同。
压辊将膜压到压花辊的结构化表面中，并轻轻地靠在压花辊上。通过改变线压力，可以改变压花区的表面并由此改变膜在辊隙中的停留时间。
通过选择线压力、膜温度和/或辊温度、辊速度和膜网幅在辊上的包络角的工艺参数，可以用给定的压花辊的粗糙度深度影响膜压花的粗糙度深度。
在这种情况下，同样，可以通过温度调节辊的辊隙直接引导膜，即不在它们周围传递。
可以特别使用交联或非交联形式的聚乙烯醇缩丁醛（PVB）作为部分缩醛化的聚乙烯醇，其与至少一种增塑剂、用于粘附调节的金属盐、有机添加剂和/或无机填料混合。
本领域中已知用于该目的的所有增塑剂，特别是多价酸、多元醇或低聚醚二醇的酯，如例如己二酸酯、癸二酸酯或邻苯二甲酸酯，特别是己二酸二正己酯、癸二酸二丁酯、邻苯二甲酸二辛酯，二甘醇、三甘醇或四甘醇与直链或支链脂族羧酸的酯、以及这些酯的混合物在一方面适于作为部分缩醛化的聚乙烯醇的增塑剂。脂族二醇与长链脂族羧酸的酯，特别是三乙二醇与含有6至10个C原子的脂族羧酸（如2-乙基丁酸或正庚酸）的酯优选用作部分缩醛化的聚乙烯醇，特别是聚乙烯醇缩丁醛的标准增塑剂。特别优选使用选自己二酸二正己酯（DHA）、癸二酸二丁酯（DBS）、邻苯二甲酸二辛酯（DOP）、二甘醇、三甘醇或四甘醇与直链或支链脂族羧酸的酯，特别是三乙二醇-双-2-乙基丁酸酯（3GH）、三乙二醇-双-正庚酸酯（3G7）、三乙二醇-双-2-乙基己酸酯（3G8）、四乙二醇-双-正庚酸酯（4G7）的一种或若干种增塑剂。
在本发明的一个特定实施方案中，通过向膜材料中添加减少粘附的物质，可以进一步减少膜对压花工具的粘附。
基于100重量份的树脂计，增塑的部分缩醛化的聚乙烯醇树脂优选含有25至45重量份、特别优选30至40重量份的增塑剂。
部分缩醛化的聚乙烯醇以已知方式通过水解的聚乙烯酯的缩醛化来生产。例如，将甲醛、乙醛、丙醛、丁醛等等，优选丁醛用作醛类。
优选的聚乙烯醇缩丁醛树脂含有10至25重量%、优选17至23重量%和特别优选19至21重量%的乙烯醇基团和/或0至20重量%、优选0.5至2.5重量%的乙酸酯基团。
在另外的工艺变体中，根据WO 2004/063231 A1，将与多醛（特别是戊二醛）和氧代羧酸（特别是乙醛酸）部分交联的PVB用作聚合物。这样的部分交联的PVB具有比类似的非交联PVB的粘度高10至50%的粘度。
优选将膜的水含量调节到0.15至0.8重量%，特别是0.3至0.5重量%。
根据本发明生产的膜特别可用于由一个或若干个玻璃嵌板和/或一个或若干个聚合物嵌板以及至少一个结构化膜制造层压件。
在制造这些层压件的过程中，首先通过压制、真空袋或真空环由玻璃/聚合物嵌板和膜生产预复合件。一般而言，预复合层压件因空气夹杂而略显浑浊。例如根据WO 03/033583，层压件的最终制造在高压釜中进行。
附图说明
图1显示了具有有色或着色区域A的挡风玻璃。
图2和图3显示了在两个透明层之间的有色中间层。
具体实施方案
根据本发明的实施例
根据WO2005090054A1中公开的方法采用以下条件挤出含有每100份PVB树脂38份增塑剂的标称含量的具有蓝色遮阳带的0.76毫米厚PVB膜。
模唇温度：195℃
熔体流量：1000千克/小时
线速度：15米/分钟。
该PVB膜在每侧上具有熔体破裂表面粗糙度，其通过33 µm（微米）的Rz熔体破裂值来表征。遮阳带层厚度为300 µm，在遮阳带区域处在夹层边缘测得的透光率为7%。
非透明区域的外层在遮阳带外部（即在透明区域中）结合成单一层，并具有相同的组成。除了颜色之外，内层具有与外层相同的组成。
该PVB膜在具有下列性质的两组压辊和压花辊之间压花：
设备参数：
橡胶辊的硬度：70 ± 5 肖氏A
压花辊的粗糙度：大约200 µm
压花辊的间距：大约500 µm
沟槽角度：45°
表面涂层：聚合物
橡胶辊温度：10℃
实施例编号 压花辊的温度(℃)
1 135
2 130
3 145
4 120
5 115
6 60
7 155
两个压花阶段的压辊和压花辊具有相同的性质。
膜性质显示在下表中，其中“熔体破裂产生的Rz”代表在熔体破裂条件下挤出后的粗糙度。“最终Rz”代表压花后的粗糙度。“最终Rv”代表压花后谷深度的粗糙度。所有值根据DIN ISO 4287测得。
实施例1-5是根据本发明的，而实施例6和7是对比实施例。
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Figure 475903DEST_PATH_IMAGE002
通过目视检查评估非透明区域的光学畸变。任何光学畸变以斑驳图案的形式被看到。
Figure 82465DEST_PATH_IMAGE003
根据（对比）实施例6的膜因低温压花而几乎未显示压花图案。导致不良的脱气和光学畸变。根据（对比）实施例7的膜因高温压花而显示过多的压花图案。因此，导致不良的边缘密封和光学畸变。
采用本发明的方法，可以生产具有遮阳带的增塑的聚乙烯醇缩醛膜，其具有良好的光学畸变和更佳的层压成品率。

Claims (11)

1.具有透明区域和非透明区域的夹层膜，其中所述非透明区域由两个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第一混合物的外层和一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第二混合物的内层来提供，并且所述透明区域由一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第三混合物的层来提供，其特征在于所述第一混合物和所述第三混合物对于波长为380至780 nm的光具有至少85%的透射率，并且所述第二混合物对于波长为380至780 nm的光具有低于80%的透射率，并且其中至少所述非透明区域设置有根据EN ISO 4287测得的Rz/Rv比为1.6至2.5的表面粗糙度。
2.根据权利要求1所述的夹层膜，其特征在于所述膜设置有深度为20至100 µm的多个沟槽。
3.根据权利要求2所述的夹层膜，其特征在于所述沟槽具有20-50 µm的深度、10-200 µm的宽度和50-2500 µm的间距。
4.根据权利要求2所述的夹层膜，其特征在于通过在至少一个压花辊和至少一个压辊之间对具有Rz = 1至70 µm的至少所述非透明区域的随机粗糙度的膜进行压花来提供所述沟槽。
5.根据权利要求1所述的夹层膜，其特征在于至少所述非透明区域的随机粗糙度通过熔体破裂挤出所述膜来提供。
6.根据权利要求1-4任一项所述的夹层膜，其特征在于所述内层包含染料或颜料。
7.根据权利要求1-4任一项所述的夹层膜，其特征在于嵌在外层之间的内层的面积是所述膜的总面积的5-40%。
8.制造具有透明区域和非透明区域的夹层膜的方法，其中所述非透明区域由两个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第一混合物的外层和一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第二混合物的内层来提供，并且所述透明区域由一个包含至少一种增塑剂和至少一种聚乙烯醇缩醛的第三混合物的层来提供，其中所述第一混合物和所述第三混合物对于波长为380至780 nm的光具有至少85%的透射率，并且所述第二混合物对于波长为380至780 nm的光具有低于80%的透射率，其特征在于通过在熔体破裂条件下挤出所述膜并随后进行压花步骤来使得至少所述非透明区域设置有Rz/Rv比为1.6至2.5的表面粗糙度。
9.根据权利要求8所述的方法，其特征在于挤出具有Rz = 1至70 µm的表面的随机粗糙度的具有透明区域和非透明区域的膜，并随后在至少一个压花辊和至少一个压辊之间进行压花。
10.根据权利要求8或9所述的方法，其特征在于所述膜压花有多个深度为20至100 µm的沟槽。
11.根据权利要求8或9所述的方法，其特征在于所述沟槽具有20-50 µm的深度、10-200µm的宽度和50-2500 µm的间距。
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