CN111918851A - 夹层玻璃用中间膜和夹层玻璃 - Google Patents
夹层玻璃用中间膜和夹层玻璃 Download PDFInfo
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- CN111918851A CN111918851A CN201980023090.7A CN201980023090A CN111918851A CN 111918851 A CN111918851 A CN 111918851A CN 201980023090 A CN201980023090 A CN 201980023090A CN 111918851 A CN111918851 A CN 111918851A
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- Prior art keywords
- laminated glass
- resin layer
- layer
- resin
- interlayer film
- Prior art date
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- 239000011229 interlayer Substances 0.000 title claims abstract description 98
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- 239000011347 resin Substances 0.000 claims abstract description 251
- 239000003086 colorant Substances 0.000 claims abstract description 46
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- 239000002245 particle Substances 0.000 claims description 87
- -1 perylene compound Chemical class 0.000 claims description 61
- 229910052751 metal Inorganic materials 0.000 claims description 46
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 36
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 5
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 18
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 13
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 2
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- 239000004925 Acrylic resin Substances 0.000 description 2
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- XCTNDJAFNBCVOM-UHFFFAOYSA-N 1h-imidazo[4,5-b]pyridin-2-ylmethanamine Chemical compound C1=CC=C2NC(CN)=NC2=N1 XCTNDJAFNBCVOM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供能够在具备被着色剂着色的树脂层的中间膜中抑制光和热导致的变色的夹层玻璃用中间膜。本发明的夹层玻璃用中间膜具有红外线反射层和包含热塑性树脂的第1树脂层,所述第1树脂层配置在所述红外线反射层的第1表面侧,所述红外线反射层在波长350nm~450nm具有第1极大反射波长,在波长800nm以上具有第2极大反射波长,所述第1极大反射波长下的反射率和所述第2极大反射波长下的反射率均为15%以上,所述第1树脂层包含着色剂。
Description
技术领域
本发明涉及具有红外线反射层的夹层玻璃用中间膜。此外,本发明涉及使用了所述夹层玻璃用中间膜的夹层玻璃。
背景技术
就夹层玻璃而言,通常即使受到外部冲击而发生破损,玻璃碎片的飞散量也较少,安全性优异。因此,所述夹层玻璃广泛用于车辆、铁道车辆、航天器、船舶和建筑物等。所述夹层玻璃通过在一对玻璃板之间夹入夹层玻璃用中间膜而制造。对于这样的车辆和建筑物的开口部中使用的夹层玻璃,需求高隔热性。
为了提高隔热性,有时使用具备红外线反射层的中间膜。下述的专利文献1中公开了具备红外线反射层的中间膜。
此外,夹层玻璃中,有时需求创意性和设计性。不仅是无色透明的夹层玻璃,还已知有被着色的夹层玻璃。下述的专利文献2中公开了,用于得到被着色的夹层玻璃的被着色的中间膜。该中间膜包含着色剂。
现有技术文献
专利文献
专利文献1:日本特开2017-81775号公报
专利文献2:日本特开2010-248026号公报
发明内容
发明所解决的技术问题
例如,使用了中间膜的夹层玻璃安装于车辆的开口部处。在安装于车辆的开口部处的夹层玻璃中,入射太阳光,使得该夹层玻璃暴露于高温下。
在以往的使用了被着色的中间膜的夹层玻璃中,有时由于光和热而导致变色。其结果,有时夹层玻璃的创意性和设计性受到损害。
本发明的目的在于,提供能够在具备被着色剂着色的树脂层的中间膜中抑制光和热导致的变色的夹层玻璃用中间膜。此外,本发明的目的在于,提供使用了所述夹层玻璃用中间膜的夹层玻璃。
解决问题的技术手段
根据本发明的广泛方案,提供夹层玻璃用中间膜(以下,有时记载为中间膜),其具有红外线反射层和包含热塑性树脂的第1树脂层,所述第1树脂层配置在所述红外线反射层的第1表面侧,所述红外线反射层在波长350nm~450nm具有第1极大反射波长,在波长800nm以上具有第2极大反射波长,所述第1极大反射波长下的反射率和所述第2极大反射波长下的反射率均为15%以上,所述第1树脂层包含着色剂。
本发明的中间膜的一个特定方案中,所述红外线反射层包含金属溅射层。
本发明的中间膜的一个特定方案中,所述着色剂为苝化合物、酞菁化合物、萘酞菁化合物或蒽酞菁化合物。
本发明的中间膜的一个特定方案中,所述第1树脂层包含隔热粒子。
所述第1树脂层中的所述热塑性树脂优选为聚乙烯醇缩醛树脂。
所述第1树脂层优选包含增塑剂。
本发明的中间膜的一个特定方案中,所述中间膜具备第2树脂层,所述第2树脂层配置在所述红外线反射层的与所述第1表面相反的第2表面侧。
所述第2树脂层中的所述热塑性树脂优选为聚乙烯醇缩醛树脂。
所述第2树脂层优选包含增塑剂。
根据本发明的广泛方案,提供夹层玻璃,其具备第1夹层玻璃部件、第2夹层玻璃部件以及所述夹层玻璃用中间膜,所述中间膜具有或不具有第2树脂层,在所述中间膜具有所述第2树脂层的情况下,所述第2树脂层配置在所述红外线反射层的与所述第1表面相反的第2表面侧,在所述中间膜具有所述第2树脂层的情况下,所述第1夹层玻璃部件配置在所述第1树脂层外侧,所述第2夹层玻璃部件配置在所述第2树脂层外侧,所述在中间膜不具有所述第2树脂层的情况下,所述第1夹层玻璃部件配置在所述第1树脂层外侧,所述第2夹层玻璃部件配置在所述红外线反射层外侧。
本发明的夹层玻璃的一个特定方案中,所述夹层玻璃在建筑物或车辆中安装于外部空间和热线从所述外部空间入射的内部空间之间的开口部处,并且使得所述第2夹层玻璃部件位于所述外部空间侧且使得所述第1夹层玻璃部件位于所述内部空间侧。
发明的效果
本发明的夹层玻璃用中间膜具有红外线反射层和包含热塑性树脂的第1树脂层。本发明的夹层玻璃用中间膜中,所述第1树脂层配置在所述红外线反射层的第1表面侧。本发明的夹层玻璃用中间膜中,所述红外线反射层在波长350nm~450nm具有第1极大反射波长,在波长800nm以上具有第2极大反射波长,所述第1极大反射波长和所述第2极大反射波长下的反射率分别为15%以上。本发明的夹层玻璃用中间膜中,所述第1树脂层包含着色剂。本发明的夹层玻璃用中间膜中,由于具备所述的构成,因此能够在具备被着色剂着色的树脂层的中间膜中抑制光和热导致的变色。
附图说明
[图1]图1是示意性地表示本发明的第1实施方式的夹层玻璃用中间膜的截面图。
[图2]图2是示意性地表示本发明的第2实施方式的夹层玻璃用中间膜的截面图。
[图3]图3是示意性地表示使用了图1表示的夹层玻璃用中间膜的夹层玻璃的一个实例的截面图。
[图4]图4是示意性地表示使用了图2表示的夹层玻璃用中间膜的夹层玻璃的一个实例的截面图。
本发明的具体实施方式
以下,对于本发明详细地进行说明。
(夹层玻璃用中间膜)
本发明的夹层玻璃用中间膜(以下,有时记载为中间膜)具有红外线反射层和包含热塑性树脂的第1树脂层。本发明的中间膜中,所述第1树脂层配置在所述红外线反射层的第1表面侧。本发明的中间膜中,所述红外线反射层在波长350nm~450nm具有第1极大反射波长,在波长800nm以上具有第2极大反射波长,所述第1极大反射波长下的反射率和所述第2极大反射波长下的反射率分别为15%以上。本发明的中间膜中,所述第1树脂层包含着色剂。
本发明的中间膜中,由于具备所述的构成,因此能够在具备被着色剂着色的树脂层的中间膜中抑制光和热导致的变色。使用了本发明的中间膜的夹层玻璃,例如可以在建筑物或车辆中安装于外部空间和热线从所述外部空间入射的内部空间之间的开口部处,以使得所述第1树脂层位于所述内部空间侧。在这种情况下,太阳光等的热线在到达所述第1树脂层前,被红外线反射层充分反射。此外,太阳光等的热线中,通常包含波长350nm~450nm的光线和波长800nm以上的光线。本发明中,由于能够提高波长350nm~450nm的第1极大反射波长和波长800nm以上的第2极大反射波长这两者下的反射率,因此能够抑制光导致的变色,并且抑制热导致的变色。
所述中间膜可以在低于波长350nm具有与第1、第2极大吸收波长不同的极大吸收波长。所述中间膜也可以在波长350nm~450nm具有与第1极大吸收波长不同的极大吸收波长,该极大吸收波长的反射率可以低于15%。所述中间膜也可以在大于波长450nm并且低于800nm具有与第1、第2极大吸收波长不同的极大吸收波长。所述中间膜也可以在波长800nm以上具有与第2极大吸收波长不同的极大吸收波长,该极大吸收波长的反射率可以低于15%。
所述红外线反射层的所述极大吸收波长通过下述方式进行测定。
基于JIS R3106:1998,使用分光光度计(HITACHI HIGH-TECH公司制“U-4100”)测定反射率,将表示得到的波谱的极大值的波长设为所述极大吸收波长。
所述第1树脂层包含着色剂。因此,所述中间膜的可见光线透射率可以较低。从进一步提高透过夹层玻璃的视觉辨认性的观点出发,所述中间膜的可见光线透射率优选为20%以上,更优选为50%以上,进一步优选为70%以上。从进一步提高夹层玻璃的创意性和设计性的观点出发,所述中间膜的可见光线透射率优选为88%以下,更优选为87%以下,进一步优选为86%以下。
就所述可见光线透射率而言,使用分光光度计(HITACHI HIGH-TECH公司制“U-4100”),基于JIS R3211:1998,在波长380nm~780nm进行测定。
所述中间膜具有或不具有第2树脂层。从进一步提高夹层玻璃部件和中间膜的粘接性的观点出发,所述中间膜可以具有第2树脂层。在所述中间膜具有所述第2树脂层的情况下,所述第2树脂层配置在所述红外线反射层的与所述第1表面相反的第2表面侧。
就所述中间膜而言,可以卷绕为卷状而制成中间膜的卷体。卷体可以具备卷芯和中间膜。中间膜可以卷绕在卷芯的外周。
以下,在参照附图的同时,对于本发明的具体的实施方式进行说明。
图1是示意性地表示本发明的第1实施方式的夹层玻璃用中间膜的截面图。
图1表示的中间膜11是具有3层以上结构的多层中间膜。中间膜11用于得到夹层玻璃。中间膜11为夹层玻璃用中间膜。中间膜11具备红外线反射层1、第1树脂层2、第2树脂层3。第1树脂层2配置并叠层在红外线反射层1的第1表面1a侧。第2树脂层3配置并叠层在红外线反射层1的与第1表面1a相反的第2表面1b侧。红外线反射层1为中间层。第1树脂层2和第2树脂层3分别为保护层,在本实施方式中为表面层。红外线反射层1配置并夹入第1树脂层2和第2树脂层3之间。因此,中间膜11具有第1树脂层2、红外线反射层1和第2树脂层3依次叠层而成的多层结构(第1树脂层2/红外线反射层1/第2树脂层3)。
图2是示意性地表示本发明的第2实施方式的夹层玻璃用中间膜的截面图。
图2表示的中间膜11A是具有2层结构的多层中间膜。中间膜11A用于得到夹层玻璃。中间膜11A为夹层玻璃用中间膜。中间膜11A具备红外线反射层1和第1树脂层2。第1树脂层2配置并叠层在红外线反射层1的第1表面1a侧。中间膜11A具有第1树脂层2和红外线反射层1依次叠层而成的多层结构(第1树脂层2/红外线反射层1)。
需要说明的是,在第1树脂层2和红外线反射层1之间和红外线反射层1和第2树脂层3之间分别可以配置有其他层。第1树脂层2和红外线反射层1、红外线反射层1和第2树脂层3分别优选直接叠层。作为其他层,可举出粘接层、包含聚对苯二甲酸乙二醇酯等的层。
以下,对于构成本发明的中间膜和夹层玻璃的各部件的其他详细内容进行说明。
(红外线反射层)
所述红外线反射层反射红外线。所述红外线反射层在波长350nm~450nm具有第1极大反射波长,在波长800nm以上具有第2极大反射波长。所述第1极大反射波长和所述第2极大反射波长下的反射率分别为15%以上。选择并使用具有这样的性质的红外线反射层。
从有效抑制光和热导致的变色的观点出发,所述红外线反射层优选包含金属溅射层。所述金属溅射层可以通过金属溅射而形成。包含所述金属溅射层的红外线反射层可以为附有金属箔的树脂膜。
作为所述红外线反射层,可举出附有金属箔的树脂膜、在树脂层上形成金属层和诱电层而得到的多层叠层膜、包含石墨的膜、多层树脂膜和液晶膜等。这些膜具有反射红外线的性能。
所述红外线反射层优选为附有金属箔的树脂膜、包含石墨的膜、多层树脂膜或液晶膜。这些膜的红外线的反射性能显著优异。因此,通过使用这些膜,得到能够使隔热性进一步提高,进一步在长时间内保持高可见光线透射率的夹层玻璃。
所述附有金属箔的树脂膜具备树脂膜、叠层在该树脂膜的外表面的金属箔。作为所述树脂膜的材料,可举出聚对苯二甲酸乙二醇酯树脂、聚萘二甲酸乙二醇酯树脂、聚乙烯醇缩醛树脂、乙烯-乙酸乙烯酯共聚物树脂、乙烯-丙烯酸共聚物树脂、聚氨酯树脂、聚乙烯醇树脂、聚烯烃树脂、聚氯乙烯树脂和聚酰亚胺树脂等。作为所述金属箔的材料,可举出铝、铜、银、金、钯、和包含这些的合金等。
在所述树脂层上形成金属层和诱电层而得到的多层叠层膜,是在树脂层(树脂膜)上交替地以任意层数叠层金属层和诱电层而得到的多层叠层膜。需要说明的是,在所述树脂层上形成金属层和诱电层而得到的多层叠层膜中,优选金属层和诱电层全部交替地进行叠层,也可以如金属层/诱电层/金属层/诱电层/金属层/金属层/诱电层/金属层这样,存在一部分未交替地进行叠层的结构部分。
作为所述多层叠层膜中的所述树脂层(树脂膜)的材料,可举出与所述附有金属箔的树脂膜中的树脂膜的材料同样的材料。作为所述多层叠层膜中的所述树脂层(树脂膜)的材料,可举出聚乙烯、聚丙烯、聚乳酸、聚(4-甲基-1-戊烯)、聚偏二氟乙烯、环状聚烯烃、聚甲基丙烯酸甲酯、聚氯乙烯、聚乙烯醇、尼龙6、11、12、66等的聚酰胺、聚苯乙烯、聚碳酸酯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚酯、聚苯硫醚和聚醚酰亚胺等。作为所述多层叠层膜中的所述金属层的材料,可举出与所述附有金属箔的树脂膜中的所述金属箔的材料同样的材料。可以在所述金属层的两面或者单面赋予金属或者金属的混合氧化物的涂层。作为所述涂层的材料,可举出ZnO、Al2O3、Ga2O3、InO3、MgO、Ti、NiCr和Cu等。
作为所述多层叠层膜中的所述诱电层的材料,例如可举出氧化铟等。
所述多层树脂膜为叠层有多个树脂膜的叠层膜。作为所述多层树脂膜的材料,可举出与所述多层叠层膜中的所述树脂层(树脂膜)的材料同样的材料。所述多层树脂膜中的树脂膜的叠层数可以为2以上、3以上或5以上。所述多层树脂膜中的树脂膜的叠层数可以为1000以下、100以下或50以下。
所述多层树脂膜可以为具有不同光学性质(折射率)的2种以上热塑性树脂层交替地或随机地以任意层数进行叠层而得到的多层树脂膜。这样的多层树脂膜以得到期望的红外线反射性能的方式而构成。
作为所述液晶膜,可举出反射任意波长的光的胆甾型液晶层以任意层数进行叠层而得到的膜。这样的液晶膜以得到期望的红外线反射性能的方式而构成。
从反射红外线的性能优异的方面出发,所述红外线反射层优选具有在800nm~2000nm的范围内的至少一个波长下红外线透射率为40%以下的性质。需要说明的是,后述实施例中使用了的红外线反射层的红外线透射率,满足所述的优选条件。在800nm~2000nm的范围内的至少一个波长下红外线透射率更优选为30%以下,进一步优选为20%以下。
所述红外线反射层的波长800nm~2000nm的范围中各波长的透射率,具体而言,通过下述方式进行测定。准备单独的红外线反射层。使用分光光度计(HITACHI HIGH-TECH公司制“U-4100”),并基于JIS R3106:1998或JIS R3107:2013,得到红外线反射层的波长800nm~2000nm中各波长的分光透射率。优选基于JIS R3107:2013,得到红外线反射层的波长800nm~2000nm中各波长的分光透射率。
(第1树脂层和第2树脂层)
热塑性树脂:
第1树脂层包含热塑性树脂(以下,有时记载为热塑性树脂(1))。第1树脂层中,作为热塑性树脂(1),优选包含聚乙烯醇缩醛树脂(以下,有时记载为聚乙烯醇缩醛树脂(1))。第2树脂层中,包含热塑性树脂(以下,有时记载为热塑性树脂(2)),作为热塑性树脂(2),优选包含聚乙烯醇缩醛树脂(以下,有时记载为聚乙烯醇缩醛树脂(2))。
所述热塑性树脂(1)和所述热塑性树脂(2)可以相同或不同。所述热塑性树脂(1)和所述热塑性树脂(2)分别可以仅使用1种或组合使用2种以上。所述聚乙烯醇缩醛树脂(1)和所述聚乙烯醇缩醛树脂(2)分别可以仅使用1种或组合使用2种以上。
作为所述热塑性树脂,可举出聚乙烯醇缩醛树脂、乙烯-乙酸乙烯酯共聚物树脂、乙烯-丙烯酸共聚物树脂、聚氨酯树脂、聚乙烯醇树脂、聚烯烃树脂、聚乙酸乙烯酯树脂、聚苯乙烯树脂和离聚物树脂等。也可以使用这些以外的热塑性树脂。
所述热塑性树脂优选为聚乙烯醇缩醛树脂。通过组合使用聚乙烯醇缩醛树脂和增塑剂,使树脂层对于夹层玻璃部件和红外线反射层等的其他层的粘接力进一步提高。
所述聚乙烯醇缩醛树脂,例如,可以通过用醛使聚乙烯醇(PVA)缩醛化而制造。所述聚乙烯醇缩醛树脂优选为聚乙烯醇的缩醛化物。所述聚乙烯醇,例如,通过使聚乙酸乙烯酯皂化而得到。所述聚乙烯醇的皂化度,通常在70~99.9摩尔%的范围内。
所述聚乙烯醇(PVA)的平均聚合度优选为200以上,更优选为500以上,进一步优选为1500以上,进一步优选为1600以上,特别优选为2600以上,最优选为2700以上,优选为5000以下,更优选为4000以下,进一步优选为3500以下。所述平均聚合度为所述下限以上时,夹层玻璃的耐贯穿性进一步提高。所述平均聚合度为所述上限以下时,树脂层的成形变得容易。
所述聚乙烯醇的平均聚合度通过基于JIS K6726“聚乙烯醇试验方法”的方法而求得。
所述聚乙烯醇缩醛树脂中包含的缩醛基的碳原子数没有特别限定。制造所述聚乙烯醇缩醛树脂时使用的醛没有特别限定。所述聚乙烯醇缩醛树脂中的缩醛基的碳原子数优选为3~5,更优选为3或4。所述聚乙烯醇缩醛树脂中的缩醛基的碳原子数为3以上时,树脂层的玻璃化转变温度充分降低。
所述醛没有特别限定。通常而言,优选使用碳原子数为1~10的醛。作为所述碳原子数为1~10的醛,例如可举出:丙醛、正丁醛、异丁醛、正戊醛、2-乙基丁醛、正己醛、正辛醛、正壬醛、正癸醛、甲醛、乙醛和苯甲醛等。优选丙醛、正丁醛、异丁醛、正己醛或正戊醛,更优选丙醛、正丁醛或异丁醛,进一步优选正丁醛。所述醛可以仅使用1种或组合使用2种以上。
所述聚乙烯醇缩醛树脂的羟基含有率(羟基量)优选为15摩尔%以上,更优选为18摩尔%以上,进一步优选为20摩尔%以上,特别优选为28摩尔%以上,优选为40摩尔%以下,更优选为35摩尔%以下,进一步优选为32摩尔%以下。所述羟基含有率为所述下限以上时,树脂层的粘接力进一步提高。此外,所述羟基含有率为所述上限以下时,树脂层的柔软性提高,树脂层的处理变得容易。
所述聚乙烯醇缩醛树脂的羟基含有率是将键合有羟基的亚乙基量除以主链的总亚乙基量而求得的摩尔分数以百分数表示的值。所述键合有羟基的亚乙基量,例如,可以基于JIS K6728“聚乙烯醇缩丁醛试验方法”而测定。
所述聚乙烯醇缩醛树脂的乙酰化度(乙酰基量)优选为0.1摩尔%以上,更优选为0.3摩尔%以上,进一步优选为0.5摩尔%以上,优选为30摩尔%以下,更优选为25摩尔%以下,进一步优选为20摩尔%以下,特别优选为15摩尔%以下,最优选为3摩尔%以下。所述乙酰化度为所述下限以上时,聚乙烯醇缩醛树脂与增塑剂的相溶性提高。所述乙酰化度为所述上限以下时,夹层玻璃的耐湿性提高。
所述乙酰化度是将键合有乙酰基的亚乙基量除以主链的总亚乙基量而求得的摩尔分数以百分数表示的值。所述键合有乙酰基的亚乙基量,例如可以基于JIS K6728“聚乙烯醇缩丁醛试验方法”而测定。
所述聚乙烯醇缩醛树脂的缩醛化度(在聚乙烯醇缩丁醛树脂的情况下为缩丁醛化度)优选为60摩尔%以上,更优选为63摩尔%以上,优选为85摩尔%以下,更优选为75摩尔%以下,进一步优选为70摩尔%以下。所述缩醛化度为所述下限以上时,聚乙烯醇缩醛树脂与增塑剂的相溶性提高。所述缩醛化度为所述上限以下时,用于制造聚乙烯醇缩醛树脂所需要的反应时间变短。
所述缩醛化度通过以下述方式求得。首先,求得从主链的总亚乙基量中减去键合有羟基的亚乙基量、键合有乙酰基的亚乙基量而得到的值。将得到的值除以主链的总亚乙基量而求得摩尔分数。该摩尔分数以百分数表示的值为缩醛化度。
需要说明的是,所述羟基含有率(羟基量)、缩醛化度(缩丁醛化度)和乙酰化度,优选根据通过基于JIS K6728“聚乙烯醇缩丁醛试验方法”的方法而测定得到的结果进行计算。但是,也可以使用基于ASTM D1396-92的测定。在聚乙烯醇缩醛树脂为聚乙烯醇缩丁醛树脂的情况下,所述羟基含有率(羟基量)、所述缩醛化度(缩丁醛化度)和所述乙酰化度,可以根据通过基于JIS K6728“聚乙烯醇缩丁醛试验方法”的方法测定得到的结果进行计算。
增塑剂:
从进一步提高树脂层的粘接力的观点出发,所述第1树脂层优选包含增塑剂。从进一步提高树脂层的粘接力的观点出发,所述第2树脂层优选包含增塑剂。树脂层中包含的热塑性树脂为聚乙烯醇缩醛树脂的情况下,树脂层特别优选包含增塑剂。包含聚乙烯醇缩醛树脂的层优选包含增塑剂。
所述增塑剂没有特别限定。作为所述增塑剂,可使用以往公知的增塑剂。所述增塑剂可以仅使用1种或组合使用2种以上。
作为所述增塑剂,可举出一元有机酸酯和多元有机酸酯等的有机酯增塑剂、以及有机磷酸增塑剂和有机亚磷酸增塑剂等的有机磷酸增塑剂等。优选有机酯增塑剂。所述增塑剂优选为液态增塑剂。
作为所述一元有机酸酯,可举出通过二醇与一元有机酸的反应而得到的二醇酯等。作为所述二醇,可举出三乙二醇、四乙二醇和三丙二醇等。作为所述一元有机酸,可举出丁酸、异丁酸、己酸、2-乙基丁酸、庚酸、正辛酸、2-乙基己酸、正壬酸和癸酸等。
作为所述多元有机酸酯,可举出多元有机酸和碳原子数4~8的具有直链或支链结构的醇形成的酯化合物等。作为所述多元有机酸,可举出己二酸、癸二酸和壬二酸等。
作为所述有机酯增塑剂,可举出三乙二醇二-2-乙基丙酸酯、三乙二醇二-2-乙基丁酸酯、三乙二醇二-2-乙基己酸酯、三乙二醇二辛酸酯、三乙二醇二正辛酸酯、三乙二醇二正庚酸酯、四乙二醇二正庚酸酯、癸二酸二丁酯、壬二酸二辛酯、二丁基卡必醇乙二酸酯、乙二醇二-2-乙基丁酸酯、1,3-丙二醇二-2-乙基丁酸酯、1,4-丁二醇二-2-乙基丁酸酯、二乙二醇二-2-乙基丁酸酯、二乙二醇二-2-乙基己酸酯、二丙二醇二-2-乙基丁酸酯、三乙二醇二-2-乙基戊酸酯、四乙二醇二-2-乙基丁酸酯、二乙二醇二辛酸酯、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、己二酸二异癸酯、己二酸庚基壬酯、癸二酸二丁酯、油改性癸二酸醇酸、和磷酸酯与己二酸酯的混合物等。也可以使用这些以外的有机酯增塑剂。也可以使用上述的己二酸酯以外的其他己二酸酯。
作为所述有机磷酸增塑剂,可举出磷酸三丁氧基乙酯、磷酸异癸基苯酯和磷酸三异丙酯等。
所述增塑剂优选为下述式(1)表示的二酯增塑剂。
[化学式1]
所述式(1)中,R1和R2分别表示碳原子数5~10的有机基团,R3表示亚乙基、亚异丙基或亚正丙基,p表示3~10的整数。所述式(1)中的R1和R2分别优选为碳原子数6~10的有机基团。
所述增塑剂优选包含三乙二醇二-2-乙基己酸酯(3GO)或三乙二醇二-2-乙基丁酸酯(3GH),更优选包含三乙二醇二-2-乙基己酸酯。
所述增塑剂的含量没有特别限定。所述包含增塑剂层(第1树脂层或第2树脂层)中,所述增塑剂相对于所述热塑性树脂100重量份的含量优选为25重量份以上,更优选为30重量份以上,进一步优选为35重量份以上。所述包含增塑剂层(第1树脂层或第2树脂层)中,所述增塑剂相对于所述热塑性树脂100重量份的含量优选为75重量份以下,更优选为60重量份以下,进一步优选为50重量份以下,特别优选为40重量份以下。所述增塑剂的含量为所述下限以上时,夹层玻璃的耐贯穿性进一步提高。所述增塑剂的含量为所述上限以下时,夹层玻璃的透明性进一步提高。
着色剂:
所述第1树脂层包含着色剂。所述第2树脂层也可以包含着色剂。所述第2树脂层中的着色剂的含量可以低于所述第1树脂层中的着色剂的含量。需要说明的是,在所述第1树脂层具有包含着色剂的阴影区域的情况下,所述第1树脂层中,除阴影区域之外的区域中,优选包含着色剂。所述着色剂可以仅使用1种或组合使用2种以上。
作为所述着色剂,可举出颜料和染料等。
颜料和染料可以通过下述方式进行区分。
准备聚乙烯醇缩丁醛树脂(使用正丁醛,聚乙烯醇的聚合度1700,羟基含有率30摩尔%,乙酰化度1摩尔%,缩丁醛化度69摩尔%)。将该聚乙烯醇缩丁醛树脂100重量份、三乙二醇二-2-乙基己酸酯(3GO)40重量份、相对于聚乙烯醇缩丁醛树脂、3GO以及着色剂的总量100重量%为0.015重量份的量的着色剂进行混炼,得到混炼物。挤出该混炼物,得到厚度760μm的树脂膜。将该树脂膜配置在基于JIS R3106:1998而测定得到的可见光线透射率为90%的2片透明玻璃(厚度2.5mm)之间,制备夹层玻璃。将使得到的夹层玻璃的雾度值为0.35%以上的着色剂定义为颜料。将雾度值低于0.35%的着色剂定义为染料。
所述颜料可以为有机颜料或无机颜料。所述有机颜料可以为具有金属原子的有机颜料或不具有金属原子的有机颜料。所述颜料可以仅使用1种或组合使用2种以上。
作为所述有机颜料,可举出酞菁化合物、喹吖啶酮化合物、偶氮化合物、二苯并菲化合物、二噁嗪化合物、苝化合物、吲哚化合物和二噁嗪化合物等。
作为所述无机颜料,可举出炭黑和氧化铁、氧化锌、氧化钛等。
所述着色剂优选为酞菁化合物、萘酞菁化合物、蒽酞菁化合物、喹吖啶酮化合物、偶氮化合物、二苯并菲化合物、二噁嗪化合物、苝化合物、吲哚化合物或炭黑。
从有效提高创意性和设计性,并且有效抑制光和热导致的变色的观点出发,所述着色剂优选为苝化合物、酞菁化合物、萘酞菁化合物和蒽酞菁化合物中的至少1种成分X-1。从进一步有效提高创意性和设计性,并且进一步有效抑制光和热导致的变色的观点出发,所述着色剂更优选为酞菁化合物、萘酞菁化合物和蒽酞菁化合物中的至少1种成分X。
所述成分X没有特别限定。作为成分X,可使用以往公知的酞菁化合物、萘酞菁化合物和蒽酞菁化合物。
作为所述成分X,可举出酞菁、酞菁衍生物、萘酞菁、萘酞菁衍生物、蒽酞菁和蒽酞菁衍生物等。所述酞菁化合物和所述酞菁衍生物分别优选具有酞菁骨架。所述萘酞菁化合物和所述萘酞菁衍生物分别优选具有萘酞菁骨架。所述蒽酞菁化合物和所述蒽酞菁衍生物分别优选具有蒽酞菁骨架。
从进一步提高隔热性的观点出发,所述成分X优选为酞菁、酞菁衍生物、萘酞菁或萘酞菁衍生物,更优选为酞菁或酞菁衍生物。
从有效提高隔热性并且进一步在长时间内将可见光线透射率保持为高水平的观点出发,所述成分X优选含有钒原子或铜原子。所述成分X优选含有钒原子,也优选含有铜原子。所述成分X更优选为含有钒原子或铜原子的酞菁和含有钒原子或铜原子的酞菁衍生物中的至少1种。从进一步抑制夹层玻璃的重影并进一步提高隔热性的观点出发,所述成分X优选具有在钒原子上键合氧原子而得到的结构单元。
从进一步提高创意性和设计性的观点出发,着色剂的含量、成分X-1和成分X的含量优选满足以下的优选范围。
包含所述着色剂的层(第1树脂层或第2树脂层)100重量%中,所述着色剂的含量优选为0.001重量%以上,更优选为0.002重量%以上,进一步优选为0.003重量%以上,特别优选为0.004重量%以上,最优选为0.005重量%以上。包含所述着色剂的层(第1树脂层或第2树脂层)100重量%中,所述着色剂的含量优选为10重量%以下,更优选为9重量%以下,进一步优选为8重量%以下,特别优选为7重量%以下。所述着色剂的含量为所述下限以上时,创意性和设计性进一步提高。所述着色剂的含量为所述上限以下时,透过夹层玻璃的视觉辨认性进一步提高。
包含所述着色剂的层(第1树脂层或第2树脂层)的除阴影区域之外的区域100重量%中,所述着色剂的含量优选为0.001重量%以上,更优选为0.002重量%以上,进一步优选为0.003重量%以上,特别优选为0.004重量%以上,最优选为0.005重量%以上。包含所述着色剂的层(第1树脂层或第2树脂层)的除阴影区域之外的区域100重量%中,所述着色剂的含量优选为10重量%以下,更优选为9重量%以下,进一步优选为8重量%以下,特别优选为7重量%以下。所述着色剂的含量为所述下限以上时,创意性和设计性进一步提高。所述着色剂的含量为所述上限以下时,透过夹层玻璃的视觉辨认性进一步提高。
包含所述成分X-1和所述成分X的层(第1树脂层或第2树脂层)100重量%中,所述成分X-1和所述成分X的含量分别优选为0.001重量%以上,更优选为0.002重量%以上,进一步优选为0.003重量%以上,特别优选为0.004重量%以上,最优选为0.005重量%以上。包含所述成分X-1和所述成分X的层(第1树脂层或第2树脂层)100重量%中,所述成分X-1和所述成分X的含量优选为10重量%以下,更优选为9重量%以下,进一步优选为8重量%以下,特别优选为7重量%以下。所述成分X-1和所述成分X的含量为所述下限以上时,创意性和设计性进一步提高。所述着色剂的含量为所述上限以下时,透过夹层玻璃的视觉辨认性进一步提高。
包含所述成分X-1和所述成分X的层(第1树脂层或第2树脂层)的除阴影区域之外的区域100重量%中,所述成分X-1和所述成分X的含量优选为0.001重量%以上,更优选为0.002重量%以上,进一步优选为0.003重量%以上。包含所述成分X-1和所述成分X的层(第1树脂层或第2树脂层)的除阴影区域之外的区域100重量%中,所述成分X-1和所述成分X的含量特别优选为0.004重量%以上,最优选为0.005重量%以上。包含所述成分X-1和所述成分X的层(第1树脂层或第2树脂层)的除阴影区域之外的区域100重量%中,所述成分X-1和所述成分X的含量优选为10重量%以下,更优选为9重量%以下,进一步优选为8重量%以下,特别优选为7重量%以下。所述成分X-1和所述成分X的含量为所述下限以上时,创意性和设计性进一步提高。所述着色剂的含量为所述上限以下时,透过夹层玻璃的视觉辨认性进一步提高。
隔热性物质:
所述第1树脂层优选包含隔热性物质。所述第2树脂层中的隔热性物质的含量可以低于所述第1树脂层中的隔热性物质的含量。所述第2树脂层优选包含隔热性物质。所述第2树脂层可以不包含隔热性物质。所述隔热性物质可以仅使用1种或组合使用2种以上。
所述隔热性物质优选包含酞菁化合物、萘酞菁化合物和蒽酞菁化合物中的至少1种成分X,或包含隔热粒子。在这种情况下,也可以包含所述成分X和所述隔热粒子这两者。
所述第1树脂层优选包含酞菁化合物、萘酞菁化合物和蒽酞菁化合物中的至少1种成分X。所述第2树脂层中的所述成分X的含量可以低于所述第1树脂层中的所述成分X的含量。所述第2树脂层优选包含所述成分X。所述第2树脂层可以不包含所述成分X。所述成分X可以仅使用1种或组合使用2种以上。
所述成分X也相当于隔热性物质。从有效提高隔热性的观点出发,所述第1树脂层优选包含所述成分X。所述第2树脂层中的所述成分X的含量可以低于所述第1树脂层中的所述成分X的含量。从有效提高隔热性的观点出发,所述第2树脂层优选包含所述成分X。所述第2树脂层也可以不包含所述成分X。所述成分X可以仅使用1种或组合使用2种以上。
从有效提高隔热性的观点出发,所述成分X的含量优选满足以下的优选范围。
在包含所述成分X的层(第1树脂层或第2树脂层)100重量%中,所述成分X的含量优选为0.001重量%以上,更优选为0.005重量%以上,进一步优选为0.01重量%以上,特别优选为0.02重量%以上。在包含所述成分X的层(第1树脂层或第2树脂层)100重量%中,所述成分X的含量优选为0.2重量%以下,更优选为0.1重量%以下,进一步优选为0.05重量%以下,特别优选为0.04重量%以下。所述成分X的含量为所述下限以上和所述上限以下时,充分提高隔热性,并且充分提高可见光线透射率。例如,可将可见光线透射率设为70%以上。
所述第1树脂层优选包含隔热粒子。所述第2树脂层中的隔热粒子的含量可以低于所述第1树脂层中的隔热粒子的含量。所述第2树脂层优选包含所述隔热粒子。所述第2树脂层也可以不包含隔热粒子。所述隔热粒子为隔热性物质。通过使用隔热粒子,能够有效隔断红外线(热线)。所述隔热粒子可以仅使用1种或组合使用2种以上。
从进一步提高夹层玻璃的隔热性的观点出发,所述隔热粒子更优选为金属氧化物粒子。所述隔热粒子优选为由金属的氧化物形成的粒子(金属氧化物粒子)。
波长大于可见光的780nm以上的红外线,与紫外线相比,能量较小。然而,红外线的热作用较大,红外线被物质吸收时作为热而被放出。因此,红外线通常被称为热线。通过使用所述隔热粒子,能够有效隔断红外线(热线)。需要说明的是,隔热粒子是指,可吸收红外线的粒子。
作为所述隔热粒子的具体例,可举出铝掺杂氧化锡粒子、铟掺杂氧化锡粒子、锑掺杂氧化锡粒子(ATO粒子)、镓掺杂氧化锌粒子(GZO粒子)、铟掺杂氧化锌粒子(IZO粒子)、铝掺杂氧化锌粒子(AZO粒子)、铌掺杂氧化钛粒子、钠掺杂氧化钨粒子、铯掺杂氧化钨粒子、铊掺杂氧化钨粒子、铷掺杂氧化钨粒子、锡掺杂氧化铟粒子(ITO粒子)、锡掺杂氧化锌粒子、硅掺杂氧化锌粒子等的金属氧化物粒子、六硼化镧(LaB6)粒子等。也可以使用这些以外的隔热粒子。由于热线的屏蔽功能较高,因此优选金属氧化物粒子,更优选ATO粒子、GZO粒子、IZO粒子、ITO粒子或氧化钨粒子,特别优选ITO粒子或氧化钨粒子。特别是,由于热线的屏蔽功能较高并且容易购入,因此优选锡掺杂氧化铟粒子(ITO粒子),也优选氧化钨粒子。
从进一步提高夹层玻璃的隔热性的观点出发,氧化钨粒子优选为金属掺杂氧化钨粒子。所述“氧化钨粒子”中包括金属掺杂氧化钨粒子。作为所述金属掺杂氧化钨粒子,具体而言,可举出钠掺杂氧化钨粒子、铯掺杂氧化钨粒子、铊掺杂氧化钨粒子和铷掺杂氧化钨粒子等。
从进一步提高夹层玻璃的隔热性的观点出发,特别优选铯掺杂氧化钨粒子。从进一步提高夹层玻璃的隔热性的观点出发,该铯掺杂氧化钨粒子优选为式:Cs0.33WO3表示的氧化钨粒子。
所述隔热粒子的平均粒径优选为0.01μm以上,更优选为0.02μm以上,优选为0.1μm以下,更优选为0.05μm以下。平均粒径为所述下限以上时,充分提高热线的屏蔽性。平均粒径为所述上限以下时,提高隔热粒子的分散性。
所述“平均粒径”表示体积平均粒径。平均粒径,可使用粒度分布测定装置(日机装公司制“UPA-EX150”)等而测定。
在包含所述隔热粒子的层(第1树脂层或第2树脂层)100重量%中,所述隔热粒子的含量优选为0.01重量%以上,更优选为0.1重量%以上,进一步优选为1重量%以上,特别优选为1.5重量%以上。在包含所述隔热粒子的层(第1树脂层或第2树脂层)100重量%中,所述隔热粒子的含量优选为6重量%以下,更优选为5.5重量%以下,进一步优选为4重量%以下,特别优选为3.5重量%以下,最优选为3重量%以下。所述隔热粒子的含量为所述下限以上和所述上限以下时,充分提高隔热性,并且充分提高可见光线透射率。
金属盐:
所述第1树脂层优选包含作为碱金属盐、碱土金属盐或镁盐的金属盐(以下,有时记载为金属盐M)。所述第2树脂层优选包含所述金属盐M。通过使用所述金属盐M,使得树脂层与红外线反射层和夹层玻璃部件的粘接性变得容易控制。所述金属盐M可以仅使用1种或组合使用2种以上。
所述金属盐M优选包含作为Li、Na、K、Rb、Cs、Mg、Ca、Sr或Ba的金属。树脂层中包含的金属盐优选包含K或Mg。
此外,所述金属盐M更优选为碳原子数2~16的有机酸的碱金属盐、碳原子数2~16的有机酸的碱土金属盐或碳原子数2~16的有机酸的镁盐,进一步优选为碳原子数2~16的羧酸镁盐或碳原子数2~16的羧酸钾盐。
作为所述碳原子数2~16的羧酸镁盐和所述碳原子数2~16的羧酸钾盐,可举出乙酸镁、乙酸钾、丙酸镁、丙酸钾、2-乙基丁酸镁、2-乙基丁酸钾、2-乙基己酸镁和2-乙基己酸钾等。
包含所述金属盐M的层(第1树脂层或第2树脂层)中Mg和K的含量的合计优选为5ppm以上,更优选为10ppm以上,进一步优选为20ppm以上,优选为300ppm以下,更优选为250ppm以下,进一步优选为200ppm以下。Mg和K的含量的合计为所述下限以上和所述上限以下时,能够进一步良好地控制树脂层与红外线反射层和夹层玻璃部件的粘接性。
紫外线屏蔽剂:
所述第1树脂层优选包含紫外线屏蔽剂。所述第2树脂层优选包含紫外线屏蔽剂。通过使用紫外线屏蔽剂,即使在长时间使用夹层玻璃的情况下,也进一步使得可见光线透射率不易降低。所述紫外线屏蔽剂可以仅使用1种或组合使用2种以上。
所述紫外线屏蔽剂中包括紫外线吸收剂。所述紫外线屏蔽剂优选为紫外线吸收剂。
作为所述紫外线屏蔽剂,例如可举出包含金属原子的紫外线屏蔽剂、包含金属氧化物的紫外线屏蔽剂、具有苯并***结构的紫外线屏蔽剂(苯并***化合物)、具有二苯甲酮结构的紫外线屏蔽剂(二苯甲酮化合物)、具有三嗪结构的紫外线屏蔽剂(三嗪化合物)、具有丙二酸酯结构的紫外线屏蔽剂(丙二酸酯化合物)、具有草酰苯胺结构的紫外线屏蔽剂(草酰苯胺化合物)和具有苯甲酸酯结构的紫外线屏蔽剂(苯甲酸酯化合物)等。
作为所述包含金属原子的紫外线屏蔽剂,例如可举出铂粒子、铂粒子的表面由二氧化硅包覆而成的粒子、钯粒子和钯粒子的表面由二氧化硅包覆而成的粒子等。紫外线屏蔽剂优选不是隔热粒子。
所述紫外线屏蔽剂优选为具有苯并***结构的紫外线屏蔽剂、具有二苯甲酮结构的紫外线屏蔽剂、具有三嗪结构的紫外线屏蔽剂或具有苯甲酸酯结构的紫外线屏蔽剂。所述紫外线屏蔽剂更优选为具有苯并***结构的紫外线屏蔽剂或具有二苯甲酮结构的紫外线屏蔽剂,进一步优选为具有苯并***结构的紫外线屏蔽剂。
作为所述包含金属氧化物的紫外线屏蔽剂,例如可举出氧化锌、氧化钛和氧化铈等。此外,就所述包含金属氧化物的紫外线屏蔽剂而言,表面可以被包覆。作为所述包含金属氧化物的紫外线屏蔽剂表面的包覆材料,可举出绝缘性金属氧化物、水解性有机硅化合物和聚硅氧烷化合物等。
作为所述绝缘性金属氧化物,可举出二氧化硅、氧化铝和氧化锆等。所述绝缘性金属氧化物例如具有5.0eV以上的带隙能量。
作为所述具有苯并***结构的紫外线屏蔽剂,例如可举出2-(2’-羟基-5’-甲基苯基)苯并***(BASF公司制“TinuvinP”)、2-(2’-羟基-3’,5’-二叔丁基苯基)苯并***(BASF公司制“Tinuvin320”)、2-(2’-羟基-3’-叔丁基-5-甲基苯基)-5-氯苯并***(BASF公司制“Tinuvin326”)和2-(2’-羟基-3’,5’-二戊基苯基)苯并***(BASF公司制“Tinuvin328”)等。从屏蔽紫外线的性能优异的方面出发,所述紫外线屏蔽剂优选为包含卤素原子的具有苯并***结构的紫外线屏蔽剂,更优选为包含氯原子的具有苯并***结构的紫外线屏蔽剂。
作为所述具有二苯甲酮结构的紫外线屏蔽剂,例如可举出OCTABENZONE(BASF公司制“Chimassorb81”)等。
作为所述具有三嗪结构的紫外线屏蔽剂,例如可举出ADEKA公司制“LA-F70”和2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]-酚(BASF公司制“Tinuvin1577FF”)等。
作为所述具有丙二酸酯结构的紫外线屏蔽剂,可举出2-(对甲氧基亚苄基)丙二酸二甲酯、四乙基-2,2-(1,4-亚苯基二亚甲基)双丙二酸酯、2-(对甲氧基亚苄基)-双(1,2,2,6,6-五甲基4-哌啶基)丙二酸酯等。
作为所述具有丙二酸酯结构的紫外线屏蔽剂的市售品,可举出HostavinB-CAP、Hostavin PR-25、Hostavin PR-31(均为CLARIANT公司制)。
作为所述具有草酰苯胺结构的紫外线屏蔽剂,可举出N-(2-乙基苯基)-N’-(2-乙氧基-5-叔丁基苯基)草酸二酰胺、N-(2-乙基苯基)-N’-(2-乙氧基苯基)草酸二酰胺、2-乙基-2’-乙氧基-草酰苯胺(CLARIANT公司制“SanduvorVSU”)等具有取代在氮原子上的芳基等的草酸二酰胺类。
作为所述具有苯甲酸酯结构的紫外线屏蔽剂,例如可举出2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯(BASF公司制“Tinuvin120”)等。
在包含所述紫外线屏蔽剂的层(第1树脂层或第2树脂层)100重量%中,所述紫外线屏蔽剂的含量优选为0.1重量%以上,更优选为0.2重量%以上,进一步优选为0.3重量%以上,特别优选为0.5重量%以上。在包含所述紫外线屏蔽剂的层(第1树脂层或第2树脂层)100重量%中,所述紫外线屏蔽剂的含量优选为2.5重量%以下,更优选为2重量%以下,进一步优选为1重量%以下,特别优选为0.8重量%以下。所述紫外线屏蔽剂的含量为所述下限以上和所述上限以下时,经过长时间后可见光线透射率的降低进一步得到抑制。特别是,在包含所述紫外线屏蔽剂的层100重量%中,通过使所述紫外线屏蔽剂的含量为0.2重量%以上,能够显著抑制夹层玻璃经过长时间后可见光线透射率的降低。
抗氧化剂:
所述第1树脂层优选包含抗氧化剂。所述第2树脂层优选包含抗氧化剂。所述抗氧化剂可以仅使用1种或组合使用2种以上。
作为所述抗氧化剂,可举出酚类抗氧化剂、硫类抗氧化剂和磷类抗氧化剂等。所述酚类抗氧化剂为具有酚骨架的抗氧化剂。所述硫类抗氧化剂为含有硫原子的抗氧化剂。所述磷类抗氧化剂为含有磷原子的抗氧化剂。
所述抗氧化剂优选为酚类抗氧化剂或磷类抗氧化剂。
作为所述酚类抗氧化剂,可举出2,6-二叔丁基对甲酚(BHT)、丁羟基苯甲醚(BHA)、2,6-二叔丁基-4-乙基酚、硬脂基-β-(3,5-二叔丁基-4-羟基苯基)丙酸酯、2,2’-亚甲基双-(4-甲基-6-丁基酚)、2,2’-亚甲基双-(4-乙基-6-叔丁基酚)、4,4’-亚丁基-双-(3-甲基-6-叔丁基酚)、1,1,3-三-(2-甲基-羟基-5-叔丁基苯基)丁烷、四[亚甲基-3-(3’,5’-丁基-4-羟基苯基)丙酸酯]甲烷、1,3,3-三-(2-甲基-4-羟基-5-叔丁基酚)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、双(3,3’-叔丁基酚)乙二醇丁酸酯和双(3-叔丁基-4-羟基-5-甲基苯丙酸)乙烯双(氧乙烯)等。优选使用这些抗氧化剂中的1种或2种以上。
作为所述磷类抗氧化剂,可举出十三烷基亚磷酸酯、三(十三烷基)亚磷酸酯、三苯基亚磷酸酯、三壬基苯基亚磷酸酯、双(十三烷基)季戊四醇二亚磷酸酯、双(癸基)季戊四醇二亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯和2,2’-亚甲基双(4,6-二叔丁基-1-苯氧基)(2-乙基己氧基)磷等。优选使用这些抗氧化剂中的1种或2种以上。
作为所述抗氧化剂的市售品,例如可举出BASF公司制“IRGANOX 245”、BASF公司制“IRGAFOS 168”、BASF公司制“IRGAFOS 38”、住友化学工业公司制“SUMILIZERBHT”、堺化学工业公司制“H-BHT”以及BASF公司制“IRGANOX 1010”等。
为了在长时间内保持夹层玻璃的高可见光线透射率,在包含所述抗氧化剂的层(第1树脂层或第2树脂层)100重量%中,所述抗氧化剂的含量优选为0.1重量%以上。此外,在包含所述抗氧化剂的层100重量%中,所述抗氧化剂的含量优选为2重量%以下。
其他成分:
所述第1树脂层和所述第2树脂层分别根据需要可以包含偶联剂、分散剂、表面活性剂、阻燃剂、抗静电剂、颜料、染料、金属盐以外的粘接力调整剂、耐湿剂、荧光增白剂和红外线吸收剂等的添加剂。这些添加剂可以仅使用1种或组合使用2种以上。
(夹层玻璃用中间膜的其他详细内容)
所述中间膜的厚度没有特别限定。从实用面的观点以及充分提高夹层玻璃的耐贯穿性和弯曲刚性的观点出发,中间膜的厚度优选为0.1mm以上,更优选为0.25mm以上,优选为3mm以下,更优选为1.5mm以下。中间膜的厚度为所述下限以上时,夹层玻璃的耐贯穿性和弯曲刚性进一步提高。中间膜的厚度为所述上限以下时,中间膜的透明性进一步得到改善。
所述中间膜可以为厚度均匀的中间膜或厚度变化的中间膜。所述中间膜的截面形状可以为矩形或楔形。
所述中间膜优选在外表面具有凹凸形状。在这种情况下,所述中间膜在两侧的外表面中的至少一个表面具有凹凸形状即可。所述中间膜优选在两侧的外表面中的至少一个表面具有凹凸形状。所述中间膜更优选在两侧的外表面具有凹凸形状。所述中间膜的外表面优选进行了雕纹加工。在这种情况下,两侧的外表面中的至少一个表面进行了雕纹加工即可。优选所述中间膜的两侧的外表面中的至少一个表面进行了雕纹加工。更优选所述中间膜的两侧的外表面进行了雕纹加工。作为形成所述的凹凸形状的方法,没有特别限定,例如可举出唇压纹法、压纹辊法、压延辊法和型材挤出法等。从能够定量性地形成作为给定凹凸模样的多个凹凸形状的雕纹的方面出发,优选压纹辊法。
(夹层玻璃)
图3是示意性地表示使用了图1表示的夹层玻璃用中间膜的夹层玻璃的一个实例的截面图。
图3表示的夹层玻璃31具备第1夹层玻璃部件21、第2夹层玻璃部件22、中间膜11。中间膜11配置并夹入第1夹层玻璃部件21和第2夹层玻璃部件22之间。
第1夹层玻璃部件21叠层在中间膜11的第1表面11a。第2夹层玻璃部件22叠层在中间膜11的与第1表面11a相反的第2表面11b。第1夹层玻璃部件21配置并叠层在第1树脂层2外侧的表面2a。第2夹层玻璃部件22配置并叠层在第2树脂层3外侧的表面3a。
图4是示意性地表示使用了图2表示的夹层玻璃用中间膜的夹层玻璃的一个实例的截面图。
图4表示的夹层玻璃31A具备第1夹层玻璃部件21、第2夹层玻璃部件22、中间膜11A。中间膜11A配置并夹入第1夹层玻璃部件21和第2夹层玻璃部件22之间。
第1夹层玻璃部件21叠层在中间膜11A的第1表面11a。第2夹层玻璃部件22叠层在中间膜11A的与第1表面11a相反的第2表面11b。第1夹层玻璃部件21配置并叠层在第1树脂层2外侧的表面2a。第2夹层玻璃部件22配置并叠层在红外线反射层1的第2表面1b(外侧的表面)。
这样,本发明的夹层玻璃具备第1夹层玻璃部件、第2夹层玻璃部件以及中间膜,该中间膜为本发明的夹层玻璃用中间膜。本发明的夹层玻璃中,在所述第1夹层玻璃部件和所述第2夹层玻璃部件之间配置有所述中间膜。在所述中间膜具有所述第2树脂层的情况下,所述第1夹层玻璃部件配置在所述第1树脂层外侧,所述第2夹层玻璃部件配置在所述第2树脂层外侧。在所述中间膜不具有所述第2树脂层的情况下,所述第1夹层玻璃部件配置在所述第1树脂层外侧,所述第2夹层玻璃部件配置在所述红外线反射层外侧。
所述夹层玻璃优选在车辆中安装于外部空间和热线从所述外部空间入射的内部空间之间的开口部处,以使得所述第1夹层玻璃部件位于所述外部空间侧并且使得所述第2夹层玻璃部件位于所述内部空间侧。
所述第1夹层玻璃部件优选为第1玻璃板。所述第2夹层玻璃部件优选为第2玻璃板。
作为所述夹层玻璃部件,可举出玻璃板和PET(聚对苯二甲酸乙二醇酯)膜等。夹层玻璃中,不仅包括在2片玻璃板之间夹入中间膜而得到的夹层玻璃,还包括在玻璃板和PET膜等之间夹入中间膜而得到的夹层玻璃。所述夹层玻璃优选为具备玻璃板的叠层体,并且使用了至少1片玻璃板。所述第1夹层玻璃部件和所述第2夹层玻璃部件分别为玻璃板或PET膜,并且所述夹层玻璃优选包含玻璃板作为所述第1夹层玻璃部件和所述第2夹层玻璃部件中的至少一者。
作为所述玻璃板,可举出无机玻璃和有机玻璃。作为所述无机玻璃,可举出浮法板玻璃、热线吸收板玻璃、热线反射板玻璃、抛光板玻璃、模板玻璃和夹丝玻璃等。所述有机玻璃为代替无机玻璃的合成树脂玻璃。作为所述有机玻璃,可举出聚碳酸酯板和聚(甲基)丙烯酸类树脂板等。作为所述聚(甲基)丙烯酸类树脂板,可举出聚(甲基)丙烯酸甲酯板等。
所述夹层玻璃部件的厚度优选为1mm以上,更优选为1.8mm以上,进一步优选为2mm以上,特别优选为2.1mm以上,优选为5mm以下,更优选为3mm以下。此外,在所述夹层玻璃部件为玻璃板的情况下,该玻璃板的厚度优选为1mm以上,更优选为1.8mm以上,进一步优选为2mm以上,特别优选为2.1mm以上,优选为5mm以下,更优选为3mm以下,进一步优选为2.6mm以下。在所述夹层玻璃部件为PET膜的情况下,该PET膜的厚度优选为0.03mm以上,优选为0.5mm以下。
所述第1夹层玻璃部件和所述第2夹层玻璃部件分别优选为透明玻璃或热线吸收板玻璃。从红外线透射率较高,夹层玻璃的隔热性进一步提高的方面出发,所述第2夹层玻璃部件优选为透明玻璃。从红外线透射率较低,夹层玻璃的隔热性进一步提高的方面出发,所述第1夹层玻璃部件优选为热线吸收板玻璃。热线吸收板玻璃优选为绿玻璃。优选所述第2夹层玻璃部件为透明玻璃,并且所述第1夹层玻璃部件为热线吸收板玻璃。所述热线吸收板玻璃为基于JIS R3208的热线吸收板玻璃。
所述夹层玻璃的制造方法没有特别限定。首先,在所述第1夹层玻璃部件和所述第2夹层玻璃部件之间夹入中间膜,得到叠层体。接下来,例如将得到的叠层体通过按压辊或装入橡胶袋进行减压抽吸,而对所述第1夹层玻璃部件、所述第2夹层玻璃部件和中间膜之间残留的空气进行脱气。然后,在约70~110℃下进行预粘接而得到进行了预压合的叠层体。接下来,将进行了预压合的叠层体投入高压釜或进行压制,在约120~150℃和1~1.5MPa的压力下进行压合。由此,可以得到夹层玻璃。所述夹层玻璃的制造中,也可以将各层进行叠层。
所述中间膜和所述夹层玻璃可用于车辆、铁道车辆、航天器、船舶和建筑物等。所述中间膜和所述夹层玻璃也可用于这些用途以外。所述中间膜和所述夹层玻璃优选为用于车辆或建筑物的中间膜和夹层玻璃,更优选为用于车辆的中间膜和夹层玻璃。所述中间膜和所述夹层玻璃可用于车辆的挡风玻璃、侧玻璃、后玻璃或顶玻璃等。所述中间膜和所述夹层玻璃优选用于车辆。所述中间膜用于得到车辆的夹层玻璃。所述夹层玻璃优选用于车的挡风玻璃。所述夹层玻璃优选为可用于车的挡风玻璃的夹层玻璃。
以下举出实施例和比较例来对于本发明进一步详细地进行说明。本发明不限于这些实施例。
(热塑性树脂)
聚乙烯醇缩醛树脂(PVB,平均聚合度1700,羟基含有率30.5摩尔%,乙酰化度1摩尔%,缩醛化度68.5摩尔%)
在所使用的聚乙烯醇缩醛树脂中,缩醛化中使用了碳原子数4的正丁醛。就聚乙烯醇缩醛树脂而言,缩醛化度(缩丁醛化度)、乙酰化度和羟基含有率通过基于JIS K6728“聚乙烯醇缩丁醛试验方法”的方法而测定。需要说明的是,在通过ASTM D1396-92进行测定的情况,也显示出与基于JIS K6728“聚乙烯醇缩丁醛试验方法”的方法同样的数值。
(增塑剂)
三乙二醇二-2-乙基己酸酯(3GO)
(着色剂)
蒽醌化合物(成分X-1,住化CHEMTEX公司制“SUMIPLAST VIOLETRR”)
酞菁化合物(成分X-1,山田科学公司制“NIR-43V”)
苝化合物(成分X-1,CLARIANT公司制“PV FAST RED B”)
(紫外线屏蔽剂)
Tinuvin326(2-(2’-羟基-3’-叔丁基-5-甲基苯基)-5-氯苯并***,BASF公司制“Tinuvin326”)0.2重量份
(抗氧化剂)
BHT(2,6-二-叔丁基对甲酚)
准备以下的红外线反射层。
(红外线反射层)
红外线反射膜1~6(在膜上形成银溅射层而得到的膜,本公司制品)
基于以下的顺序制备红外线反射膜1。作为基材,使用了聚对苯二甲酸乙二醇酯(PET)膜(厚度50μm)。在所述基材上以铌为靶进行溅射。在溅射功率为中波(MF)1500W,作为氛围气体的氩气的气体流量为225sccm和氧气的气体流量为65sccm,溅射时压力为0.177Pa的条件下进行溅射,形成由氧化铌(Nb2O3)形成的厚度30nm的金属氧化物层。
接着,在所述金属氧化物层上以铌为靶进行溅射。在溅射功率为中波(MF)1500W,作为氛围气体的氩气的气体流量为225sccm和氧气的气体流量为30sccm,溅射时压力为0.170Pa的条件下进行溅射,形成由缺氧的氧化铌(Nb2Ox,x低于3)形成的厚度4nm的缺氧金属氧化物层。
接着,在所述缺氧金属氧化物层上以银为靶进行溅射。在溅射功率为直流(DC)1150W,氛围气体的氩气的气体流量为225sccm,溅射时压力为0.28Pa的条件下进行溅射,形成由银形成的厚度16nm的银层。
除了变更溅射的各层的厚度以外,将溅射金属氧化物层、缺氧金属氧化物层和银层时的条件分别设为与上述的条件相同。形成在基材上依次叠层有金属氧化物层(30nm)/缺氧金属氧化物层(4nm)/银层(16nm)/缺氧金属氧化物层(4nm)/金属氧化物层(80nm)/缺氧金属氧化物层(4nm)/银层(16nm)/缺氧金属氧化物层(4nm)/金属氧化物层(30nm)的导电层。由此,得到红外线反射膜1。
红外线反射膜2~6的情况下,从红外线反射膜1的制造方法出发,对溅射时金属氧化物层、缺氧金属氧化物层和银层的厚度进行变更,以设为下述的表1、2表示的第1、第2极大反射波长和下述的表1、2表示的第1、第2极大反射波长下的反射率的方式进行调整,得到红外线反射膜2~6。
Nano90S(3M,多层树脂膜,住友3M公司制“MULTILAYER Nano 90S”)
准备以下的夹层玻璃部件。
(夹层玻璃部件)
绿玻璃(热线吸收板玻璃,厚度2mm)
透明玻璃(厚度2.5mm)
(实施例1)
第1树脂层的制备:
混合以下的成分,通过混合辊充分进行混炼,得到用于形成第1树脂层的组合物。
聚乙烯醇缩醛树脂(PVB,平均聚合度1700,羟基含有率30.5摩尔%,乙酰化度1摩尔%,缩醛化度68.5摩尔%)100重量份
三乙二醇二-2-乙基己酸酯(3GO)40重量份
在得到的树脂层中成为0.77重量%的量的蒽醌化合物(成分X-1,住化CHEMTEX公司制“SUMIPLAST VIOLET RR”)
在得到的树脂层中成为0.2重量%的量的Tinuvin326(2-(2’-羟基-3’-叔丁基-5-甲基苯基)-5-氯苯并***,BASF公司制“Tinuvin326”)
在得到的树脂层中成为0.2重量%的量的BHT(2,6-二叔丁基对甲酚)
将得到的用于形成第1树脂层的组合物使用挤出机而挤出,得到第1树脂层。第1树脂层为矩形的,第1树脂层的厚度为380μm。
第2树脂层的制备:
混合以下的成分,通过混合辊充分进行混炼,得到用于形成第2树脂层的组合物。
聚乙烯醇缩醛树脂(PVB,平均聚合度1700,羟基含有率30.5摩尔%,乙酰化度1摩尔%,缩醛化度68.5摩尔%)100重量份
三乙二醇二-2-乙基己酸酯(3GO)40重量份
在得到的树脂层中成为0.2重量%的量的Tinuvin326(2-(2’-羟基-3’-叔丁基-5-甲基苯基)-5-氯苯并***,BASF公司制“Tinuvin326”)
在得到的树脂层中成为0.2重量%的量的BHT(2,6-二叔丁基对甲酚)
将得到的用于形成第2树脂层的组合物使用挤出机而挤出,得到第2树脂层。第2树脂层为矩形的,第2树脂层的厚度为380μm。
红外线反射层、第1、第2夹层玻璃部件的准备:
作为红外线反射层,准备红外线反射膜1。
作为第1夹层玻璃部件,准备绿玻璃(热线吸收板玻璃,厚度2mm)。
作为第2夹层玻璃部件,准备透明玻璃(厚度2.5mm)
夹层玻璃的制备:
将第1夹层玻璃部件、第1树脂层、红外线反射层、第2树脂层、第2夹层玻璃部件依次进行叠层,得到夹层玻璃。第1夹层玻璃部件、第1树脂层形成的第1叠层体的楔角与第1树脂层的楔角相同。
(实施例2~6和比较例1~6)
除了将中间膜的构成如下述的表1、2表示的进行变更以外,以与实施例1同样的方式,得到夹层玻璃。
比较例1~3中,未使用红外线反射层。需要说明的是,实施例2~6和比较例1~6中,在第1、第2树脂层中,将与实施例1同样的紫外线屏蔽剂和抗氧化剂在树脂层中以与实施例1同样的混合量进行混合。着色剂在得到的树脂层100重量%中以与下述的表1、2表示的混合量进行混合。
(评价)
(1)耐光性试验
将得到的夹层玻璃在氙弧灯耐候试验机NX25(SUGA TEST INSTRUME NTS公司制)中保持3000小时后,以下述的基准进行判定。优选色差ΔE较低的。
[耐光性试验的判定基准]
○:耐光试验前后的色差ΔE低于4
×:耐光试验前后的色差ΔE为4以上
(2)耐热性试验
将得到的夹层玻璃在100℃的恒温槽中保持12周,以下述的基准进行判定。优选色差ΔE较低的。
[耐热性试验的判定基准]
○:耐热试验前后的色差ΔE低于1
×:耐热试验前后的色差ΔE为1以上
详细内容和结果如下述的表1、2表示。需要说明的是,表中省略了紫外线屏蔽剂和抗氧化剂的记载。
符号说明
1…红外线反射层
1a…第1表面
1b…第2表面
2…第1树脂层
2a…外侧的表面
3…第2树脂层
3a…外侧的表面
11,11A…中间膜
11a…第1表面
11b…第2表面
21…第1夹层玻璃部件
22…第2夹层玻璃部件
31,31A…夹层玻璃
Claims (11)
1.一种夹层玻璃用中间膜,其具有红外线反射层和包含热塑性树脂的第1树脂层,其中,
所述第1树脂层配置在所述红外线反射层的第1表面侧,
所述红外线反射层在波长350nm~450nm具有第1极大反射波长,在波长800nm以上具有第2极大反射波长,所述第1极大反射波长下的反射率和所述第2极大反射波长下的反射率分别为15%以上,
所述第1树脂层包含着色剂。
2.根据权利要求1所述的夹层玻璃用中间膜,其中,
所述红外线反射层包含金属溅射层。
3.根据权利要求1或2所述的夹层玻璃用中间膜,其中,
所述着色剂为苝化合物、酞菁化合物、萘酞菁化合物或蒽酞菁化合物。
4.根据权利要求1~3中任一项所述的夹层玻璃用中间膜,其中,
所述第1树脂层包含隔热粒子。
5.根据权利要求1~4中任一项所述的夹层玻璃用中间膜,其中,
所述第1树脂层中的所述热塑性树脂为聚乙烯醇缩醛树脂。
6.根据权利要求1~5中任一项所述的夹层玻璃用中间膜,其中,
所述第1树脂层包含增塑剂。
7.根据权利要求1~6中任一项所述的夹层玻璃用中间膜,其具备第2树脂层,其中,
所述第2树脂层配置在所述红外线反射层的与所述第1表面相反的第2表面侧。
8.根据权利要求7所述的夹层玻璃用中间膜,其中,
所述第2树脂层中的所述热塑性树脂为聚乙烯醇缩醛树脂。
9.根据权利要求7或8所述的夹层玻璃用中间膜,其中,
所述第2树脂层包含增塑剂。
10.一种夹层玻璃,其具备第1夹层玻璃部件、第2夹层玻璃部件以及权利要求1~6中任一项所述的夹层玻璃用中间膜,其中,
所述中间膜具有或不具有第2树脂层,
在所述中间膜具有所述第2树脂层的情况下,所述第2树脂层配置在所述红外线反射层的与所述第1表面相反的第2表面侧,
在所述中间膜具有所述第2树脂层的情况下,所述第1夹层玻璃部件配置在所述第1树脂层外侧,所述第2夹层玻璃部件配置在所述第2树脂层外侧,
在中间膜不具有所述第2树脂层的情况下,所述第1夹层玻璃部件配置在所述第1树脂层外侧,所述第2夹层玻璃部件配置在所述红外线反射层外侧。
11.根据权利要求10所述的夹层玻璃,其在建筑物或车辆中安装于外部空间和热线从所述外部空间入射的内部空间之间的开口部处,并且使得所述第2夹层玻璃部件位于所述外部空间侧且使得所述第1夹层玻璃部件位于所述内部空间侧。
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