CN106132891B - 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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- CN106132891B CN106132891B CN201580016376.4A CN201580016376A CN106132891B CN 106132891 B CN106132891 B CN 106132891B CN 201580016376 A CN201580016376 A CN 201580016376A CN 106132891 B CN106132891 B CN 106132891B
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- light
- laminated glass
- interlayer film
- emitting layer
- layer
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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
- B32B17/10559—Shape of the cross-section
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- 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
- B32B17/10009—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
- B32B17/1055—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
- B32B17/10669—Luminescent agents
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Abstract
本发明的目的在于提供一种夹层玻璃用中间膜、以及使用了该夹层玻璃用中间膜的夹层玻璃,所述夹层玻璃用中间膜在夹层玻璃的特定区域中不发生双重显示,并且在一定范围的亮度下能够显示对比度高的图像。本发明是包含发光层和树脂层的多层结构的夹层玻璃用中间膜,所述发光层含有热塑性树脂、增塑剂和发光材料的发光层,所述树脂层层叠在所述发光层的至少一侧的面上,且含有热塑性树脂和增塑剂的,夹层玻璃用中间膜的截面形状为楔形,且所述发光层的最大厚度与最小厚度之差为100μm以下。
Description
技术领域
本发明涉及一种夹层玻璃用中间膜、以及使用了该夹层玻璃用中间膜的夹层玻璃,所述夹层玻璃用中间膜在夹层玻璃的特定区域中不发生双重显示,并且在一定范围的亮度下能够显示对比度高的图像。
背景技术
近年来,从安全性提高的角度出发,例如,对于汽车用的前玻璃,在与该前玻璃相同的视野内,使汽车行驶数据的速度信息等的仪表显示以平视显示器(HUD)的方式显示的要求不断提高。
作为HUD的机制,至今为止开发了各种方式。例如,有HUD显示部不在前玻璃表面上,而通过将由控制单元发送的速度信息等从仪表板的显示单元反射到前玻璃上,从而在与前玻璃相同的位置(即同一视野内)被驾驶员视觉确认的方式。这样的反射型的HUD中,通过适当调节焦点距离,视觉确认到显示的信息仿佛存在于远方,具有驾驶员的眼睛的焦点无需变更而安全的优点。
专利文献1中公开了将作为发光材料含有羟基对苯二甲酸酯的中间层层叠在2片透明板之间的夹层玻璃。专利文献1中记载的夹层玻璃通过照射光线,可以显示对比度高的图像。鉴于各HUD的优点,存在将利用使用了这样的发光材料的夹层玻璃的HUD与反射型的HUD组合的期望。然而,专利文献1中记载的夹层玻璃中,构成前玻璃的夹层玻璃由2片平行的玻璃构成,因此存在映在驾驶员的视野中的仪表显示有时看起来重影这样的问题。
现有技术文献
专利文献
专利文献1:国际公开第2010/139889号
发明内容
发明要解决的课题
本发明人等基于专利文献1中记载的发明,研究了在具有规定的楔角的楔形的夹层玻璃用中间膜中配合发光材料。已知使用了截面形状为楔形的夹层玻璃用中间膜的夹层玻璃通过调整该楔角,由一片玻璃反射的仪表显示和由另一片玻璃反射的仪表显示在驾驶员的视野内可归结至1点,能够解决仪表显示看起来重影的问题。
然而,实际上使用配合了发光材料的截面形状为楔形的夹层玻璃用中间膜时,产生了由发光材料显示的图像的亮度根据夹层玻璃的部位不同而不同这样的新问题。
本发明鉴于上述现状,目的在于提供一种夹层玻璃用中间膜、以及使用了该夹层玻璃用中间膜的夹层玻璃,所述夹层玻璃用中间膜在夹层玻璃的特定区域中不发生双重显示,并且在一定范围的亮度下能够显示对比度高的图像。
用于解决课题的手段
本发明是包含发光层和树脂层的多层结构的夹层玻璃用中间膜,所述发光层含有热塑性树脂、增塑剂和发光材料,所述树脂层层叠在所述发光层的至少一侧的面上,且含有热塑性树脂和增塑剂,夹层玻璃用中间膜的截面形状为楔形,且所述发光层的最大厚度与最小厚度的差为100μm以下。
以下详述本发明。
本发明人等对使用配合了发光材料的截面形状为楔形的夹层玻璃用中间膜的夹层玻璃中显示的图像的亮度不同的理由进行了研究。其结果,发现原因是通过使夹层玻璃用中间膜的厚度方向的截面形状为楔状,与厚度薄的部分相比厚度厚的部分中荧光材料的面密度变高。
本发明人等进一步深入研究的结果发现,通过将含有发光材料的发光层的厚度设为最大厚度与最小厚度之差为100μm以下,并将荧光材料的面密度的变动设为规定以下,同时将树脂层设为层叠的多层结构,并将作为夹层玻璃用中间膜整体的截面形状设为楔形,可以得到防止重影发生并且在一定范围的亮度下能够显示图像的夹层玻璃,从而完成了本发明。
首先,对本发明的夹层玻璃用中间膜的形状进行详细说明。
本发明的夹层玻璃用中间膜的截面形状为楔形。通过根据夹层玻璃的安装角度调整楔形的楔角θ,防止重影产生的图像显示成为可能。从进一步抑制重影的观点来看,上述楔角θ的优选下限为0.1mrad,更优选下限为0.2mrad,进一步优选下限为0.3mrad,优选上限为1mrad,更优选上限为0.9mrad。
需要说明的是,通过例如使用挤出机挤出成形树脂组合物的方法制造截面形状为楔形的夹层玻璃用中间膜的情况下,有时成为这样的形状:在从薄的一侧的端部起稍微内侧的区域(具体来说,将一端与另一端之间的距离设为X时,从薄的一侧的一端起向内侧0X~0.2X的距离的区域)具有最小厚度,在从厚的一侧的端部起稍微内侧的区域(具体来说,将一端与另一端之间的距离设为X时,从厚的一侧的一端起向内侧0X~0.2X的距离的区域)具有最大厚度的形状。本说明书中,这样的形状也包含在楔形中。
本发明的夹层玻璃用中间膜具有多层结构,该多层结构包含含有发光材料的发光层、以及树脂层(以下,也称为“形状辅助层”。)。将上述发光层的厚度设为一定范围,另一方面,通过层叠上述形状辅助层,从而将作为夹层玻璃用中间膜整体的截面形状调整为楔形。
上述形状辅助层可以仅层叠在上述发光层一侧的面上,也可以层叠在两侧的面上。此外,也可以层叠多个形状辅助层。
上述发光层的截面形状可以是楔形,也可以是矩形。上述发光层优选截面形状为楔形。将由本发明涉及的夹层玻璃用中间膜得到的夹层玻璃用作HUD的情况下,按照上述发光层的最小厚度位于HUD的下部、上述发光层的最大厚度位于HUD的上部的方式配置,进一步优选在使反射型的HUD的光源配置在HUD的下部附近、使发光型的HUD的激发光光源配置在HUD的上部附近的状态下使用。在这样的情况下,通过自发光层为楔形,并通过使接近反射型的HUD的光源的自发光层变薄,即使反射型的HUD的光源中包含发光材料的激发光,也能抑制发光材料未预期的发光,并且能够鲜明地显示反射型的HUD的图像。进一步通过自发光层为楔形,在接近发光型的HUD的激发光光源的HUD的上部,为了显示鲜明的图像可以存在充分量的发光材料,并且可以鲜明地显示发光型的HUD的图像。
上述发光层的最大厚度与最小厚度之差为100μm以下。由此,可在一定范围的亮度下显示图像。上述发光层的最大厚度与最小厚度之差优选为95μm以下,更优选为90μm以下,进一步优选为60μm以下,特别优选为50μm以下。上述发光层的最大厚度与最小厚度之差的下限没有特别限定,但优选为0。
上述发光层的厚度没有特别限定,但优选下限为50μm,优选上限为700μm。若上述发光层的厚度在该范围内,则可以显示足够高对比度的图像。上述发光层的厚度的更优选下限为70μm,更优选上限为400μm,进一步优选下限为80μm,进一步优选上限为150μm。需要说明的是,上述发光层的厚度的下限是指发光层的最小厚度的部分的厚度,上述发光层的厚度的上限是指发光层的最大厚度的部分的厚度。
上述形状辅助层层叠在上述发光层上,具有将作为夹层玻璃用中间膜整体的截面形状调整为楔形的作用。作为上述夹层玻璃用中间膜整体的截面形状优选为一定楔角的楔形。作为上述夹层玻璃用中间膜整体的截面形状是楔形的话,也可以不具有一定的楔角。
上述形状辅助层的截面形状优选为楔形、三角形、或梯形。通过层叠截面形状为楔形、三角形、或梯形的形状辅助层,可将作为夹层玻璃用中间膜整体的截面形状调整为楔形。需要说明的是,只要能起到作为上述形状辅助层的作用的话,上述形状辅助层也可以为例如五角形、六角形、椭圆形等形状。另外,也可以组合多个形状辅助层,从而调整作为夹层玻璃用中间膜整体的截面形状。这种情况下,全部的形状辅助层的截面形状不必相同,也可以不同。
上述形状辅助层的厚度没有特别限定,但从实用面的观点以及充分提高粘合力和耐贯通性的观点出发,优选下限为10μm,优选上限为1000μm,更优选下限为200μm,更优选上限为800μm,进一步优选下限为300μm。
需要说明的是,上述形状辅助层的厚度的下限是指形状辅助层的最小厚度的部分的厚度,上述形状辅助层的厚度的上限是指形状辅助层的最大厚度的部分的厚度。另外,组合使用多个形状辅助层的情况是指其总厚度。
本发明的夹层玻璃用中间膜整体的厚度没有特别限定,优选下限为100μm,优选上限为3000μm,更优选下限为250μm,更优选上限为2000μm,进一步优选下限为500μm,进一步优选上限为1500μm,特别优选下限为800μm。
需要说明的是,上述夹层玻璃用中间膜整体的厚度的下限是指夹层玻璃用中间膜整体的最小厚度的部分的厚度,上述夹层玻璃用中间膜整体的厚度的上限是指夹层玻璃用中间膜全体的最大厚度的部分的厚度。
说明本发明的夹层玻璃用中间膜的方式的一例的示意图在图1~3中示出。需要说明的是,在图1~3中,为了便于图示,与实际的厚度和楔角不同地示出夹层玻璃用中间膜和构成该夹层玻璃用中间膜的各层的厚度和楔角θ。
图1中示出了夹层玻璃用中间膜1的厚度方向的截面。
夹层玻璃用中间膜1具有在含有发光材料的发光层11一侧的面上层叠形状辅助层12的2层结构。
这里与发光层11为矩形相对,通过将形状辅助层12的形状设为楔形、三角形、或梯形,作为夹层玻璃用中间膜1整体成为楔角θ为0.1~1mrad的楔形。
图2中示出了夹层玻璃用中间膜2的厚度方向的截面。
夹层玻璃用中间膜2具有在含有发光材料的发光层21的两面上层叠形状辅助层22和形状辅助层23的3层结构。
这里与发光层21和形状辅助层23为厚度一定的矩形相对,通过将形状辅助层22的形状设为楔形、三角形、或梯形,作为夹层玻璃用中间膜2整体成为楔角θ为0.1~1mrad的楔形。
图3中示出了夹层玻璃用中间膜3的厚度方向的截面。
夹层玻璃用中间膜3具有在含有发光材料的发光层31的两面上层叠形状辅助层32和形状辅助层33的3层结构。
这里发光层31是最大厚度与最小厚度之差为100μm以下的平缓的楔形,通过层叠楔形的形状辅助层32、33,作为夹层玻璃用中间膜3整体成为楔角θ为0.1~1mrad的楔形。
接着,对构成本发明的夹层玻璃用中间膜的发光层和形状辅助层的成分进行详细说明。
上述发光层含有热塑性树脂、增塑剂和发光材料。通过具有含有发光材料的发光层,本发明的夹层玻璃用中间膜通过照射光线,可以显示对比度高的图像。
上述热塑性树脂没有特别限制,可举出例如,聚乙烯醇缩醛树脂、乙烯-乙酸乙烯基共聚物树脂、乙烯-丙烯酸系共聚物树脂、聚氨酯树脂、含有硫元素的聚氨酯树脂、聚乙烯醇树脂、氯乙烯树脂、聚对苯二甲酸乙二醇酯树脂等热塑性树脂。其中,与增塑剂并用的情况下,从得到发挥对玻璃的优异粘合性的夹层玻璃用中间膜出发,优选聚乙烯醇缩醛树脂。
上述聚乙烯醇缩醛树脂只要是用醛将聚乙烯醇缩醛化得到的聚乙烯醇缩醛树脂就没有特别限定,优选聚乙烯醇缩丁醛树脂。另外,根据需要也可以并用2种以上的聚乙烯醇缩醛树脂。
上述聚乙烯醇缩醛树脂的缩醛化度的优选下限为40摩尔%,优选上限为85摩尔%,更优选下限为60摩尔%,更优选上限为75摩尔%。
上述聚乙烯醇缩醛树脂的羟基量的优选下限为10摩尔%,优选上限为32摩尔%。若上述发光层中所含聚乙烯醇缩醛树脂的羟基量为该范围,则发光层的成形容易,并且,所得夹层玻璃用中间膜的耐贯通性变高。上述聚乙烯醇缩醛树脂的羟基量的更优选下限为15摩尔%,更优选上限为30摩尔%,进一步优选下限为18摩尔%,进一步优选上限为28摩尔%,特别优选下限为20摩尔%,特别优选上限为25摩尔%。
需要说明的是,上述缩醛化度和羟基量可以依据例如JIS K6728“聚乙烯醇缩丁醛试验方法”进行测定。
上述聚乙烯醇缩醛树脂可以通过用醛将聚乙烯醇缩醛化来制备。
上述聚乙烯醇一般使用通常通过将聚乙酸乙烯酯皂化得到的皂化度70~99.8摩尔%的聚乙烯醇。上述聚乙烯醇的皂化度优选为80~99.8摩尔%。
上述聚乙烯醇的聚合度的优选下限为500,优选上限为4000。若上述聚乙烯醇的聚合度为500以上,则所得夹层玻璃的耐贯通性变高。若上述聚乙烯醇的聚合度为4000以下,则夹层玻璃用中间膜的成形变得容易。上述聚乙烯醇的聚合度的更优选下限为1000,更优选上限为3600。
上述醛没有特别限定,但通常适合使用碳数为1~10的醛。上述碳数为1~10的醛没有特别限制,可举出例如,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、苯甲醛等。其中,优选正丁醛、正己醛、正戊醛,更优选正丁醛。这些醛可以单独使用,也可以并用2种以上。
上述增塑剂没有特别限定,可举出例如,一元有机酸酯、多元有机酸酯等有机酯增塑剂,有机磷酸增塑剂、有机亚磷酸增塑剂等磷酸增塑剂等。上述增塑剂优选为液态增塑剂。
上述一元有机酸酯没有特别限定,可举出例如,通过三乙二醇、四乙二醇、三丙二醇等二醇与丁酸、异丁酸、己酸、2-乙基丁酸、庚酸、正辛酸、2-乙基己酸、壬酸(正壬酸)、癸酸等一元有机酸反应得到的二醇酯等。其中,优选二己酸三乙二醇酯,二-2-乙基丁酸三乙二醇酯,二正辛酸三乙二醇酯,二-2-乙基己酸三乙二醇酯等。
上述多元有机酸酯没有特别限定,可举出例如,己二酸、癸二酸、壬二酸等多元有机酸与具有碳数4~8的直链或分支结构的醇的酯化合物。其中,优选癸二酸二丁酯、壬二酸二辛酯、己二酸二丁基卡必醇酯等。
上述有机酯增塑剂没有特别限定,可举出二-2-乙基丁酸三乙二醇酯、二-2-乙基己酸三乙二醇酯、二辛酸三乙二醇酯、二正辛酸三乙二醇酯、二正庚酸三乙二醇酯、二正庚酸四乙二醇酯、二-2-乙基己酸四乙二醇酯、癸二酸二丁酯、壬二酸二辛酯、己二酸二丁基卡必醇酯、二-2-乙基丁酸乙二醇酯、二-2-乙基丁酸-1,3-丙二醇酯、二-2-乙基丁酸-1,4-丁二醇酯、二-2-乙基丁酸二乙二醇酯、二-2-乙基己酸二乙二醇酯、二-2-乙基丁酸二丙二醇酯、二-2-乙基戊酸三乙二醇酯、二-2-乙基丁酸四乙二醇酯、二辛酸二乙二醇酯、己二酸二己酯、己二酸二辛酯、己二酸己环己酯、己二酸二异壬酯、己二酸庚壬酯、癸二酸二丁酯、油改性癸二酸醇酸、磷酸酯与己二酸酯的混合物、由己二酸酯、碳数4~9的烷基醇和碳数4~9的环状醇制作的混合型己二酸酯、己二酸己酯等碳数6~8的己二酸酯等。
上述有机磷酸增塑剂没有特别限定,可举出例如,三丁氧基乙基磷酸酯,异癸基苯基磷酸酯,三异丙基磷酸酯等。
此外,作为上述增塑剂,为了难以发生水解,优选含有二-2-乙基己酸三乙二醇酯(3GO)、二-2-乙基丁酸三乙二醇酯(3GH)、二-2-乙基己酸四乙二醇酯(4GO)、己二酸二己酯(DHA),更优选含有二-2-乙基己酸四乙二醇酯(4GO)、二-2-乙基己酸三乙二醇酯(3GO),特别更优选含有二-2-乙基己酸三乙二醇酯。
上述发光层中的上述增塑剂的含量没有特别限定,相对于上述聚乙烯醇缩醛树脂100重量份的优选下限为30重量份,优选上限为100重量份。若上述增塑剂的含量为30重量份以上,则夹层玻璃用中间膜的熔融粘度变低,将其作为夹层玻璃用中间膜制造夹层玻璃时的脱气性变高。若上述增塑剂的含量为100重量份以下,则夹层玻璃用中间膜的透明性变高。上述增塑剂的含量的更优选下限为35重量份,更优选上限为80重量份,进一步优选下限为45重量份,进一步优选上限为70重量份,特别优选下限为50重量份,特别优选上限为63重量份。
上述发光材料为选自发光粒子、发光颜料和发光染料中的至少一种。
上述发光粒子和上述发光颜料可举出例如,以Y2O2S:Eu、BaMg2Al16O27:Eu,Mn、(SrCaBaMg)5(PO4)3Cl:Eu、BaMg2Al16O27:Eu、BaMg2Al16O27:Eu,Mn、Sr5(PO4)3Cl:Eu、LaPO4:Ce,Tb、MgAl11O19:Ce,Tb、Y2O3:Eu、Y(PV)O4:Eu、3.5MgO·0.5MgF2·GeO2:Mn、Ca10(PO4)6FCl:Sb,Mn、Sr10(PO4)6FCl:Sb,Mn、(SrMg)2P2O7:Eu、Sr2P2O7:Eu、CaWO4、CaWO4:Pb、MgWO4、(BaCa)5(PO4)3Cl:Eu、Sr4Al14O25:Eu、Zn2SiO4:Mn等表示的荧光体和由它们构成的复合体,以及ZnS粒子、GaSe粒子、SiC粒子、CdTe粒子等粒子型等。
上述发光染料,可举出例如,(咔唑-萘酰亚胺)染料、(乙腈-三亚苯胺)染料、芳基磺酸酯花菁染料、苝染料、香豆素染料、三(4,4,4-三氟-1-(2-噻吩基)-1,3-丁二酮-O,O’)双(三苯基氧化膦-O-)铕等。
作为上述发光染料,其中,优选具有萘酰亚胺骨架的化合物或具有香豆素骨架的化合物。由于具有萘酰亚胺骨架的化合物、具有香豆素骨架的化合物对于用作粘合剂树脂的热塑性树脂的亲和性高,因此可均匀地分散在粘合剂树脂中,能够得到透明性高、雾度低的夹层玻璃用中间膜。另外,由于具有萘酰亚胺骨架的化合物、具有香豆素骨架的化合物对紫外线的耐久性也极其优异,因此使用了它们的夹层玻璃用中间膜能够发挥优异的耐光性。
上述具有萘酰亚胺骨架的化合物具体可举出例如,4-溴-1,8-萘酰亚胺、4-氨基-1,8-萘酰亚胺、4-甲氧基-N-甲基萘酸酰亚胺、萘酰亚胺、4-氨基萘酰亚胺、N-甲基-4-氨基萘酰亚胺、N-乙基-4-氨基萘酰亚胺、N-丙基-4-氨基萘酰亚胺、N-正丁基-4-氨基萘酰亚胺、4-乙酰氨基萘酰亚胺、N-甲基-4-乙酰氨基萘酰亚胺、N-乙基-4-乙酰氨基萘酰亚胺、N-丙基-4-乙酰氨基萘酰亚胺、N-正丁基-4-乙酰氨基萘酰亚胺、N-甲基-4-甲氧基萘酰亚胺、N-乙基-4-甲氧基萘酰亚胺、N-丙基-4-甲氧基萘酰亚胺、N-正丁基-4-甲氧基萘酰亚胺、N-甲基-4-乙氧基萘酰亚胺、N-乙基-4-乙氧基萘酰亚胺、N-丙基-4-乙氧基萘酰亚胺、N-正丁基-4-乙氧基萘酰亚胺、Lumogen F Violet 570(BASF日本公司制)、Lumogen F Blue 650(BASF日本公司制)等。
上述具有香豆素骨架的化合物具体可举出例如,在香豆素环7位上具有供电子性取代基的衍生物。更具体来说,可举出作为以在香豆素环7位上具有氨基为特征的衍生物的3-(2’-苯并噻唑)-7-二乙基氨基香豆素(香豆素6)、3-(2’-苯并咪唑基)-7-N,N-二乙基氨基香豆素(香豆素7)、3-(2’-N-甲基苯并咪唑基)-7-N,N-二乙基氨基香豆素(香豆素30)、和2,3,5,6-1H,4H-四氢-8-三氟甲基喹嗪(9,9a,1-gh)香豆素(香豆素153)等香豆素色素、碱性黄51等香豆素色素染料,另外,以在香豆素环7位上具有羟基为特征的7-羟基香豆素、3-氰基-7-羟基香豆素、7-羟基-4-甲基香豆素、7-二乙基氨基-4-甲基香豆素、7-二甲基氨基环戊[c]-香豆素、1,2,4,5,3H,6H,10H-四氢-8-甲基[1]苯并吡喃[9,9a,1-gH]喹嗪-10-酮、7-氨基-4-三氟甲基香豆素、1,2,4,5,3H,6H,10H-四氢-9-氰基[1]苯并吡喃[9,9a,1-gH]喹嗪-10-酮、1,2,4,5,3H,6H,10H-四氢-9-羰基叔丁氧基[1]苯并吡喃[9,9a,1-gH]喹嗪-10-酮、7-乙基氨基-6-甲基-4-三氟甲基香豆素、1,2,4,5,3H,6H,10H-四氢-9-乙氧羰基[1]苯并吡喃[9,9a,1-gH]喹嗪-10-酮、7-二乙基氨基-3-(1-甲基苯并咪唑基)香豆素、7-二甲基氨基-4-三氟甲基香豆素,1,2,4,5,3H,6H,10H-四氢-9-羧基[1]苯并吡喃[9,9a,1-gH]喹嗪-10-酮、1,2,4,5,3H,6H,10H-四氢-9-乙酰[1]苯并吡喃[9,9a,1-gH]喹嗪-10-酮、3-(2-苯并咪唑基)-7-N,N-二乙基氨基香豆素、1,2,4,5,3H,6H,10H-四氢-8-三氟甲基[1]苯并吡喃[9,9a,1-gH]喹嗪-10-酮、3-(2-苯并噻唑)-7-二乙基氨基香豆素、7-二乙基氨基香豆素、7-二乙基氨基-4-三氟甲基香豆素、2,3,6,7-四氢-9-(三氟甲基)-1H,5H,11H-[1]苯并吡喃[6,7,8-ij]喹嗪-11-酮、7-氨基-4-甲基香豆素、4,6-二甲基-7-乙基氨基香豆素等。
作为上述发光材料,优选使用具有对苯二甲酸酯结构的发光材料。上述具有对苯二甲酸酯结构的发光材料可举出例如,具有由下述通式(1)表示的结构的化合物和具有由下述通式(2)表示的结构的化合物。这些可以单独使用,也可以使用2种以上。
【化1】
上述通式(1)中,R1表示有机基团,x为1、2、3或4。从夹层玻璃用中间膜的透明性变得更高出发,x优选为1或2,优选在苯环的2位或5位上具有羟基,进一步优选在苯环的2位和5位上具有羟基。
上述R1的有机基团优选为烃基,更优选碳数为1~10的烃基,进一步优选碳数为1~5的烃基,特别优选碳数为1~3的烃基。若上述烃基的碳数为10以下,则上述具有对苯二甲酸酯结构的发光材料可以容易地分散至夹层玻璃用中间膜。上述烃基优选为烷基。
作为具有由上述通式(1)表示的结构的化合物,可举出例如,2,5-二羟基对苯二甲酸二乙酯,2,5-二羟基对苯二甲酸二甲酯等。其中,从能够显示对比度更高的图像出发,具有由上述通式(1)表示的结构的化合物优选为2,5-二羟基对苯二甲酸二乙酯(Aldrich公司制,“2,5-二羟基对苯二甲酸二乙酯”)。例如,具有由上述通式(1)表示的结构的化合物可由具有405nm波长的光线容易地激发。
上述通式(2)中,R2表示有机基团,R3和R4表示氢原子或有机基团,y为1、2、3或4。
上述R2的有机基团优选为烃基,更优选碳数为1~10的烃基,进一步优选碳数为1~5的烃基,特别优选碳数为1~3的烃基。若上述烃基的碳数为上述上限以下,则上述具有对苯二甲酸酯结构的发光材料可以容易地分散至夹层玻璃用中间膜。上述烃基优选为烷基。上述通式(2)中,NR3R4为氨基。R3和R4优选为氢原子。具有由上述通式(2)表示的结构的化合物的苯环的氢原子中,可以一个氢原子为上述氨基,可以两个氢原子为上述氨基,可以三个氢原子为上述氨基,也可以四个氢原子为上述氨基。
作为具有由上述通式(2)表示的结构的化合物,从能够显示对比度更高的图像出发,优选2,5-二氨基对苯二甲酸二乙酯(Aldrich公司制)。
上述发光层中的上述发光材料的含量相对于上述热塑性树脂100重量份的优选下限为0.005重量份,优选上限为5重量份。为了获得充分的发光,有必要配合一定量以上的发光材料,但另一方面若配合大量的发光材料,则有时发光性反而降低。这被认为是因为,激发的发光材料的相互作用导致吸收的能量向不发光的非辐射过程转移,而产生发光强度反而减小这样的浓度淬灭现象。若上述发光材料的含量在该范围内,则照射特定的波长的光时可以得到对比度充分高的发光。上述发光材料的含量的更优选下限为0.01重量份,更优选上限为3重量份,进一步优选下限为0.05重量份,进一步优选上限为1重量份。
上述发光层中的上述发光材料的含量在上述发光层100重量%中优选下限为0.005重量%,优选上限为5重量%。若上述发光材料的含量为0.005重量%以上,则可以得到能以更高的对比度显示图像的夹层玻璃用中间膜。若上述发光材料的含量为5重量%以下,则可以得到具有更高的透明性的夹层玻璃用中间膜。上述发光材料的含量的更优选下限为0.01重量%,更优选上限为3重量%,进一步优选下限为0.02重量%,进一步优选上限为1重量%。
上述发光层优选进一步含有分散剂。通过含有分散剂,可以使上述发光材料微分散至层中,可以更均匀地发光。
上述分散剂可以使用例如,直链烷基苯磺酸盐等具有磺酸结构的化合物、二酯化合物、蓖麻油酸烷基酯、邻苯二甲酸酯、己二酸酯、癸二酸酯、磷酸酯等具有酯结构的化合物;聚氧乙二醇、聚氧丙二醇或烷基苯基-聚氧乙烯-醚等具有醚结构的化合物;聚羧酸等具有羧酸结构的化合物;月桂胺、二甲基月桂胺、油烯基丙二胺、聚氧乙烯的仲胺、聚氧乙烯的叔胺、聚氧乙烯的二胺等具有胺结构的化合物;聚亚烷基多胺氧化烯等具有多胺结构的化合物;油酸二乙醇酰胺、烷醇脂肪酸酰胺等具有酰胺结构的化合物;聚乙烯基吡咯烷酮、聚酯酸酰胺胺盐等具有高分子量型酰胺结构的化合物等;三乙氧基丙基异氰酸酯硅烷、三乙氧基丁基硅烷等具有含有烷基的硅烷结构的化合物;三乙氧基丙基丙烯酰氧基硅烷等具有含有丙烯酰氧基的硅烷结构的化合物;三乙氧基丙基乙烯基硅烷等具有含有乙烯基的硅烷结构的化合物;具有作为含有环氧基或磷酸基、羧基、巯基等侧链的高分子量体的聚硅氧烷结构的化合物;异氰酸酯等具有异氰酸酯基的化合物;以及异氰脲酸酯等具有异氰脲酸酯基的化合物等以往公知的分散剂。另外,可使用聚氧乙烯烷基醚磷酸(盐)或高分子聚羧酸、缩合蓖麻油酸酯等高分子量分散剂。需要说明的是,高分子量分散剂被定义为其分子量为1万以上的分散剂。
配合上述分散剂的情况下,相对于上述发光层中的发光材料100重量份的上述分散剂的含量的优选下限为1重量份,优选上限为50重量份。若上述分散剂的含量在该范围内,则可使上述发光材料均匀地分散在发光层中。上述分散剂的含量的更优选下限为3重量份,更优选上限为30重量份,进一步优选下限为5重量份,进一步优选上限为25重量份。
上述发光层可进一步含有紫外线吸收剂。上述发光层通过含有紫外线吸收剂,上述发光层的耐光性变高。
上述紫外线吸收剂可举出例如,具有丙二酸酯结构的化合物,具有乙二酰苯胺结构的化合物、具有苯并三唑结构的化合物、具有二苯甲酮结构的化合物、具有三嗪结构的化合物、具有苯甲酸酯结构的化合物,具有受阻胺结构的化合物等紫外线吸收剂。
含有上述紫外线吸收剂的情况下,相对于上述发光层中的上述聚乙烯醇缩醛树脂100重量份的上述紫外线吸收剂的含量的优选上限为1重量份,更优选上限为0.5重量份,进一步优选上限为0.2重量份,特别优选上限为0.1重量份。
从能够得到优异的耐光性出发,上述发光层优选含有抗氧化剂。
上述抗氧化剂没有特别限定,可举出具有酚结构的抗氧化剂、含硫的抗氧化剂、含磷的抗氧化剂等。
具有上述酚结构的抗氧化剂是具有酚骨架的抗氧化剂。作为上述具有酚结构的抗氧化剂,可举出例如,2,6-二叔丁基对甲酚(BHT)、丁基化羟基苯甲醚(BHA)、2,6-二叔丁基-4-乙基苯酚、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-丁基苯酚)、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)、4,4’-亚丁基双(3-甲基-6-叔丁基苯酚)、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-叔丁基苯酚)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’-叔丁基苯酚)丁酸乙二醇酯,季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]等。上述抗氧化剂可以单独使用,也可以2种以上并用。
在对本发明的夹层玻璃用中间膜要求隔热性的情况下,上述发光层可以含有热辐射吸收剂。
上述热辐射吸收剂只要具有遮蔽红外线的性能就没有特别限定,优选为选自锡掺杂氧化铟(ITO)粒子、锑掺杂氧化锡(ATO)粒子、铝掺杂氧化锌(AZO)粒子、铟掺杂氧化锌(IZO)粒子、锡掺杂氧化锌粒子、硅掺杂氧化锌粒子、六硼化镧粒子和六硼化铈粒子中的至少1种。
上述发光层根据需要可进一步含有光稳定剂、抗静电剂等添加剂。另外,在本发明的夹层玻璃用中间膜的一部分区域设置着色带的情况下,可以在上述发光层的一部分配合蓝色颜料、蓝色染料、绿色颜料、绿色染料等着色剂。
上述发光层的镁元素的浓度优选为80ppm以下。上述发光材料是具有对苯二甲酸酯结构的发光材料的情况下,该具有对苯二甲酸酯结构的发光材料与镁元素形成络合物,导致夹层玻璃用中间膜的变色特别容易发生。通过将上述发光层的镁元素的浓度设为80ppm以下,可以抑制夹层玻璃用中间膜的变色。从进一步抑制夹层玻璃用中间膜的变色出发,上述发光层的镁元素的浓度优选为75ppm以下,更优选为60ppm以下,进一步优选为50ppm以下,特别优选为40ppm以下,最优选为30ppm以下,进一步最优选为25ppm以下。上述发光层的镁元素的浓度也可以是0ppm。
上述镁元素可以以例如金属镁或镁盐的形式包含在上述发光层中。
需要说明的是,变色是指,夹层玻璃用中间膜层叠在2片透明玻璃(厚度2.5mm)之间的夹层玻璃的YI值超过20。YI值可通过使用分光光度计(日立高科技公司制、“U-4100”),以JIS Z 8722为基准来测定。上述YI值优选为20以下,更优选为15以下,进一步优选为10以下。另外,上述YI值优选为0以上。
上述发光层的锂元素的浓度优选为25ppm以下。在上述发光层大量含有锂元素的情况下,夹层玻璃用中间膜发生变色的原因被认为是由于上述具有对苯二甲酸酯结构的发光材料与锂元素形成络合物。通过将上述发光层的锂元素的浓度设为25ppm以下,可进一步抑制夹层玻璃用中间膜的变色。上述发光层的锂元素的浓度的更优选上限为20ppm,进一步优选上限为10ppm以下,优选下限为0ppm,更优选下限为1ppm。
上述形状辅助层含有热塑性树脂和增塑剂。上述形状辅助层所含的热塑性树脂和增塑剂可以使用与上述发光层所含的热塑性树脂和增塑剂相同的。从在一定范围的亮度下能够显示对比度更高的图像出发,优选上述形状辅助层不含发光材料,或者上述形状辅助层中的上述发光材料的浓度(重量%)低于上述发光层中的上述发光材料的浓度(重量%)。上述形状辅助层的热塑性树脂优选为聚乙烯醇缩醛树脂。
上述形状辅助层优选进一步包含粘接力调节剂。
上述粘接力调节剂没有特别限定,优选为金属盐,优选为选自碱金属盐、碱土金属盐和镁盐中的至少1种金属盐。上述金属盐优选含有钾和镁中的至少1种金属。上述金属盐更优选为碳数1~16的有机酸的碱金属盐、碳数1~16的有机酸的碱土金属盐或碳数1~16的有机酸的镁盐,进一步优选为碳数2~16的有机酸的碱金属盐、碳数2~16的有机酸的碱土金属盐或碳数2~16的镁盐,特别优选为碳数2~16的羧酸的镁盐或碳数2~16的羧酸的钾盐。作为上述碳数2~16的羧酸的镁盐和上述碳数2~16的羧酸的钾盐没有特别限定,可举出例如,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、2-乙基己酸钾等。上述有机酸的碳数的优选下限为1,优选上限为10,更优选下限为2,更优选上限为8。
上述形状辅助层中的上述粘接力调节剂的含量没有特别限定,相对于上述热塑性树脂100重量份的优选下限为0.0005重量份,优选上限为0.05重量份。若上述粘接力调节剂的含量为0.0005重量份以上,则夹层玻璃的耐贯通性变高。若上述粘接力调节剂的含量为0.05重量份以下,则夹层玻璃用中间膜的透明性变高。上述粘接力调节剂的含量的更优选下限为0.002重量份,更优选上限为0.02重量份。
从上述形状辅助层的耐湿性变高出发,优选上述形状辅助层中的碱金属、碱土金属和镁的含量的总和为300ppm以下。例如,上述碱金属、碱土金属和镁可包含来自上述粘接力调节剂的金属,也可包含来自合成聚乙烯醇缩醛树脂时使用的中和剂的金属。上述形状辅助层中的碱金属、碱土金属和镁的含量的总和更优选为200ppm以下,进一步优选为150ppm以下,特别优选为100ppm以下。
从进一步防止夹层玻璃用中间膜的变色出发,上述形状辅助层所含镁元素的浓度优选为150ppm以下,更优选为100ppm以下,进一步优选为50ppm以下,特别优选为30ppm以下。上述形状辅助层所含镁浓度可以是0ppm,也可以超过0ppm。
上述形状辅助层根据需要可进一步含有紫外线吸收剂、抗氧化剂、热辐射吸收剂、光稳定剂、抗静电剂等添加物。
另外,在本发明的夹层玻璃用中间膜的一部分区域设置着色带的情况下,也可以在上述形状辅助层的一部分配合蓝色颜料、蓝色染料、绿色颜料、绿色染料等着色剂。
本发明的夹层玻璃用中间膜中,上述发光层和形状辅助层所含热塑性树脂同时为聚乙烯醇缩醛树脂的情况下,优选按照上述发光层所含聚乙烯醇缩醛树脂的羟基量低于上述形状辅助层所含聚乙烯醇缩醛树脂的羟基量的方式选择各层的聚乙烯醇缩醛树脂的组合。由此,可以防止发光材料从发光层向形状辅助层移动。
从进一步防止发光材料从发光层向形状辅助层移动出发,优选上述发光层所含聚乙烯醇缩醛树脂的羟基量与上述形状辅助层所含聚乙烯醇缩醛树脂的羟基量之差不足6.5摩尔%。上述羟基量之差优选为6.4摩尔%以下,进一步优选为6.2摩尔%以下,特别优选为6.0摩尔%以下,最优选为5.8摩尔%以下。
另外,上述羟基量之差优选为1摩尔%以上,更优选为2摩尔%以上,进一步优选为3摩尔%以上。
通过选择上述发光层和形状辅助层所含热塑性树脂和增塑剂的组合,也可对所得的夹层玻璃用中间膜赋予各种性能。
例如,通过使上述发光层所含增塑剂的含量多于上述形状辅助层所含增塑剂的含量更多,可对本发明的夹层玻璃用中间膜赋予隔音性能。具体来说,通过使上述增塑剂的含量之差为优选5重量份以上、更优选10重量份以上、进一步优选15重量份以上,可赋予高的隔音性。上述增塑剂的含量之差优选为50重量份以下,更优选为40重量份以下,进一步优选为35重量份以下。
从进一步提高隔音性的观点出发,上述发光层所含聚乙烯醇缩醛树脂的乙酰化度优选高于上述形状辅助层所含聚乙烯醇缩醛树脂的乙酰化度。具体来说,上述聚乙烯醇缩醛树脂的乙酰化度之差优选设为0.1摩尔%以上,更优选设为1摩尔%以上,进一步优选设为5摩尔%以上,特别优选设为10摩尔%以上。
从进一步提高隔音性的观点出发,上述发光层所含聚乙烯醇缩醛树脂的羟基量优选低于上述形状辅助层所含聚乙烯醇缩醛树脂的羟基量。具体来说,上述羟基量之差优选设为1摩尔%以上,更优选设为3摩尔%以上,进一步优选设为5摩尔%以上。
从进一步提高隔音性的观点出发,上述发光层所含聚乙烯醇缩醛树脂的缩醛化度优选高于上述形状辅助层所含聚乙烯醇缩醛树脂的缩醛化度。
本发明的夹层玻璃用中间膜的制造方法没有特别限定。例如,将含有增塑剂和发光材料的增塑剂溶液与聚乙烯醇缩醛树脂充分混合,制作用于形成上述发光层的树脂组合物。接着,将含有粘接力调节剂和增塑剂的增塑剂溶液与聚乙烯醇缩醛树脂充分混合,制作用于形成上述形状辅助层的树脂组合物。然后,用共挤出机将上述用于形成发光层的树脂组合物和上述用于形成形状辅助层的树脂组合物共挤出,可以制造层叠了发光层和形状辅助层的夹层玻璃用中间膜。
本发明的夹层玻璃用中间膜由于具有上述发光层,所以通过照射特定波长的光线而发光。通过利用该性质,能够以高对比度显示信息。
作为用于照射上述特定波长的光线的装置,可举出例如,点光源(浜松Photonic公司制,“LC-8”)、氙气闪光灯(Heraeus公司制,“CW Lamp”)、黑光灯(井内盛荣堂公司制,“Carry hand”)等。
将本发明的夹层玻璃用中间膜层叠在一对玻璃板之间的夹层玻璃也是本发明之一。
上述玻璃板可以使用通常所用的透明板玻璃。例如,可举出浮法板玻璃、抛光板玻璃、模塑板玻璃(molded plate glass)、夹丝板玻璃、着色的板玻璃、热辐射吸收玻璃、热辐射反射玻璃、生玻璃等无机玻璃。另外,也可以使用在玻璃的表面形成了紫外线遮蔽涂层的紫外线遮蔽玻璃,但优选用作与照射特定波长的光线一侧相反的一侧的玻璃板。进一步,作为上述玻璃板可以使用聚对苯二甲酸乙二醇酯、聚碳酸酯、聚丙烯酸酯等有机塑料板。
作为上述玻璃板,可以使用2种以上的玻璃板。例如,可举出在透明浮法板玻璃与生玻璃这样的着色的玻璃板之间层叠了本发明的夹层玻璃用中间膜的夹层玻璃。另外,作为上述玻璃板,也可使用2种以上的厚度不同的玻璃板。
发明效果
根据本发明,可以提供一种夹层玻璃用中间膜、以及使用了该夹层玻璃用中间膜的夹层玻璃,所述夹层玻璃用中间膜在夹层玻璃的特定区域中不发生双重显示,并且在一定范围的亮度下能够显示对比度高的图像。
附图说明
图1是说明本发明的夹层玻璃用中间膜的方式的一例的示意图。
图2是说明本发明的夹层玻璃用中间膜的方式的一例的示意图。
图3是说明本发明的夹层玻璃用中间膜的方式的一例的示意图。
具体实施方式
以下列举出实施例对本发明的方式进行更详细的说明,但本发明并不只限定于这些实施例。
(实施例1)
(1)发光层用树脂组合物的制备
向60重量份二-2-乙基己酸三乙二醇酯(3GO)中加入1.5重量份作为发光材料的具有由上述通式(1)表示的结构的化合物即2,5-二羟基对苯二甲酸二乙酯(Aldrich公司制,“2,5-二羟基对苯二甲酸二乙酯”),制备发光性的增塑剂溶液。用混合辊充分混炼所得的全部增塑剂溶液和100重量份通过将聚合度为2300的聚乙烯醇用正丁醛缩醛化得到聚乙烯醇缩丁醛(乙酰基量12.5摩尔%、羟基量23.6摩尔%、缩丁醛化度63.9摩尔%),从而制备发光层用树脂组合物。
(2)形状辅助层用树脂组合物的制备
向40重量份二-2-乙基己酸三乙二醇酯(3GO)中加入作为粘接力调节剂的乙酸镁,制备增塑剂溶液。用混合辊充分混炼所得的全部增塑剂溶液和100重量份通过将聚合度为1700的聚乙烯醇用正丁醛缩醛化得到聚乙烯醇缩丁醛(乙酰基量0.9摩尔%、羟基量30.0摩尔%、缩丁醛化度69.1摩尔%),从而制备形状辅助层用树脂组合物。
需要说明的是,按照形状辅助层中的镁元素的浓度成为70ppm的方式向二-2-乙基己酸三乙二醇酯(3GO)中添加乙酸镁。
(3)夹层玻璃用中间膜的制造
通过用挤出机将所得发光层用树脂组合物和形状辅助层用树脂组合物共挤出,按形状辅助层、发光层和形状辅助层的顺序层叠,得到图3中记载的3层结构的夹层玻璃用中间膜。
需要说明的是,测定相对于所得中间膜的挤出方向的垂直方向的一端与另一端的最短距离,为1m。
另外,所得夹层玻璃用中间膜中的发光层具有最小厚度90μm、最大厚度140μm的楔形的截面形状,夹层玻璃用中间膜整体具有最小厚度800μm、最大厚度1200μm的楔形的截面形状。需要说明的是,夹层玻璃用中间膜的一端具有最小厚度,且另一端具有最大厚度,用光学显微镜观察并测定最小厚度和最大厚度。
(4)夹层玻璃的制造
用2片透明的浮法玻璃(纵1000mm×横300mm×厚2.5mm)夹住所得中间膜,得到层叠体。使用230℃的加热辊,对所得层叠体进行临时压接。其后,通过加热辊法,用高压反应釜,在135℃、压力1.2MPa的条件下压接临时压接的层叠体20分钟,制作夹层玻璃(纵1000mm×横300mm)。
(5)亮度测定用夹层玻璃的制造
在一端与另一端的最短距离上,以从一端起10cm的点为中心,切下纵10cm×横10cm的中间膜(薄的部分)。同样地,在一端与另一端的最短距离上,以从另一端起10cm的点为中心,切下纵10cm×横10cm的中间膜(厚的部分)。
用2片透明的浮法玻璃(纵100mm×横100mm×厚2.5mm)分别夹住所得的中间膜(薄的部分)和中间膜(厚的部分),得到层叠体。使用230℃的加热辊,对所得层叠体进行临时压接。其后,通过加热辊法,用高压反应釜,在135℃、压力1.2MPa的条件下压接临时压接的层叠体20分钟,制作亮度测定用夹层玻璃(纵100mm×横100mm)。
(实施例2、3)
将发光材料的种类、发光层的厚度方向的最大厚度和最小厚度设为表1所示那样,除此以外,与实施例1同样地得到夹层玻璃用中间膜和夹层玻璃。
(比较例1、2)
将发光材料的种类、发光层的厚度方向的最大厚度和最小厚度设为表1所示那样,并且未层叠形状辅助层,除此以外,与实施例1同样地得到夹层玻璃用中间膜和夹层玻璃。
(实施例4~8、比较例3、4)
将发光层的厚度方向的最大厚度和最小厚度、以及中间膜的最小厚度、最大厚度和楔角改变为表2所示那样,除此以外,与实施例1同样地得到夹层玻璃用中间膜和夹层玻璃。
(实施例9~12、比较例5、6)
将使用的聚乙烯醇缩丁醛的组成、增塑剂的含量、发光层的厚度方向的最大厚度和最小厚度、以及中间膜的最小厚度、最大厚度和楔角改变为表3所示那样,除此以外,与实施例1同样地得到夹层玻璃用中间膜和夹层玻璃。
(实施例13)
(1)发光层用树脂组合物的制备
向40重量份二-2-乙基己酸三乙二醇酯(3GO)中加入1.5重量份作为发光材料的具有由上述通式(1)表示的结构的化合物即2,5-二羟基对苯二甲酸二乙酯(Aldrich公司制,“2,5-二羟基对苯二甲酸二乙酯”),制备发光性的增塑剂溶液。用混合辊充分混炼所得的全部增塑剂溶液和100重量份通过将聚合度为1700的聚乙烯醇用正丁醛缩醛化得到聚乙烯醇缩丁醛(乙酰基量0.9摩尔%、羟基量30.0摩尔%、缩丁醛化度69.1摩尔%),从而制备发光层用树脂组合物。
(2)第一树脂层和第二树脂层用树脂组合物的制备
向40重量份二-2-乙基己酸三乙二醇酯(3GO)中加入作为粘接力调节剂的乙酸镁,制备增塑剂溶液。用混合辊充分混炼所得的全部增塑剂溶液和100重量份通过将聚合度为1700的聚乙烯醇用正丁醛缩醛化得到聚乙烯醇缩丁醛(乙酰基量0.9摩尔%、羟基量30.0摩尔%、缩丁醛化度69.1摩尔%),从而制备第一树脂层和第二树脂层用树脂组合物。
需要说明的是,按照第一树脂层和第二树脂层中的镁元素的浓度成为70ppm的方式向二-2-乙基己酸三乙二醇酯(3GO)中添加乙酸镁。
(3)隔音层用树脂组合物的制备
用混合辊充分混炼60重量份二-2-乙基己酸三乙二醇酯(3GO)和100重量份通过将聚合度为2300的聚乙烯醇用正丁醛缩醛化得到聚乙烯醇缩丁醛(乙酰基量12.5摩尔%、羟基量23.6摩尔%、缩丁醛化度63.9摩尔%),从而制备隔音层用树脂组合物。
(4)形状辅助层的制作
通过用共挤出机共挤出第一树脂层和第二树脂层用树脂组合物以及隔音层用树脂组合物,按第一树脂层、隔音层和第二树脂层的顺序层叠,得到作为形状辅助层的3层结构的层叠体。
(5)夹层玻璃用中间膜的制造
通过以单层挤出所得发光层用树脂组合物得到发光层。通过按第一树脂层、隔音层、第二树脂层、发光层的顺序层叠形状辅助层和发光层,得到4层结构的夹层玻璃用中间膜。
需要说明的是,测定相对于所得中间膜的挤出方向的垂直方向的一端与另一端的最短距离,为1m。
另外,所得夹层玻璃用中间膜中的发光层具有最小厚度90μm、最大厚度140μm的楔形的截面形状,夹层玻璃用中间膜整体具有最小厚度800μm、最大厚度1200μm的楔形的截面形状。此外,所得夹层玻璃用中间膜中的第一树脂层具有最小厚度305μm、最大厚度480μm的楔形的截面形状,隔音层具有平均厚度100μm的矩形的截面形状,第二树脂层具有最小厚度305μm、最大厚度480μm的楔形的截面形状。需要说明的是,夹层玻璃用中间膜的一端具有最小厚度,且另一端具有最大厚度,用光学显微镜观察并测定最小厚度和最大厚度。
(6)夹层玻璃的制造
用2片透明的浮法玻璃(纵1000mm×横300mm×厚2.5mm)夹住所得中间膜,得到层叠体。使用230℃的加热辊,对所得层叠体进行临时压接。其后,通过加热辊法,用高压反应釜,在135℃、压力1.2MPa的条件下压接临时压接的层叠体20分钟,制作夹层玻璃(纵1000mm×横300mm)。
(7)亮度测定用夹层玻璃的制造
在一端与另一端的最短距离上,以从一端起10cm的点为中心,切下纵10cm×横10cm的中间膜(薄的部分)。同样地,在一端与另一端的最短距离上,以从另一端起10cm的点为中心,切下纵10cm×横10cm的中间膜(厚的部分)。
用2片透明的浮法玻璃(纵100mm×横100mm×厚2.5mm)分别夹住所得的中间膜(薄的部分)和中间膜(厚的部分),得到层叠体。使用230℃的加热辊,对所得层叠体进行临时压接。其后,通过加热辊法,用高压反应釜,在135℃、压力1.2MPa的条件下压接临时压接的层叠体20分钟,制作亮度测定用夹层玻璃(纵100mm×横100mm)。
(实施例14、比较例7、8)
将发光层的最小厚度和最大厚度、第一树脂层的最小厚度和最大厚度、以及第二树脂层的最小厚度和最大厚度改变为表4所示那样,除此以外,与实施例13同样地得到夹层玻璃用中间膜和夹层玻璃。
(评价)
通过以下的方法对实施例和比较例中得到的夹层玻璃进行评价。
将结果示于表1~4。
(1)重影的发生的评价
将所得夹层玻璃(纵1000mm×横300mm)设置在前玻璃的位置。从设置在夹层玻璃的下方的显示单元使显示信息反射至夹层玻璃,在规定的位置用目视确认重影的有无。将未确认到重影的情况评价为“○”,将确认到重影的情况评价为“×”。
(2)亮度的偏差的评价
在暗室下,由相对于所得亮度测定用夹层玻璃的面的垂直方向上距离夹层玻璃10cm的位置处配置的High Power氙灯光源(朝日分光公司制,“REX-250”,照射波长405nm)向夹层玻璃的整面照射光,并通过配置于与照射光的夹层玻璃的面呈45度的角度、距离夹层玻璃面的最短距离为35cm的位置处的亮度计(TOPCON TECHNOHOUSE公司制,“SR-3AR”)来测定亮度。
将中间膜(薄的部分)和中间膜(厚的部分)的亮度差的绝对值为200以下的情况评价为“○”,将超过200的情况评价为“×”。
【表1】
【表2】
【表3】
【表4】
工业上的可利用性
根据本发明,可以提供一种夹层玻璃用中间膜、以及使用了该夹层玻璃用中间膜的夹层玻璃,所述夹层玻璃用中间膜在夹层玻璃的特定区域中不发生双重显示,并且在一定范围的亮度下能够显示对比度高的图像。
附图标记说明
1 夹层玻璃用中间膜
11 发光层
12 形状辅助层
2 夹层玻璃用中间膜
21 发光层
22 形状辅助层
23 形状辅助层
3 夹层玻璃用中间膜
31 发光层
32 形状辅助层
33 形状辅助层
Claims (7)
2.根据权利要求1所述的夹层玻璃用中间膜,其特征在于,夹层玻璃用中间膜的截面形状是楔角θ为0.1~1mrad的楔形。
3.根据权利要求1或2所述的夹层玻璃用中间膜,其特征在于,发光层的厚度为50~700μm。
4.根据权利要求1或2所述的夹层玻璃用中间膜,其特征在于,树脂层的厚度为10~1000μm。
5.根据权利要求1或2所述的夹层玻璃用中间膜,其特征在于,发光层和树脂层所含的热塑性树脂是聚乙烯醇缩醛树脂。
6.根据权利要求5所述的夹层玻璃用中间膜,其特征在于,发光层所含的聚乙烯醇缩醛树脂的羟基量低于树脂层所含的聚乙烯醇缩醛树脂的羟基量。
7.一种夹层玻璃,其特征在于,权利要求1、2、3、4、5或6所述的夹层玻璃用中间膜层叠在一对玻璃板之间。
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