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CN114521174A - 多层构造体 - Google Patents

多层构造体 Download PDF

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Publication number
CN114521174A
CN114521174A CN202080066849.2A CN202080066849A CN114521174A CN 114521174 A CN114521174 A CN 114521174A CN 202080066849 A CN202080066849 A CN 202080066849A CN 114521174 A CN114521174 A CN 114521174A
Authority
CN
China
Prior art keywords
layer
resin
multilayer structure
glass
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202080066849.2A
Other languages
English (en)
Inventor
村重毅
稻垣淳一
佐藤启介
岸敦史
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of CN114521174A publication Critical patent/CN114521174A/zh
Pending legal-status Critical Current

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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
    • B32B17/10761—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 containing vinyl acetal
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    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/10119—Properties of the bulk of a glass sheet having a composition deviating from the basic composition of soda-lime glass, e.g. borosilicate
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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
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    • 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
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Abstract

一种多层构造体，其具有厚度为10μm以上200μm以下的玻璃层、以及树脂层，将一个玻璃层与一个树脂层的层叠构造作为单位层叠构造，在该多层构造体的厚度方向中，该单位层叠构造的数量为5层以上20000层以下。

Description

多层构造体
技术领域
本发明涉及具有玻璃层和树脂层的多层构造体。
背景技术
将玻璃和树脂薄膜重叠多层而成的多层构造体作为同时具有玻璃所具有的刚性和树脂所具有的韧性的复合材料为人所知。该多层构造体具有如下效果，即，对于高强度的冲击，通过反复对玻璃的破坏以及树脂的冲击吸收，使外部冲击急剧减小。由于这样的特征，该多层构造体被广泛用于作为防弹玻璃、安全防御用的玻璃相对于来自外部的冲击防止龟裂破损的用途。
现有技术文献
专利文献
专利文献1：日本特开2003-192402号公报
发明内容
发明所要解决的问题
以往的多层构造体使用多张具有数mm厚度的平板玻璃，多层的数量越多耐冲击性越高，但是由于玻璃比重较大，因此重量的问题成为课题。为了扩展玻璃的活用场景，使玻璃弯曲的曲面玻璃虽然从设计性的观点出发被用于陈列柜、建筑部件等，但是为了将多层构造体应用于曲面玻璃，需要使多层构造体热变形为曲面形状，在数百度的玻璃的软化点下树脂层热分解，因此不现实。虽然也存在事先形成玻璃曲面，然后与树脂层叠的方式，但是难以获得较高生产率。
另外，若能获得圆筒的多层构造体，则能够用作高强度的配管坯料，至今为止虽然能够向在金属表面实施了玻璃处理的化学设备等提供不破裂的透明的可视化的配管，但使玻璃管和树脂管多层叠却极其困难。
本发明鉴于上述的点而成，其目的在于，提供一种具有玻璃层与树脂层的多层复合构造，且能够成形为任意形状的多层构造体。
解决问题的方法
本多层构造体具有厚度为10μm以上200μm以下的玻璃层、以及树脂层，将一个玻璃层与一个树脂层的层叠构造作为单位层叠构造，在该多层构造体的厚度方向中，该单位层叠构造的数量为5层以上20000层以下。
发明的效果
根据公开的技术，能够提供一种具有玻璃层与树脂层的多层复合构造，且能够成形为任意形状的多层构造体。
附图说明
图1是举例示出本实施方式的多层构造体的立体图。
图2是举例示出本实施方式的变形例1的多层构造体的立体图。
图3是举例示出本实施方式的变形例2的多层构造体的立体图。
图4A是举例示出本实施方式的多层构造体的横剖面的形状的剖视图(其一)。
图4B是举例示出本实施方式的多层构造体的横剖面的形状的剖视图(其二)。
图4C是举例示出本实施方式的多层构造体的横剖面的形状的剖视图(其三)。
图4D是举例示出本实施方式的多层构造体的横剖面的形状的剖视图(其四)。
图5A是举例示出本实施方式的多层构造体的树脂层的构造的剖视图(其一)。
图5B是举例示出本实施方式的多层构造体的树脂层的构造的剖视图(其二)。
图6是举例示出树脂层仅由粘接层构成的情况下的多层构造体的制造方法的图。
图7是举例说明树脂层由树脂薄膜和粘接层构成的情况下的多层构造体的制造方法的图(其一)。
图8是举例说明树脂层由树脂薄膜和粘接层构成的情况下的多层构造体的制造方法的图(其二)。
图9A是举例说明树脂层由树脂薄膜和粘接层构成的情况下的多层构造体的制造方法的图(其三)。
图9B是举例说明树脂层由树脂薄膜和粘接层构成的情况下的多层构造体的制造方法的图(其四)。
图10是表示截断本实施方式的多层构造体的柱状构造的例子的立体图(其一)。
图11是表示截断本实施方式的多层构造体的柱状构造的例子的立体图(其二)。
符号说明
10、10A、10B 多层构造体
10C、10D 板
11 玻璃层
12 树脂层
13 单位层叠构造
121 树脂薄膜
122 粘接层
122A 粘接剂
具体实施方式
以下，参照附图对用于实施发明的方式进行说明。在各附图中，对于相同的构成部分付与相同附图标记，并且有时省略重复的说明。
[多层构造体]
图1是举例示出本实施方式的多层构造体的立体图。如图1所示，多层构造体10是玻璃层11与树脂层12交替配置多层的构造。
更具体而言，多层构造体10为如下构造，即，设定一个玻璃层11与一个树脂层12的层叠构造为单位层叠构造13，在多层构造体10的厚度方向(层叠方向)上，单位层叠构造13是以玻璃层11与树脂层12交替配置的方式层叠固定多个的构造。需要说明的是，单位层叠构造13也可以彼此通过粘接层或粘合层进行层叠。
在单位层叠构造13中，例如，玻璃层11与树脂层12是相同的厚度。但是，在单位层叠构造13中，玻璃层11与树脂层12也可以厚度不同。另外，也可以是对玻璃层11与树脂层12的厚度为任意的厚度而层叠的厚度不同的多种的单位层叠构造进行组合。
单位层叠构造13的层数为5层～20000层，优选为10层～1000层，更优选为20层～100层。若在该范围内，则能够获得兼顾轻便和耐冲击性的多层构造体10。需要说明的是，在各图中，为了便于制作附图，存在单位层叠构造13的层叠数比5层少的情况，但实际上，单位层叠构造13的层数为5层以上20000层以下。
图2是举例示出本实施方式的变形例1的多层构造体的立体图。多层构造体的构造可以如图1所示多层构造体10那样，玻璃层11与树脂层12的主面为平面，也可以如图2所示多层构造体10A那样，玻璃层11与树脂层12的主面为曲面。或者，对于本实施方式的多层构造体的构造，也可以是玻璃层11与树脂层12的主面为平面的部分与曲面的部分组合。
图3是举例示出本实施方式的变形例2中的多层构造体的立体图。如图3所示多层构造体10B那样，若将单位层叠构造13层叠为辊状，则能够代表性地构成圆筒形状。在图3中，多层构造体10B的中心附近的S表示空间。
如图4A所示，多层构造体10B的柱状构造的横剖面例如为圆。但是，多层构造体10B的柱状构造的横剖面不限定为圆，可以为如图4B所示的椭圆，也可以为如图4C、图4D所示的直线与曲线的组合。图4C的剖面的例子为角部带有圆角的长方形，图4D的剖面的例子为角部带有圆角的六边形。
[玻璃层]
玻璃层11不特别限定，能够根据目的采用合适的玻璃。根据基于组成的分类，玻璃层11例如能够举出碱石灰玻璃、硼酸玻璃、铝硅酸盐玻璃、石英玻璃等。另外，根据基于碱成分的分类，能够举出无碱玻璃、低碱玻璃。优选上述玻璃的碱金属成分(例如，Na2O、K2O、Li2O)的含有量为15重量％以下，更优选为10重量％以下。
玻璃层11的厚度t1例如为10μm以上200μm以下。这里，10μm～200μm的厚度的玻璃层是指，玻璃层的平均厚度为10μm～200μm的玻璃层。
考虑玻璃所具有的表面硬度、气密性以及耐腐蚀性，优选玻璃层11的厚度t1为10μ以上。另外，由于期望在获得曲面构造基础上单一的玻璃层11具有薄膜那样的挠性，因此优选玻璃层11的厚度t1为200μm以下。特别优选为50μm～100μm。
优选玻璃层11的波长550nm中的透光率为85％以上。优选玻璃层11的波长550nm中的折射率为1.4～1.65。优选玻璃层11的密度为2.3g/cm3～3.0g/cm3，更优选为2.3g/cm3～2.7g/cm3。
玻璃层11的成形方法不特别限定，能够根据目的采用合适的方法。代表而言，玻璃层11可以将包含硅和/或氧化铝等的主原料、芒硝和/或氧化锑等的消泡剂、以及碳等的还原剂的混合物以1400℃～1600℃左右的温度熔融，使其成形为薄板状后，进行冷却来制作。作为玻璃层11的成形方法，例如可以举出狭缝下拉法、熔融法、浮法等。通过这些方法成形为板状的玻璃层为了薄板化、提高平滑性，也可以根据需要，通过氢氟酸等的溶剂进行化学研磨。
[树脂层]
本申请中，树脂层是指包含树脂成分的层。树脂层也可以包括用于形成树脂层的无机粒子等的添加剂。具体而言，仅由粘接层、粘合层或者中间膜构成的层符合树脂层。图5A是树脂层12仅由粘接层、粘合层或者中间膜构成的例子。
另外，将具有挠性的树脂薄膜与玻璃层通过粘接层或者粘合层进行层叠的情况下，具有树脂薄膜与粘接层或粘合层的层符合树脂层。也就是说，在单位层叠构造中，树脂层可以是包括具有挠性的树脂薄膜、以及设于玻璃层与树脂薄膜之间的粘接层或粘合层的构成。图5B是树脂层12由树脂薄膜121和粘接层122构成的例子。树脂层12也可以替代粘接层122而具有粘合层。
树脂层12的厚度t2例如为0.1μm～2mm。这里，0.1μm～2mm的厚度的树脂层是指，树脂层的平均厚度为0.1μm～2mm的树脂层。
[树脂薄膜]
作为挠性的树脂基材，例如，可以举出聚醚砜类树脂；聚碳酸酯类树脂；丙烯酸类树脂；聚对苯二甲酸乙二醇酯类树脂、聚萘二甲酸乙二醇酯类树脂等的聚酯类树脂；聚烯烃类树脂；降冰片烯类树脂等的环烯烃类树脂；聚酰亚胺类树脂；聚酰胺类树脂；聚酰亚胺酰胺类树脂；聚芳酯类树脂；聚砜类树脂；聚醚酰亚胺类树脂等。其中，优选使用聚对苯二甲酸乙二醇酯、聚碳酸酯、聚烯烃。树脂基材的颜色不特别限定，但从透明性的观点来说不优选不透明的树脂基材。优选树脂薄膜的厚度为25μm～1mm左右。特别优选为50μm～500μm。
[粘接剂、粘合剂、中间膜]
作为粘接剂或粘合剂，可以使用任意的适合的粘接剂或粘合剂。具体而言，能够举出丙烯酸类粘合剂、硅树脂类粘合剂、橡胶类粘合剂、紫外线固化性丙烯酸类粘接剂、紫外线固化性环氧树脂类粘接剂、热固化性环氧树脂类粘接剂、热固化性三氯氰胺类粘接剂、热固化性苯酚类粘接剂。
另外，作为中间膜，可以利用乙烯-醋酸乙烯酯共聚物(EVA)的中间膜、聚乙烯醇缩丁醛(PVB)等的聚乙烯醇缩醛类树脂的中间膜、聚氯乙烯(PVC)等的聚卤乙烯树脂的中间膜等。粘接层、粘合层以及中间膜的厚度在树脂层的厚度的范围内即可，不特别限定。
[多层构造体的制造方法]
(树脂层12仅由粘接层、粘合层、或中间膜构成的情况)
图6是举例示出树脂层仅由粘接层构成的情况的多层构造体的制造方法的图。树脂层12仅由粘接层构成的情况下，例如，通过如图6所示方法，可以制造多层构造体10B。树脂层12仅由粘合层或中间膜构成的情况下，通过与图6相同的方法，能够制造多层构造体10B。
具体而言，一边自放出辊300沿箭头方向放出缠卷于放出辊300的玻璃层11，一边在玻璃层11的一个面层叠粘接剂122A，然后卷绕于具有期望的内径卷取辊350。粘接剂122A为液状的情况下，使用固化装置400使粘接剂122A固化而作为树脂层12。固化装置400例如为紫外线照射装置、加热装置。之后，通过除去卷取辊350，可以获得作为玻璃层11与树脂层12的层叠构造的单位层叠构造13被层叠为期望的层数的多层构造体10B。树脂层12由粘接剂122A固化后的粘接层构成。
需要说明的是，作为树脂层12使用EVA、PVB等的中间膜时，优选一边给予热量一边用卷取辊350进行卷绕。
另外，树脂层12仅由中间膜构成的情况下，也可以通过将玻璃层11与树脂层12的单位层叠构造13的中间膜一侧的面与别的单位层叠构造13的玻璃层11一侧热压接来制作多层构造体10B。就原理而言，使其层叠时，通过将单位层叠构造13的温度升高至玻璃层11与中间膜能够粘接的温度，从而能够制作多层构造体10B。
例如，作为提高温度的方法，在制作任意的柱状构造(筒状)的多层构造体10B时，能够举出与层叠同时或在层叠后通过将加热的辊按压于最外层来进行压接的方法。另外，在预先制作使玻璃层11与中间膜层叠的单位层叠构造13的薄片的情况下，通过提高层压的辊的温度，能够获得单位层叠构造13的薄片。作为获得单位层叠构造13的其它方法，也可以在使玻璃层11与中间膜重叠的状态下暂时卷绕后，将辊置于真空下，使用红外线等提高温度进行粘接。
(树脂层12由树脂薄膜与粘接层或粘合层构成的情况)
图7是举例示出树脂层由树脂薄膜与粘接层构成的情况的多层构造体的制造方法的图。树脂层12由树脂薄膜与粘接层构成的情况下，例如，通过如图7所示方法，能够制造多层构造体10B。树脂层12由树脂薄膜与粘合层构成的情况下，也能够通过与图7相同的方法制造多层构造体10B。
具体而言，一边自放出辊300和放出辊310沿箭头方向放出缠卷于放出辊300的玻璃层11、缠卷于放出辊310的树脂薄膜121，一边在树脂薄膜121的两个面层叠粘接剂122A，然后卷绕于具有期望的内径的卷取辊350。之后，通过除去卷取辊350，能够获得作为玻璃层11与树脂层12的层叠构造的单位层叠构造13被层叠期望的层数的多层构造体10B。树脂层12由树脂薄膜121、粘接剂122A固化后的粘接层122构成。
需要说明的是，如图8所示，代替在树脂薄膜121的两个面层叠粘接剂122A的方法，也可以使用在玻璃层11的一个面以及在树脂薄膜121的一个面分别层叠粘接剂122A的方法。图8中，缠卷于放出辊320A和320B的薄膜状的粘接剂122A供给至玻璃层11的一个面和树脂薄膜121的一个面。
另外，也可以使用以下的方法。
首先，如图9A所示，一边自放出辊300和放出辊310沿箭头方向放出缠卷于放出辊300的玻璃层11和缠卷于放出辊310的树脂薄膜121，一边使用涂布机500向树脂薄膜121的一个面层叠粘接剂122A，然后穿过夹持辊330而卷绕于卷取辊360。由此，制作使玻璃层11与树脂薄膜121通过粘接剂122A层叠的复合辊10X。
接下来，如图9B所示，一边沿箭头方向放出复合辊10X，一边使用涂布机500在树脂薄膜121的一个面层叠粘接剂122A，然后卷绕于具有期望的内径的卷取辊350。之后，通过除去卷取辊350，能够获得作为玻璃层11与树脂层12的层叠构造的单位层叠构造13被层叠为期望的层数的多层构造体10B。该情况下，单位层叠构造13彼此通过粘接层被层叠。图9B中，也可以在树脂薄膜121的两个面层叠粘接剂122A。
需要说明的是，在图6～图9B所示的任意的方法中，对于需要固化的粘接剂，需要一边卷绕一边通过热量、光进行固化，或者在卷绕之后通过热量、光进行固化。另外，对于液状的粘接剂，能够举出如图9A和图9B所示的、使用涂布机500在树脂薄膜121上进行涂布使其层叠的方法，或者如图7所示的、在卷绕部分制作积液从而在卷绕的同时形成粘接剂的层的方法。
在图6～图9B所示任意的方法中，多层构造体10B的厚度能够根据卷绕的次数进行控制。另外，多层构造体10B的内径能够通过选择卷取辊350的外径来任意进行控制。
另外，组合两种以上的多层构造体时，例如，通过上述方法卷绕一种多层构造体之后，在其上卷绕多层由其他的厚度、材质构成的薄膜，从而能够制作在圆筒的内侧与外侧由不同的多层构造体构成的层叠体。该情况下，当然也可以加入通过粘接剂仅卷绕不包含玻璃的树脂薄膜等的构成。
多层构造体10B一般为圆筒，但通过改变卷取辊350的形状，能够制作如图4A～图4D所示的各种形状的多层构造体10B。
而且，通过截断多层构造体10B的柱状构造，如图10所示板10C、图11所示板10D那样，能够获得半圆、任意的曲面形状的板。通过组合板10C和板10D，能够制作出各种立体构造。另外，通过截断多层构造体10B的柱状构造，能够制作如图1所示多层构造体10、如图2所示多层构造体10A。
[用途]
本实施方式的多层构造体例如能够用于工业用的配管、建筑材料、陈列柜、曲面窗等。
这样，本实施方式的多层构造体为具有厚度10μm以上200μm以下的玻璃层与树脂层的多层构造体，以一个玻璃层与一个树脂层的层叠构造为单位层叠构造，在多层构造体的厚度方向中，单位层叠构造的数量为5层以上20000层以下。由此，本实施方式的多层构造体在采用吸收高强度的冲击的玻璃层与树脂层的多层复合构造的同时轻量，并且不止平面，其能够任意成形为曲面、圆筒的形状。
以上，对优选实施方式等进行了详细说明，但不限于上述实施方式等，能够不超出权利要求书记载的范围地对上述实施方式等添加各种变形和置换。
本国际申请要求基于2019年9月26日申请的日本专利申请2019-175837号的优先权，在本国际申请中引用日本专利申请2019-175837号的全部内容。

Claims (6)

1.一种多层构造体，其具有厚度为10μm以上200μm以下的玻璃层、以及树脂层，
将一个玻璃层与一个树脂层的层叠构造作为单位层叠构造，
在上述多层构造体的厚度方向上，上述单位层叠构造的数量为5层以上20000层以下。
2.根据权利要求1所述的多层构造体，其中，
在上述单位层叠构造中，上述树脂层具有:
树脂薄膜，其具有挠性；以及
粘接层或粘合层，其设于上述玻璃层与上述树脂薄膜之间。
3.根据权利要求1所述的多层构造体，其中，
在上述单位层叠构造中，上述树脂层为中间膜。
4.根据权利要求3所述的多层构造体，其中，
上述中间膜为聚乙烯醇缩醛类树脂或聚卤乙烯树脂。
5.根据权利要求1至4中任一项所述的多层构造体，其中，
上述单位层叠构造彼此通过粘接层或粘合层层叠。
6.根据权利要求1至5中任一项所述的多层构造体，其中，
该多层构造体为筒状。
CN202080066849.2A 2019-09-26 2020-09-17 多层构造体 Pending CN114521174A (zh)

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