CN1604932A - 用于复合安全玻璃的具有较小自粘性的薄膜 - Google Patents
用于复合安全玻璃的具有较小自粘性的薄膜 Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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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- B32B17/10761—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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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/31627—Next to aldehyde or ketone condensation product
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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- Laminated Bodies (AREA)
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- Adhesives Or Adhesive Processes (AREA)
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Abstract
本发明涉及基于部分缩醛化的聚乙烯醇，特别是PVB的含增塑剂的薄膜，其作为复合安全玻璃的中间层，该薄膜除了与玻璃具有所需的足够粘合力外，还没有不希望的自粘性(粘着倾向)。量为0.001－0.1重量％的季戊四醇酯被用作降低自粘性的添加剂。该添加剂不改变薄膜与玻璃的粘合力。本发明用来制备用于复合安全玻璃制备中的薄膜。大大降低了为了堆叠或卷绕而冷却薄膜的必要性。
Description
技术领域
复合安全玻璃，由两块玻璃和一层连结玻璃的粘合薄膜组成，该粘合薄膜由部分缩醛化的含增塑剂的聚乙烯醇，优选由聚乙烯醇缩丁醛(PVB)制成，该复合安全玻璃尤其在汽车中做为挡风玻璃使用，如果需要，可以用塑料代替玻璃，尤其是由无定形聚酰胺、透明PMMA、聚碳酸酯或聚酯制成的塑料。这样的硅酸盐玻璃/硅酸盐玻璃或硅酸盐玻璃/塑料的复合材料还使用在建筑业，例如作为窗玻璃或隔离墙，其中，如果需要，根据其用途，例如做为复合防弹玻璃，也可以使用多层复合材料，即由两块以上承载层构成的复合材料。
用于建筑业的复合安全玻璃，玻璃和粘合薄膜之间一般应具有尽可能高的粘合力，但汽车的复合安全玻璃并不要求太高的粘合力。复合安全玻璃一般是由两块玻璃块和一层连结合玻璃的粘合薄膜构成的。
通常，为制备复合安全玻璃，将粘合薄膜挤出，并在宽槽模具中成型后卷绕成大卷。然而粘合薄膜(以下也简称为PVB-薄膜)不仅对玻璃，而且还对邻接的绕组层具有良好的粘合力。上述性质的粘着倾向增加了操作薄膜的困难，尤其是卷起或退卷时。除卷绕制品外，含有增塑剂的PVB还作为堆叠的剪裁制品(所谓的坯料)销售，同样粘着倾向是不希望的。
因此，就本申请使用的概念聚乙烯醇缩丁醛(PVB)而言，同时还应包括这样的聚合物，其在可用性方面具有和(含有增塑剂的)聚乙烯醇缩丁醛类似的性质。例如乙烯乙酸乙烯酯或某些其它的乙烯共聚物属于此类。这里的相关性质尤其是室温时的表面粘性、柔软性和橡胶弹性。
现有技术
DE1704568A1公开了一种含有增塑剂的且表面无光泽的聚乙烯醇缩丁醛薄膜的制备方法，该方法中，含有需要水量的PVB-薄膜与一个起分离层作用的衬层卷绕在一起，该衬层任选由无光泽的聚烯烃薄膜构成，这样得到的卷气密地和不透湿气地包装。不过这些所谓中间分隔薄膜的使用是相当繁琐的。
DE1927936A1公开了一种含有增塑剂的且粘合倾向较小的聚乙烯醇缩丁醛薄膜的制备方法，洗涤后的薄膜具有两侧粗糙化的表面。此外，对挤出后仍处于热状态的薄膜敷粉，或如果需要，将相对薄膜呈惰性的、水溶且不吸湿的物质(优选晶体和无色物质)，通过热压固定在薄膜上。不过该方法耗费很大。
此外，很多发明通过特殊的表面冲压或其它方式形成特别的表面结构，来暂时减小含增塑剂的聚乙烯醇缩丁醛薄膜的粘性(例如EP0710545A1、EP0185863B1)。不过，由此达到的效果都不足以使薄膜绕组在通常的环境温度下传送。尽管进行了表面形态最优化，但由PVB-薄膜制成的卷几乎都是或者与中间分隔薄膜一起提供，或者作为所谓的冷薄膜使用。对此卷绕前还将薄膜冷却到4-10℃。必须在10℃下，不间断地将制成的薄膜绕组冷藏，直到进一步加工。
通过改性PVB-树脂、增塑剂，或通过加入粘性减小的物质，来减小PVB-薄膜的粘着倾向的配方已经公开了(US4999078A1、EP0067022B2)。不过一般来说，这些方法的缺点在于，在之后的层压时薄膜在玻璃上的粘合力受到影响，或者其作用不够高，不能避免耗费很大的冷却。这些方法的另一缺点在于，改性的PVB-树脂和增塑剂的商业供应是很有限的。因此迄今这些方案不能在市场上实施。
目的
本发明的目的是，提供一种适合作为复合安全玻璃的中间层的含有增塑剂的基于部分缩醛化的聚乙烯醇的薄膜，以及具有这种薄膜的复合安全玻璃，该薄膜适合作为复合安全玻璃的中间层，并无上述缺陷。
发明描述
本发明的核心是使用某些季戊四醇酯来阻止薄膜自身的粘合。
令人惊奇地发现，特别小的浓度的某些季戊四醇酯已经适合于显著减小塑性聚乙烯醇缩丁醛薄膜的自粘性，而不影响层合后与玻璃的粘合力。而且完全未改变所有其它的薄膜性质，例如薄膜机械性能或高的透明度。
本发明应用的季戊四醇酯尤其是四硬脂酸季戊四醇酯和(单、二或三)—己二酸—硬脂基季戊四醇酯，尤其后者为同分异构体的混合物时，是特别适合的添加剂。
本发明使用的季戊四醇酯是季戊四醇(一种四元醇)的酯，其中一个或多个醇基团被一元或多元羧酸所取代。酯化所用的酸优选长链酸，尤其是带有12
至21碳原子的。权利要求2至5中给出了优选的季戊四醇酯。
优选的季戊四醇酯的量为0.002-0.005重量％，即20-50ppm时，业已具有可察觉的抗粘结作用。以薄膜的重量计，优选使用0.01-0.1重量％的季戊四醇酯。用量大于1重量％，存在薄膜混浊的危险，所以通常应避免使用季戊四醇酯含量高的薄膜作为复合安全玻璃的中间层。
特别有利的是将季戊四醇酯首先加入并分散在所用的增塑剂中，或者，如果其是可溶的，则将其溶解在增塑剂中。然后以已知方式制备薄膜，例如根据EP0185863B1，在宽槽模具上通过挤出制备。挤出时季戊四醇酯如果是不溶的，则熔融在挤出物中，并均匀分布在熔融物中。
适合作为增塑剂的可以是现有技术中所有已知的增塑剂，尤其是多元酸、多元醇或低聚醚二醇的酯，例如己二酸酯、癸二酸酯或邻苯二甲酸酯，尤其是己二酸二正己酯、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肪羧酸的酯和这些酯的混合物。优选脂肪二醇与长链脂肪羧酸的酯作为标准增塑剂，尤其是三甘醇与诸如2-乙基丁酸或正庚酸的含6-10个碳原子的脂肪羧酸的酯。特别优选一种或多种选自下述的增塑剂：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肪羧酸的酯，特别是双-2-乙基丁酸三乙二醇酯(3GH)、双正庚酸三乙二醇酯(3G7)、双-2-乙基己酸三乙二醇酯(3G8)、双正庚酸四乙二醇酯(4G7)。
但本发明使用的季戊四醇酯还容许使用特别的增塑剂，例如其能够起到使薄膜隔音改善的效果，还可以参见DE19938159A1，在此引入其全部内容作为参考。其中，增塑剂尤其选自：
●聚(亚烷基)二醇，通式为
HO-(R-O)n-H，R＝亚烷基，其中，n＞5，
●由亚乙基二醇和亚丙基二醇构成的嵌段共聚物，通式为HO-(CH2-CH2-O)n-(CH2-CH(CH3)-O)m-H，其中，n＞2，m＞3，并且(n+m)＜25，
●由亚乙基二醇和亚丙基二醇构成的嵌段共聚物的衍生物，
通式为R1O-(CH2-CH2-O)n-(CH2-CH(CH3)-O)m-H或
HO-(CH2-CH2-O)n-(CH2-CH(CH3)-O)m-R1，其中，n＞2，m＞3，并且(n+m)＜25，R1是有机取代基，
●聚(亚烷基)二醇的衍生物，通式为R1-O-(R2-O)n-H，其中R2＝亚烷基并且n≥2，其中，聚(亚烷基)二醇两个端羟基之一的氢被有机取代基R1取代，
●聚(亚烷基)二醇的衍生物，通式为R1-O-(R2-O)n-R3，其中R2＝亚烷基并且n＞5，其中，聚(亚烷基)二醇的端羟基的氢分别被有机取代基R1或R3取代。
优选这些特别的增塑剂与一种或多种标准增塑剂结合使用。
通常，如果没有使用本发明的季戊四醇酯，这些特别增塑剂将使薄膜有特别高的粘着倾向，这样，在随后的层合操作时，尤其是卷绕和退卷操作将是特别成问题的。本发明使用的季戊四醇酯以协同方式造成内在地特别易于粘着的、基于部分缩醛化的聚乙烯醇缩丁醛薄膜的粘着性降低，所以特别推荐使用带有这些增塑剂的薄膜。
塑化的部分缩醛化的聚乙烯醇-树脂，以100重量份的树脂计，含有25-45重量份，特别优选30-40重量份的增塑剂。业已知道，较高含量的增塑剂造成薄膜自粘性较高。不过，使用本发明所用的季戊四醇酯容许使用较高量的增塑剂，没有这种加入则不能加工。
以已知方式通过水解的聚乙烯酯的缩醛化来制备部分缩醛化的聚乙烯醇。使用的醛例如甲醛、乙醛、丙醛、丁醛等，优选丁醛。优选的聚乙烯醇缩丁醛树脂含有10-25重量％，优选17-23重量％，特别优选19-21重量％的乙烯醇基团。需要时聚乙烯缩丁醛可以额外含有0-20重量％，优选0.5-2.5重量％的乙酯基。
薄膜的含水量优选是0.15-0.8重量％，特别是0.2-0.5重量％。
根据本发明使用的季戊四醇酯的主要优点在于，一方面，适合在复合安全玻璃中作为中间层的基于部分缩醛化的聚乙烯醇的含增塑剂的薄膜自粘合显著减少，另一方面不影响薄膜与玻璃的粘合力。
为了量化自粘性(粘着力)，EP0067022B2公开了一种所谓的T-剥离-强度-测试：两个3cm×10cm的待测试的薄膜条，在60N负载下，在20℃温度下，重叠放置48小时。随后，该条在2×90°角度下以确定的速度500mm/分钟拉开，测量拉力。此外，参见EP0067022B2中描述的T-剥离-强度-测试的部分。
T-剥离-强度-测试很适合用于确定本发明使用的季戊四醇酯有效性所需的最小量。优选以这样的浓度使用季戊四醇酯，即，其可以减小拉力至少20％，优选至少50％，特别优选至少90％。
为了评价在无机玻璃上PVB-薄膜的粘合力，根据DE19756274A1进行所谓的压缩剪切测试。为了制备试样，将待测试的PVB-粘薄膜放在两块规格是300mm×300mm、厚4mm的平面硅酸盐玻璃块之间，在具有压辊的预复合炉中排除空气，形成玻璃预复合体，然后在高压釜中，在12巴压力下和140℃温度下压制30分钟，形成平面的复合安全玻璃。将所得的复合安全玻璃切成10片尺寸为25.4mm×25.4mm的试样。将这些样品以45°角度夹紧在DE19756274A1附图1中所示的由两部分构成的试验设备中。在试样的上半部施加连续增加的、完全垂直向下的力，直到试体，即，受试的复合安全玻璃片的内部被剪开。
试验参数如下：
表1：
| 试体 | 25.4mm×25.4mm正方形 |
| 安装： | 下面的玻璃块在每种情况下朝向薄膜的是空气侧或火焰侧(空气/空气)，或者上和下面的玻璃块在每种情况下朝向薄膜的是锡侧(槽/槽) |
| 试验前放置： | 标准气氛(23℃/50％相对湿度)下，4小时 |
| 进刀： | 2.5mm/分钟 |
| 样品数量： | 10 |
| 计量： | 将薄膜剪离玻璃所需的最大力。该力与样品表面相关(单位N/mm2或psi) |
对于每个实施例，将10个同样的样品剪离时所施加的力进行算术平均。随后的实施例和权利要求中如果涉及平均压缩剪切值，均是指10次测量的平均值。其余按照DE19756274A1所述。
实施本发明和对比实施例的方法
对比实施例1和实施例2-4
向乙烯醇基团含量为20.5重量％和乙烯基乙酸酯基团含量为0.8重量％的74重量份聚乙烯醇缩丁醛树脂中，加入26重量份作为增塑剂的双-2-庚酸三乙二醇酯(3G7)与0.15重量份的UV吸收剂TinuvinP(制造商：Ciba公司)。将含量如下表中给出的四硬脂酸季戊四醇酯(Lonza公司的Fabrikat GlycolubeP)事先分散在增塑剂中。在约200℃的熔体温度下，将该混合物在装配有宽缝模头的双螺杆挤出机中挤压成透明的膜，膜厚0.38mm，带有粗糙的表面RZ＝18μm。所有样品的薄膜的含水量均约为0.45重量％。
表2
| 配方 | 对比实施例1 | 实施例2 | 实施例3 | 实施例4 |
| 聚乙烯醇缩丁醛-树脂[重量份] | 74.0 | 74.0 | 74.0 | 74.0 |
| 增塑剂3G7[重量份] | 26.0 | 26.0 | 26.0 | 26.0 |
| UV吸收剂[重量份] | 0.15 | 0.15 | 0.15 | 0.15 |
| 四硬脂酸-季戊四醇酯[重量％] | 0 | 0.001％ | 0.0025％ | 0.005％ |
| 压缩剪切测试空气/空气[N/mm2] | 27.7 | 28.1 | 30.1 | 29.7 |
| 锡/锡[N/mm2] | 17.5 | 18.3 | 17.9 | 17.4 |
| 粘着力(按照EP0067022B2)[N/30mm] | 25 | 24 | 17 | 8 |
可以看出，加入约0.0025重量％＝25ppm的四硬脂酸-季戊四醇酯作为季戊四醇酯已经明显引起粘着力减小，而玻璃粘合力(压缩剪切测试)在测量精度内保持改变。加入约0.005重量％＝50ppm的四硬脂酸-季戊四醇酯已经产生几乎70％的粘着力降低，降到8[N/30mm]。
对比实施例5、实施例6-9
如实施例1描述的同样方式进行操作，不过按下表3所示，采用更大梯度的四硬脂酸-季戊四醇酯(GlycolubeP)。使用乙烯醇基团含量为20.5重量％和乙烯基乙酸酯基团含量为0.8重量％的聚乙烯醇缩丁醛树脂。只使用0.01重量％的四硬脂酸-季戊四醇酯类型的季戊四醇酯使粘着力减少到1.2[N/30mm]，即减少约95％。将四硬脂酸-季戊四醇酯份额提高到0.02％＝200ppm，使粘着力进一步下降到小于初始值的1.5％，而进一步提高四硬脂酸-季戊四醇酯的份额只使粘着力减小很小。
表3
| 配方 | 对比实施例5 | 实施例6 | 实施例7 | 实施例8 | 实施例9 |
| 聚乙烯醇缩丁醛-树脂[重量份] | 74.0 | 74.0 | 74.0 | 74.0 | 74.0 |
| 增塑剂3G7[重量份] | 26.0 | 26.0 | 26.0 | 26.0 | 26.0 |
| UV吸收剂[重量份] | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| 四硬脂酸-季戊四醇酯[重量％] | 0 | 0.01％ | 0.02％ | 0.03％ | 0.04％ |
| 压缩剪切测试空气/空气[N/mm2] | 27.7 | 28.7 | 27.4 | 24.5 | 22.5 |
| 锡/锡[N/mm2] | 17.5 | 19.1 | 19.3 | 17.7 | 15.2 |
| 粘着力(按照EP0067022B2)[N/30mm] | 25 | 1.2 | 0.30 | 0.22 | 0.20 |
四硬脂酸-季戊四醇酯的量的影响如此显著，以至于完全可以不用将薄膜冷却到约30-40℃温度。在制备、运输和使用本发明薄膜时大大地节省了。
(对比)实施例10-12
如实施例1描述的同样方式进行操作，但按下表4所示，采用己二酸-硬脂基-季戊四醇酯(Pentaerythrit-adipato-stearat)，类型为Rohm & Haas公司的AdvalubeE-2100。AdvalubeE-2100是单-己二酸-硬脂基-季戊四醇酯、二-己二酸-硬脂基-季戊四醇酯和三-己二酸-硬脂基-季戊四醇酯的异构体混合物，即一至三取代的季戊四醇酯的混合物。使用0.04重量％的这种季戊四醇酯使粘着力减少到1.0[N/30mm]，即减少约95％。将(单、二、三)-己二酸-硬脂基-季戊四醇酯提高到0.1％＝1000ppm，使粘着力进一步下降到小于初始值的1％。
表4
| 配方 | 对比实施例10 | 实施例11 | 实施例12 |
| 聚乙烯醇缩丁醛-树脂[重量份] | 74.0 | 74.0 | 74.0 |
| 增塑剂3G7[重量份] | 26.0 | 26.0 | 26.0 |
| UV吸收剂[重量份] | 0.15 | 0.15 | 0.15 |
| 己二酸-硬脂基-季戊四醇酯[重量％] | 0 | 0.04％ | 0.10％ |
| 压缩剪切测试空气/空气[N/mm2] | 27.7 | 24.1 | 23.9 |
| 锡/锡[N/mm2] | 17.5 | 16.1 | 14.9 |
| 粘着力(按照EP0067022B2)[N/30mm] | 25 | 1.0 | 0.2 |
对比实施例13、实施例14
如实施例1描述的同样方式进行操作，但作为增塑剂应用增加量的由己二酸二正己酯(DHA)和Condea公司的MarlophenNP构成的混合物，后者为双侧被取代的PEG，聚乙二醇含量为6个DP，并且在两个羟基封端之一为异壬基苯酚。如DE19938159A1所述，该薄膜配方使薄膜具有明显改善的吸音性能。没有根据本发明添加四硬脂酸-季戊四醇酯产生(明显看出)小的粘着力，为11[N/30mm]。不过由于所用的增塑剂量和配方的原因，薄膜基本上比标准薄膜软，自粘性已经妨碍了对薄膜进行大量的操作。添加0.04重量％的四硬脂酸-季戊四醇酯使该值下降到0.12[N/30mm]，或约初始值的1％，根本上改善了薄膜的可操作性。
表6
| 配方 | 对比实施例13 | 实施例14 |
| 聚乙烯醇缩丁醛-树脂[重量份] | 66.0 | 66.0 |
| 增塑剂DNA[重量份] | 22.0 | 22.0 |
| 增塑剂NP6(重量份) | 12.0 | 12.0 |
| UV吸收剂[重量份] | 0.15 | 0.15 |
| 四硬脂酸-季戊四醇酯[重量％] | 0 | 0.04％ |
| 压缩剪切测试空气/空气[N/mm2] | 20.5 | 20.5 |
| 锡/锡[N/mm2] | 10.5 | 11.5 |
| 粘着力(按照EP0067022B2)[N/30mm] | 10.9 | 0.12 |
Claims (13)
1.一种基于部分缩醛化的聚乙烯醇的适合作为复合安全玻璃中间层的含增塑剂的薄膜，其特征在于，加入一种或多种下述通式组成的组成季戊四醇酯：
其中
R1、R2、R3＝
或者
或者
-CH2-O-R7
其中R5、R5’＝带有1-26个碳原子的饱和或不饱和的烃基，并且R7＝H、烷基或芳基，
并且，R4＝
其中R5、R5’＝带有1-26个碳原子的饱和或不饱和的烃基。
2.根据权利要求1的含增塑剂的薄膜，其特征在于，加入一种或多种下述通式组成的季戊四醇酯：
其中
R1、R2、R3＝
或者
或者
-CH2-O-R7
在各种情况下，R7、R8、R8’、R9、R9’＝H、烷基或芳基，并且m、m’＝1-26
并且，R4＝
在各种情况下，R8、R8’、R9、R9’＝H、烷基或芳基，并且m、m’＝1-26。
3.根据权利要求2的含增塑剂的薄膜，其特征在于，使用下式的季戊四醇酯：
其中
n＝0-2
并且m＝11-20
或者
其中
n’＝1-3
并且m’＝11-20。
4.根据权利要求3的含增塑剂的薄膜，其特征在于，使用四硬脂酸-季戊四醇酯作为季戊四醇酯。
5.根据权利要求4的含增塑剂的薄膜，其特征在于，使用下式的(单、二或三)己二酸-硬脂基-季戊四醇酯作为季戊四醇酯：
其中n＝1、2或3。
6.根据权利要求1至5之一的含增塑剂的薄膜，其特征在于，以薄膜总量计，使用总量大于0.002重量％，尤其是0.01-0.1重量％的一种或多种季戊四醇酯。
7.根据权利要求1至6之一的含增塑剂的薄膜，其特征在于，季戊四醇酯或者均匀溶解在薄膜中，或者分散在薄膜中。
8.权利要求1至7之一的含增塑剂的薄膜，含有的一种或多种增塑剂，选自：
·己二酸酯，
·癸二酸酯，，
·邻苯二甲酸酯，
·二甘醇、三甘醇或四甘醇与直链或支链脂肪羧酸的酯，特别是双-2-乙基丁酸三乙二醇酯(3GH)、双正庚酸三乙二醇酯(3G7)、双-2-乙基己酸三乙二醇酯(3G8)、双正庚酸四乙二醇酯(4G7)。
9.根据权利要求1至8之一的含增塑剂的薄膜，含有的一种或多种增塑剂，选自：
·聚亚烷基二醇，通式为
HO-(R-O)n-H，R＝亚烷基，n＞5，
·由亚乙基二醇和亚丙基二醇构成的嵌段共聚物，通式为HO-(CH2-CH2-O)n-(CH2-CH(CH3)-O)m-H，n＞2，m＞3，并且(n+m)＜25，
·由亚乙基二醇和亚丙基二醇构成的嵌段共聚物的衍生物，
通式为R1O-(CH2-CH2-O)n-(CH2-CH(CH3)-O)m-H或
HO-(CH2-CH2-O)n-(CH2-CH(CH3)-O)m-R1，其中n＞2，m＞3，并且(n+m)＜25，R1是有机取代基，
·聚亚烷基二醇的衍生物，通式为R1-O-(R2-O)n-H，R2＝亚烷基并且n≥2，其中，聚亚烷基二醇两个端羟基之一的氢被有机取代基R1取代，
·聚亚烷基二醇的衍生物，通式为R1-O-(R2-O)n-R3，其中R2＝亚烷基并且n＞5，其中，聚亚烷基二醇的端羟基的氢分别被有机取代基R1或R3取代。
10.一种或多种酯在制备用于复合安全玻璃的基于部分缩醛化的聚乙烯醇挤出薄膜中作为降低自粘性的添加剂的用途，该酯选自：
-以下通式组成的季戊四醇酯：
其中
R1＝H、烷基或芳基
R2＝H、烷基或芳基
R3＝H、烷基或芳基
n＝0-3
m＝1-26
-以下通式组成的季戊四醇己二酰羧酸酯：
其中
R1＝H、烷基或芳基
R2＝H、烷基或芳基
R3＝H、烷基或芳基
n＝0-3
m＝1-26。
11.根据权利要求10的用途，其特征在于，使用这样浓度的季戊四醇酯，即，该浓度减小自粘性(粘着力)，按照EP0067022B2的T-剥离-强度-测试测得的拉力至少50％。
12.复合安全玻璃，至少具有一玻璃块和一与该玻璃块邻接的根据权利要求1至9之一的基于部分缩醛化的聚乙烯醇的薄膜。
13.一种没有中间层、直接卷绕成卷轴的根据权利要求1至9之一的薄膜的运输和/或存放，其特征在于，至少暂时加热卷轴到至少20℃温度。
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| DE10162338A DE10162338A1 (de) | 2001-12-18 | 2001-12-18 | Folie für Verbundsicherheitsscheiben mit verringerter Eigenklebrigkeit |
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| JP (1) | JP2005511881A (zh) |
| CN (1) | CN100343319C (zh) |
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| AU (1) | AU2002357978B2 (zh) |
| BR (1) | BR0215150B1 (zh) |
| CA (1) | CA2469014A1 (zh) |
| DE (3) | DE10162338A1 (zh) |
| DK (1) | DK1430094T3 (zh) |
| ES (1) | ES2231730T3 (zh) |
| MX (1) | MXPA04006448A (zh) |
| PT (1) | PT1430094E (zh) |
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| CN102203157B (zh) * | 2008-08-28 | 2014-11-26 | 埃默里油脂化学有限公司 | 用于聚醚多元醇的降粘剂 |
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| DE10327517A1 (de) | 2003-06-17 | 2005-01-13 | Ht Troplast Ag | Ionenleitende thermoplastische Zusammensetzungen für elektrochrome Verglasungen |
| DE10331648A1 (de) * | 2003-07-12 | 2005-01-27 | Ht Troplast Ag | Folie für Verbundsicherheitsscheiben mit geringer Eigenklebrigkeit und guter Glashaftung |
| DE102004030411A1 (de) * | 2004-06-23 | 2006-01-19 | Kuraray Specialities Europe Gmbh | Solarmodul als Verbundsicherheitsglas |
| DE102004000053A1 (de) * | 2004-11-23 | 2006-05-24 | Kuraray Specialities Europe Gmbh | Verbundverglasungen mit hoher Energieaufnahme und hierfür geeignete Zwischenschichtfolien |
| TW200741037A (en) | 2006-01-30 | 2007-11-01 | Ibiden Co Ltd | Plating apparatus and plating method |
| US8197928B2 (en) * | 2006-12-29 | 2012-06-12 | E. I. Du Pont De Nemours And Company | Intrusion resistant safety glazings and solar cell modules |
| DE102007021103A1 (de) | 2007-05-03 | 2008-11-06 | Kuraray Europe Gmbh | Herstellung von Folien für Verbundverglasungen durch Spritzgieß- oder Spritzprägeverfahren |
| EP2067813A1 (de) | 2007-12-03 | 2009-06-10 | Kuraray Europe GmbH | Glykol- und Glycerinester als Antiblockmittel für Zwischenschichtfolien für Verbundglas |
| JP5308444B2 (ja) * | 2007-12-18 | 2013-10-09 | 株式会社クラレ | 合わせガラス用中間膜、その製造方法及びそれを用いた合わせガラス |
| DE102008043393B4 (de) | 2008-11-03 | 2011-03-17 | Kuraray Europe Gmbh | Verfahren zum Spritzgießen von thermoplastischen Polymermassen mit kontinuierlichen Eigenschaftsübergängen |
| DE102009007762A1 (de) * | 2009-02-06 | 2010-08-12 | Bayer Materialscience Ag | Folienmehrschichtverbund mit einer Schicht aus Polycarbonat |
| DE102009001629A1 (de) * | 2009-03-18 | 2010-09-23 | Kuraray Europe Gmbh | Photovoltaikmodule enthaltend plastifizierte Zwischenschicht-Folien mit hoher Strahlungstransmission |
| EP2259335A1 (de) | 2009-05-15 | 2010-12-08 | Kuraray Europe GmbH | Photovoltaikmodule enthaltend plastifizierte Zwischenschicht-Folien mit reduzierter Eigenklebrigkeit |
| JP6978315B2 (ja) | 2014-10-13 | 2021-12-08 | モノソル リミテッド ライアビリティ カンパニー | 水溶性ポリビニルアルコールブレンドフィルム、関連方法及び関連物品 |
| TWI689547B (zh) | 2014-10-13 | 2020-04-01 | 美商摩諾索公司 | 具有塑化劑摻合物的水溶性聚乙烯醇膜、相關方法及相關物品 |
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| US4128694A (en) * | 1977-05-09 | 1978-12-05 | Monsanto Company | Laminates comprising a plasticized interlayer |
| US4537828A (en) * | 1983-08-12 | 1985-08-27 | Monsanto Company | Laminates comprising plasticized polyvinyl butyral interlayers |
| DE3466701D1 (en) * | 1983-08-12 | 1987-11-12 | Monsanto Co | Plasticized polyvinyl butyral interlayers process for forming same and plasticizer blend therefor |
| US5852158A (en) * | 1997-08-29 | 1998-12-22 | General Electric Company | Thermoplastically moldable compositions |
| DE19938159A1 (de) | 1999-08-16 | 2001-02-22 | Huels Troisdorf | Verbundsicherheitsglas sowie PVB-Folie zu seiner Herstellung |
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| Publication number | Publication date |
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| US20050079363A1 (en) | 2005-04-14 |
| CN100343319C (zh) | 2007-10-17 |
| ATE284431T1 (de) | 2004-12-15 |
| BR0215150B1 (pt) | 2012-03-06 |
| JP2005511881A (ja) | 2005-04-28 |
| MXPA04006448A (es) | 2005-02-24 |
| US7250217B2 (en) | 2007-07-31 |
| EP1430094A1 (de) | 2004-06-23 |
| DE10162338A1 (de) | 2003-07-03 |
| WO2003051974A1 (de) | 2003-06-26 |
| DE10295843D2 (de) | 2004-11-04 |
| RU2325408C9 (ru) | 2009-04-10 |
| AU2002357978A1 (en) | 2003-06-30 |
| PT1430094E (pt) | 2005-03-31 |
| RU2004122117A (ru) | 2006-01-20 |
| DE50201754D1 (de) | 2005-01-13 |
| UA77734C2 (en) | 2007-01-15 |
| DK1430094T3 (da) | 2005-01-24 |
| CA2469014A1 (en) | 2003-06-26 |
| RU2325408C2 (ru) | 2008-05-27 |
| AU2002357978B2 (en) | 2007-11-01 |
| BR0215150A (pt) | 2004-10-19 |
| ES2231730T3 (es) | 2005-05-16 |
| ZA200404076B (en) | 2005-07-27 |
| EP1430094B1 (de) | 2004-12-08 |
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