CN1173823C - 由部分缩醛化的聚乙烯醇制成的含增塑剂的薄膜 - Google Patents
由部分缩醛化的聚乙烯醇制成的含增塑剂的薄膜 Download PDFInfo
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Abstract
本发明涉及由部分缩醛化的聚乙烯醇，特别是聚乙烯缩丁醛(PVB)制成的含增塑剂的薄膜，该薄膜大规模地作为复合安全玻璃的中间层使用。所述的薄膜的硅酸盐玻璃上的粘结力通常通过加入碱金属或碱土金属化合物来调节。然而，已知的调节粘结力的添加剂不利地改变薄膜的光学和化学性能。根据本发明，通过加入无定形二氧化硅，特别是热解硅酸提高粘结力。将以薄膜的重量计0.01至0.25重量%的无定形二氧化硅分散在增塑剂中，并与聚乙烯缩丁醛树脂一起挤压。无定形二氧化硅的加入使平均压缩剪切试验值提高10%以上。本发明的薄膜在复合安全玻璃中作为中间层使用。
Description
技术领域
本发明涉及由部分缩醛化的聚乙烯醇制成的含增塑剂的薄膜，该薄膜作为复合安全玻璃的中间层使用。
复合安全玻璃由二块玻璃板和用于粘结玻璃的由部分缩醛化的聚乙烯醇，优选聚乙烯醇缩丁醛(PVB)制成的粘结薄膜组成，其特别地在汽车工业中作为挡风玻璃使用，这里，如果需要，一块玻璃板可由塑料板，特别是由无定形聚酰胺、透明PMMA、聚碳酸酯或聚酯制成的塑料板代替。这样的硅酸盐玻璃/硅酸盐玻璃或硅酸盐玻璃/塑料复合材料同样也在建筑领域中作为窗玻璃或隔墙，其中，如果需要，根据其用途，例如作为复合装甲玻璃，也可以使用多层复合材料，即由二块以上承压层组成的复合材料。
用于建筑领域的复合安全玻璃，玻璃和粘结薄膜之间一般应该具有尽可能高的粘结力，而对于汽车工业中的复合安全玻璃力求一定的、不太高的粘结力。
现有技术
已知通过加入各种不同的例如以氢氧化物、盐、络合物形式存在的碱金属或碱土金属化合物来降低薄膜对玻璃的粘结力(DE 15 96 902B、DE 15 96 894 B、US 3,249,488 A、US 3,249,489A、US 3,262,835 A、US 3,262,836A)。
这类碱性反应性化合物的缺陷在于增塑聚乙烯缩丁醛树脂的化学变化，即由于聚乙烯缩丁醛/增塑剂体系的损坏出现变色，以及由于不太令人满意的耐湿性所获得的复合安全玻璃出现混浊现象。变色和混浊影响复合安全玻璃的透明性。此外，另一结果是，由于碱度分子大小例如聚合物的摩尔重量和摩尔质量分布以及抗老化性发生变化。此外在薄膜周围润湿时，粘结力降低，薄膜从玻璃上脱落。
由DE 24 10 153 C3已知，借助于硅官能化和硅有机官能化硅烷调节部分缩醛化的含增塑剂的聚乙烯醇的粘结力，其中硅官能化的硅烷降低粘结力，硅有机官能化的硅烷提高粘结力。
然而，根据工艺条件，硅烷化合物的加入导致所使用的树脂有时发生难以控制的局部交联反应，因此形成明显的凸起。
由EP 0 227 633 A2已知一种用于具有高耐湿性的复合安全玻璃的中间层，其中加入大量的改善耐湿性的添加剂如有机磷酸盐和亚磷酸盐以及成核添加剂如硅灰。但该申请中没有公开少量无定形二氧化硅对中间层在玻璃上的粘结力的有利影响。
发明目的
因此，本发明的目的是提供由部分缩醛化的聚乙烯醇制成的含增塑剂的薄膜以及其制备方法，该薄膜适合于作为复合安全玻璃中的中间层，并且无上述缺陷。
发明描述
本发明的目的是通过权利要求1的含增塑剂的薄膜和权利要求6和7的方法并优选组合从属权利要求的一个或多个特征来实现的。
令人惊奇地发现，加入少量无定形二氧化硅可以明显提高由部分缩醛化的聚乙烯醇制成的薄膜和硅酸盐玻璃之间的粘结力。
无定形二氧化硅在大工业生产中作为沉淀硅酸是通过使用无机酸由碱金属硅酸盐的水溶液沉淀出的，或者是作为高温水解产生的热解硅酸制备的(参见Roempp-Chemie-Lexikon(Roempp化学百科全书)，第9版，第3卷，第2236页)。对于本发明特别适合的是热解硅酸。
优选无定形二氧化硅的用量在每种情况下以薄膜的重量计是0.001至0.25重量％，特别优选是0.01至0.25重量％。在使用高含量的无定形二氧化硅时存在薄膜混浊的危险，所以，一般不考虑使用无定形二氧化硅含量高的薄膜作为复合安全玻璃的中间层。
证明特别有利地是，首先将加入的无定形二氧化硅分散在所使用的增塑剂中。部分缩醛化的聚优选醇薄膜的制备按照本身已知的方法进行，例如通过借助于EP 0 185 863 B1的宽缝式设备进行挤压。
适合的增塑剂是所有现有技术中已知的增塑剂，特别是多元酸、多元醇或低聚醚甘醇的酯，例如己二酸二正己酯、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和这些酯的混合物。
优选的增塑剂首先是脂肪二元醇与长链脂族羧酸的酯，特别是三乙二醇与含6至10个碳原子的脂族羧酸如2-乙基丁酸或正庚酸的酯。以100重量份树脂计，部分缩醛化的增塑聚乙烯醇树脂优选包括25至45重量份，特别优选包括30至40重量份的增塑剂。
部分缩醛化聚乙烯醇以已知的方式通过水解聚乙烯酯的缩醛化反应制备。使用的醛例如是甲醛、乙醛、丙醛、丁醛等，优选是丁醛。优选的聚乙烯缩丁醛树脂包括10至25重量％，优选17至23重量％，特别优选19至21重量％的乙烯醇基团。聚乙烯缩丁醛如果需要还附加地包括0至20重量％，优选0.5至2.5重量％的乙酸酯基团。
薄膜的含水量优选是0.15至0.8重量％，特别是0.2至0.5重量％。
为了制备复合安全玻璃，将本发明的薄膜例如放置在厚度相同或不同的玻璃板之间，在40至100℃下压制成预复合材料。最终的复合材料的制备例如在高压釜中，在120至150℃和8至14巴下压制10至60分钟，优选20至40分钟。
为了评价PVB薄膜在无机玻璃上的粘结力。根据下面的描述进行所谓的压缩剪切试验。为了制备试件，将待试验的PVB粘结薄膜放置在二块规格是300毫米×300毫米、厚度是4毫米的硅酸盐玻璃之间，在具有压辊的预复合炉中排除空气，形成玻璃预复合材料，然后在高压釜中，在12巴压力和140℃温度下，压制30分钟，形成平坦的复合安全玻璃。将这样制备的复合安全玻璃切割成10个尺寸是25.4毫米×25.4毫米的试样。将这些试样以45℃的角度夹紧在附图1所示的由二部分组成的试验设备中。给上半部分供给持续增大的完全垂直向下的力，直至试件即受试的复合安全玻璃的内部被剪断。
试验参数如下：
表1
| 试件 | 25.4毫米×25.4毫米正方形 |
| 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)或上和下的玻璃块在每种情况下朝向薄膜的是锡侧(锡槽/锡槽) |
| 试验之前存放 | 在正常气候(23℃/50％RLF)下4小时 |
| 进刀 | 2.5毫米/分钟 |
| 试样数目 | 10 |
| 计量 | 将薄膜与玻璃剪断所需的最大力。该力与试样表面有关(单位N/mm2或psi) |
对于每个实施例，在剪断上所施加的力是10个相同试件的线性平均值。在随后的实施例和权利要求书中只要涉及平均压缩剪切试验值均是指10次测试的平均值。
量非常少的无定形二氧化硅可以明显提高PVB薄膜和玻璃之间的粘结力。优选无定形二氧化硅的加入量使粘结力(平均压缩剪切试验值)提高至少10％。优选该平均压缩剪切试验的绝对值是(空气/空气)＞4000[psi](＞27.57N/mm2)或者(锡槽/锡槽)＞3000[psi](＞20.68N/mm2)。
实施本发明的实施例和对比实施例
在100重量份乙烯醇含量是20.5重量％和乙烯基乙酸酯含量是0.7重量％的聚乙烯缩丁醛树脂中加入32重量份作为增塑剂的三甘醇双-2-庚酸酯和0.15重量份UV-吸收剂TinuvinP(制造商：Fa.Ciba)。含量如下表中给出的不同类的无定形二氧化硅首先分散在增塑剂中。将该混合物在具有宽缝喷嘴的双螺杆挤压机中在约200℃的物科温度下挤压成厚度是0.38毫米的透明薄膜。在所有的试样中湿含量总计是0.47重量％。
表2
| 无定形二氧化硅的种类 | 硅酸中二氧化硅的含量(重量％) | 薄膜中的含量(重量％) | 平均压缩剪切试验值空气/空气(psi) | 平均压缩剪切试验值锡槽/锡槽(psi) |
| Sylobloc41 | 99.9 | 0.15 | 4900 | 3320 |
| Sylobloc47 | 99.9 | 0.15 | 5040 | 3290 |
| Sylobloc622 | 约50 | 0.15 | 4760 | 2930 |
| 无 | - | - | 3640 | 2210 |
如上面的实施例所述，表3中的无定形二氧化硅以不同的浓度加入薄膜中，并试验由含每种PVB薄膜的复合安全玻璃对无机薄膜的粘结力。为了进行比较，制备不加入无定形二氧化硅的薄膜(表3)。在所有的试样中湿含量总计是0.47重量％。
表3
| 无定形二氧化硅的种类 | 薄膜中的含量(重量％) | 平均压缩剪切试验值空气/空气(psi) | 平均压缩剪切试验值锡槽/锡槽(psi) |
| Sylobloc47 | 0.05 | 4820 | 2574 |
| Sylobloc47 | 0.10 | 4980 | 2950 |
| Sylobloc47 | 0.15 | 5040 | 3290 |
| Sylobloc47 | 0.25 | 4540 | 3300 |
| 无 | - | 3640 | 2210 |
在无定形硅酸含量超过0.25重量％，复合安全玻璃出现明显混浊。
Claims (8)
1.一种由部分缩醛化的聚乙烯醇制成的作为复合安全玻璃的中间层的含增塑剂的薄膜，其特征在于，以所述薄膜的重量计，加入0.01至0.25重量％的无定形二氧化硅。
2.权利要求1的含增塑剂的薄膜，其特征在于，使用热解硅酸作为无定形二氧化硅。
3.由部分缩醛化的聚乙烯醇制成的具有0.01至0.25重量％无定形二氧化硅的含增塑剂薄膜作为复合安全玻璃的中间层的应用。
4.权利要求3的应用，其特征在于，复合安全玻璃的压缩剪切试验值是空气/空气＞27.57N/mm2或者锡槽/锡槽＞20.68N/mm2。
5.一种由部分缩醛化的聚乙烯醇制成的作为复合安全玻璃的中间层的含增塑剂的薄膜的制备方法，其特征在于，加入基于所述薄膜重量的0.01至0.25重量％无定形二氧化硅。
6.一种由部分缩醛化的聚乙烯醇制成的作为复合安全玻璃的中间层的含增塑剂的薄膜的制备方法，其特征在于，无定形二氧化硅的加入量使粘结力，即测定的平均压缩剪切试验值，提高10％以上；
条件是所述无定形二氧化硅的量在0.01至0.25重量％之间。
7.权利要求5的方法，其特征在于，二氧化硅首先分散在增塑剂中。
8.权利要求6的方法，其特征在于，二氧化硅首先分散在增塑剂中。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19756274.4 | 1997-12-18 | ||
| DE19756274A DE19756274A1 (de) | 1997-12-18 | 1997-12-18 | Weichmacherhaltige Folie aus teilacetalisierten Polyvinylalkoholen |
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| Publication Number | Publication Date |
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| CN1284911A CN1284911A (zh) | 2001-02-21 |
| CN1173823C true CN1173823C (zh) | 2004-11-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB988136880A Expired - Fee Related CN1173823C (zh) | 1997-12-18 | 1998-12-17 | 由部分缩醛化的聚乙烯醇制成的含增塑剂的薄膜 |
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| Country | Link |
|---|---|
| EP (1) | EP1042121B1 (zh) |
| JP (1) | JP4371579B2 (zh) |
| KR (1) | KR100554212B1 (zh) |
| CN (1) | CN1173823C (zh) |
| BR (1) | BR9813742A (zh) |
| CZ (1) | CZ299771B6 (zh) |
| DE (2) | DE19756274A1 (zh) |
| ES (1) | ES2210859T3 (zh) |
| WO (1) | WO1999032283A1 (zh) |
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|---|---|---|---|---|
| DE10129422A1 (de) * | 2001-06-19 | 2003-01-02 | Huels Troisdorf | Weichmacherhaltige PVB-Folie |
| JP4578140B2 (ja) * | 2004-04-21 | 2010-11-10 | 株式会社クラレ | ポリビニルアルコールフィルム |
| AU2005260458B2 (en) * | 2004-07-06 | 2010-06-24 | Sekisui Chemical Co., Ltd. | Intermediate film for laminated glass and laminated glass |
| DE102004043907A1 (de) * | 2004-09-10 | 2006-03-16 | Kuraray Specialities Europe Gmbh | Weichmacherhaltige PVB-Folien mit Etherbindungen enthaltenden Carbonsäureestern als Co-Weichmacher |
| DE102004000053A1 (de) * | 2004-11-23 | 2006-05-24 | Kuraray Specialities Europe Gmbh | Verbundverglasungen mit hoher Energieaufnahme und hierfür geeignete Zwischenschichtfolien |
| EP1845070B1 (en) * | 2005-02-03 | 2012-10-24 | Sekisui Chemical Co., Ltd. | Intermediate film for laminated glass and laminated glass |
| US7348062B2 (en) * | 2006-06-10 | 2008-03-25 | Solutia Incorporated | Interlayers comprising modified fumed silica |
| JP4904095B2 (ja) * | 2006-06-25 | 2012-03-28 | 積水化学工業株式会社 | 含水ポリビニルアセタール樹脂フィルムの製造方法 |
| EP1977886A1 (en) * | 2007-04-05 | 2008-10-08 | Kuraray Europe GmbH | Interlayer films for laminated glazing containing modified silica |
| EP1977885A1 (en) | 2007-04-05 | 2008-10-08 | Kuraray Europe GmbH | Interlayer films for laminated glazing containing silica with specific refractive index |
| EP1977887A1 (en) * | 2007-04-05 | 2008-10-08 | Kuraray Europe GmbH | Interlayer films for laminated glazing with improved mechanical properties |
| EP2234807B1 (en) * | 2007-12-18 | 2011-06-15 | Kuraray Co., Ltd. | Interlayer film for laminated glass, method for manufacturing the same, and laminated glass containing the same |
| DE102008001505A1 (de) * | 2008-04-30 | 2009-11-05 | Kuraray Europe Gmbh | Photovoltaikmodule enthaltend plastifizierte Zwischenschicht-Folien mit niedrigem Polyvinylacetatgehalt |
| DE102008001512A1 (de) | 2008-04-30 | 2009-11-05 | Kuraray Europe Gmbh | Dünnschicht-Solarmodul als Verbundsicherheitsglas |
| DE102008001502A1 (de) * | 2008-04-30 | 2009-11-05 | Kuraray Europe Gmbh | Photovoltaikmodule mit Kieselsäure-haltigen plastifizierten Zwischenschicht-Folien |
| DE102008001507A1 (de) * | 2008-04-30 | 2009-11-05 | Kuraray Europe Gmbh | Photovoltaikmodule enthaltend plastifizierte Zwischenschicht-Folien mit hohem Alkalititer |
| DE102008042218A1 (de) * | 2008-04-30 | 2009-11-05 | Kuraray Europe Gmbh | Photovoltaikmodule enthaltend plastifizierte Zwischenschicht-Folien mit niedriger Glasübergangstemperatur |
| DE102008001654A1 (de) * | 2008-05-08 | 2009-11-12 | Kuraray Europe Gmbh | Photovoltaikmodule enthaltend plastifizierte Zwischenschicht-Folien mit hohem Durchgangswiderstand und guter Penetrationsfestigkeit |
| EP2153989B1 (de) * | 2008-08-01 | 2021-09-29 | Kuraray Europe GmbH | Mehrschichtfolien aus weichmacherhaltigem Polyvinylacetal mit schalldämpfenden Eigenschaften |
| EP2259335A1 (de) * | 2009-05-15 | 2010-12-08 | Kuraray Europe GmbH | Photovoltaikmodule enthaltend plastifizierte Zwischenschicht-Folien mit reduzierter Eigenklebrigkeit |
| EP2325001A1 (de) * | 2009-11-11 | 2011-05-25 | Kuraray Europe GmbH | Verbundverglasungen mit weichmacherhaltigen Folien geringer Kriechneigung |
| EP2425969A1 (de) | 2010-09-05 | 2012-03-07 | Kuraray Europe GmbH | Photovoltaikmodule mit mineralischen Füllstoff enthaltenden Klebefolien auf Basis Polyvinylacetal |
| EP2650267A1 (en) * | 2010-12-10 | 2013-10-16 | Kuraray Co., Ltd. | Laminated glass interlayer, method for producing same, and laminated glass using same |
| EP2722359A1 (de) | 2012-10-18 | 2014-04-23 | Kuraray Europe GmbH | PVB-Folie mit hohem UV-Schutz und geringem Gelbwert für Verbundsicherheitsglas |
| EP2813543B1 (de) | 2013-06-14 | 2018-10-24 | Kuraray Europe GmbH | PVB-Folie mit UV-Schutz und geringem Gelbwert für Verbundsicherheitsglas |
| CN103820045B (zh) * | 2014-03-08 | 2015-05-27 | 浙江天台锐华塑胶有限公司 | 一种低光畸变pvb胶片配方 |
| EP3192783B1 (en) * | 2014-09-12 | 2020-12-30 | Sekisui Chemical Co., Ltd. | Interlayer for laminated glass, and laminated glass |
| EP3095601B1 (en) | 2015-05-22 | 2023-07-05 | Kuraray Europe GmbH | Penetration resistant laminated glass manufactured with interlayer film layers having reduced adhesion and low plasticizer content |
| US10293517B2 (en) | 2015-08-30 | 2019-05-21 | Kuraray Europe Gmbh | Process for extrusion of plasticized PVB film with reduced plate-out of adhesion control agent residues |
| US20190047261A1 (en) | 2016-02-22 | 2019-02-14 | Kuraray Europe Gmbh | Laminated glass as optical combiner of hud system having an interlayer comprising a transparent insert |
| KR102368873B1 (ko) | 2018-02-21 | 2022-02-28 | 고정애 | 기업의 사회복지사 직접 고용을 통한 사회복지서비스 제공시스템 및 그 방법 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US538419A (en) * | 1895-04-30 | hunton | ||
| NL262593A (zh) * | 1960-03-31 | 1900-01-01 | ||
| DE2820780A1 (de) * | 1978-05-12 | 1979-11-15 | Dynamit Nobel Ag | Weichmacherhaltige folien aus teilacetalisierten polyvinylalkoholen |
| US4681810A (en) * | 1985-12-23 | 1987-07-21 | Monsanto Company | Fire-resistant interlayer |
| JPH0218048A (ja) * | 1988-07-07 | 1990-01-22 | Toray Ind Inc | 防曇性被膜 |
| DE4309638A1 (de) * | 1993-03-25 | 1994-09-29 | Hoechst Ag | Weichmacherhaltige Polyvinylbutyrale mit gegenüber Silikatglas verbesserten haftungsreduzierenden Eigenschaften, Verfahren zu ihrer Herstellung und ihre Verwendung |
-
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- 1997-12-18 DE DE19756274A patent/DE19756274A1/de not_active Withdrawn
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1998
- 1998-12-17 DE DE59810107T patent/DE59810107D1/de not_active Expired - Lifetime
- 1998-12-17 KR KR1020007006799A patent/KR100554212B1/ko not_active IP Right Cessation
- 1998-12-17 EP EP98965127A patent/EP1042121B1/de not_active Expired - Lifetime
- 1998-12-17 CN CNB988136880A patent/CN1173823C/zh not_active Expired - Fee Related
- 1998-12-17 WO PCT/DE1998/003703 patent/WO1999032283A1/de active IP Right Grant
- 1998-12-17 BR BR9813742-5A patent/BR9813742A/pt not_active IP Right Cessation
- 1998-12-17 JP JP2000525249A patent/JP4371579B2/ja not_active Expired - Fee Related
- 1998-12-17 ES ES98965127T patent/ES2210859T3/es not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100554212B1 (ko) | 2006-02-22 |
| JP4371579B2 (ja) | 2009-11-25 |
| KR20010024781A (ko) | 2001-03-26 |
| EP1042121B1 (de) | 2003-11-05 |
| ES2210859T3 (es) | 2004-07-01 |
| DE59810107D1 (de) | 2003-12-11 |
| CN1284911A (zh) | 2001-02-21 |
| CZ299771B6 (cs) | 2008-11-19 |
| JP2001526165A (ja) | 2001-12-18 |
| BR9813742A (pt) | 2000-10-10 |
| DE19756274A1 (de) | 1999-06-24 |
| WO1999032283A1 (de) | 1999-07-01 |
| CZ20002239A3 (cs) | 2000-11-15 |
| EP1042121A1 (de) | 2000-10-11 |
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