CN101279506A - 具有经单面压纹的基于部分缩醛化的聚乙烯醇膜的多层层压件 - Google Patents
具有经单面压纹的基于部分缩醛化的聚乙烯醇膜的多层层压件 Download PDFInfo
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Abstract
本发明涉及一种制备基于部分缩醛化的聚乙烯醇膜的方法,该膜的压纹面的粗糙度Rz=20-80μm,该方法通过在相应粗糙的压纹辊和具有一定肖氏-硬度-A的压辊之间压纹膜面。调节该膜和辊的温度以固化该结构。
Description
技术领域
本发明涉及一种用于制备基于部分缩醛化的聚乙烯醇的膜的方法,该膜一面呈光滑面和另一面通过压纹形成粗糙度,本发明还涉及该膜在制备多层层压件中的应用。
通常的复合玻璃板由玻璃/聚乙烯醇缩丁醛(PVB)/玻璃/层压件组成,并长期来均用于建筑领域或作为汽车的风挡。为改进这种复合玻璃(Verbundverglasung)的反射特性和吸收辐射的特性,如按WO97/03763可使用由两层PVB膜和一层中间功能层组成的层压件代替唯一的PVB膜。该中间层膜在玻璃上的粘附性还是通过PVB的已知的优良粘附特性来确定,该附加功能(如反射性)由功能层(如经金属蒸镀的PET膜)来实现。
在这种层压件中使用的PVB膜的两膜面必需具有不同的表面。该面向玻璃的面必需具有一定的粗糙度或结构,以可实现无泡和无混浊的层压过程。相反,该面向功能层的面必需尽可能地光滑。
已知一系列的方法可用于制备具有预定粗糙度或表面结构的PVB膜。
背景技术
一种典型的用于制备具有粗糙表面的膜的方法是由EP 0185863B1已知的熔体断裂法。熔体断裂法导改不规则(随机的)的粗糙表面。
在现有技术中还描述过的用于制备中间层膜的粗糙表面的方法是压纹法。所有通过压纹法制备的膜表面的共同特征均为规则的(非随机的)表面结构,该表面结构特别是在用真空袋压法的玻璃层压件的制备过程中具有优良的排气特性,由此可实现短的过程时间和宽的加工窗口。
EP 0741640B1描述了一种通过双压纹辊来制备两面经压纹的表面的压纹法,通过该压纹辊给该膜提供了规则的锯齿形线结构。在该膜每面上压纹的线以大于25°的角交叉,以致可防止在复合玻璃中的所谓波纹图案。
EP 1233007A1中公开了一种用于避免波纹效果的压纹方法,该方法在膜的每面上产生规则的线状压纹结构。为避免干涉现象,该两膜面的线结构具有不同的重复频率。
另一在US 5972280中描述的方法是仅应用单辊代替双压纹辊,和通过滚动和压缩空气紧贴在该辊上的结构化钢带,在压纹过程中使该膜通过压纹辊和钢带之间的间隙。
US 4671913中公开了一种用于压纹PVB膜的方法,其中该膜以单次加工过程在两个结构化的辊之间经压纹。该辊和由此该受压纹的膜具有的粗糙度Rz为10-60μm。
该所述的两面压纹方法的缺点在于,膜在辊隙中的停留时间短。由此随压纹速度提高使该压纹效果大大降低,过对工业生产过程是不利的。此外,该两面经压纹的膜不适合用于与其它中间层膜如WO97/03763中的功能膜相层压,因为在功能膜上压纹了该压纹结构。
在单面压纹方法中不出现该结果,或该结果可通过相应的选用辊表面和压纹压力来克服。如US 2003/0022015、WO 01/72509、US6077374和US 6093471中描述了一阶段和两阶段的压纹方法,其通过钢压纹辊和具有橡胶涂层的压辊来压纹PVB膜。其对该橡胶涂层或辊之间在膜上施加的力未加详述。如果辊表面太硬,则产生小的压纹区,实际上减少到一条线。这导致膜在压纹区中的停留时间短,并由此导致压纹速度低。相反,如果应用太软的辊表面,那么仅可在膜上施加不足的力,降低了压纹品质。
现有方法在压纹效率上是值得改进的。
因此本发明的任务在于,研发一种用于单面压纹基于部分缩醛化的聚乙烯醇膜的方法,其无这些缺点。
令人意外地发现,在一定肖氏-A-硬度的压纹辊和压辊之间可以足够的品质和速度压纹基于部分缩醛化的聚乙烯醇的膜。
发明内容
本发明的目的是提供一种制备基于部分缩醛化的聚乙烯醇膜的方法,该膜的第一面的粗糙度Rz=1-30μm,第二面的粗糙度Rz=20-100μm,所述方法具有下列方法步骤:
a.制备其两面粗糙度Rz=1-30μm的基于部分缩醛化的聚乙烯醇的膜,和
b.在相应的温度为80-170℃的粗糙压纹辊和温度为0-60℃的压辊之间压纹该膜的另一面,得到经压纹的表面粗糙度Rz=20-100μm的膜,
其中该压辊的肖氏-A-硬度为50-80。
本发明方法优选导致该膜的经压纹面有非随机的粗糙度。
按DIN EN ISO 4287和DIN ISO 4288测定该膜的表面粗糙度值Rz。为测定表面粗糙度所用的测量仪必需符合EN ISO 3274的要求。所用的轮廓滤波器(Profilfilter)必需符合DIN EN ISO 11562。
步骤a)的该膜的表面结构或粗糙度例如可通过相应于EP 0185863B1的所谓的流动断裂法或熔体断裂法施加,这里特别参考其内容。不同的粗糙度程度可通过有目的地改变出口缝宽和直接在喷嘴出口上的喷嘴管口温度来产生。
也可通过无熔体断裂的挤压来制备膜。备选地,还可通过US4671913中的经冷辊压的挤出和光滑化来制备膜。在本发明方法中使用其两面均有尽可能小的粗糙度的膜是优选的,因为粗结构仅可用较高的压纹耗费进行过度压纹。此外,该原始粗糙度在预复合件制备中会重新调节,以致与通过熔体断裂而粗糙化的表面相比,减少了经压纹的膜的优点。
在接下来的步骤b)的压纹方法中,在膜的一面上提供粗糙深度Rz=20-100μm,优选Rz=20-80μm,尤其是Rz=30-50μm的表面结构。
该膜的另一未经压纹的面上的粗糙深度优选为Rz=1-30,优选Rz=1-20,尤其是Rz=1-10。这种粗糙度可与步骤a)的膜的粗糙度一样,但也可在b)的压纹方法中受影响。因此通过使用相应的压辊可减少或增加原始粗糙度。
在压纹过程b)之前和/或之后可使该膜冷却到-10~+20℃,并由此固化该膜的表面结构。该冷却优选通过相应的调温冷辊进行。这时该所谓的正面冷却是可能的,即该膜的经压纹的面被冷却。备选的是该所谓的背面冷却,这时该膜的未经压纹的面被冷却。
该膜的冷却也可限于其表面。因此该膜的待压纹面的表面温度可调节到-10~+20℃。备选地,该膜的未经压纹的表面也可调节到该温度。
该压纹辊优选由金属制成,并具有与其后在膜表面所存在的结构呈负像表面平整性(Profilierung)的表面。在本发明方法中使用的压纹辊必须具有与所需膜粗糙度相当的粗糙度。在一个方法变型方案中,该经压纹的膜和压纹辊具有相同或几乎相同的粗糙度。依工艺参数、膜温度、线压力、辊压温度、辊压速度或膜速度不同,该经压纹的膜的粗糙度也可显著小于压纹辊的粗糙度。由此该压纹辊的粗糙度RZ可超过用该辊压纹的膜表面的粗糙度RZ400%,优选300%,尤其是100%。该压纹辊的温度为80-170℃,优选100-150℃和优其是110-140℃。特别优选是该压纹辊具有经涂覆的钢表面(如PTFE),以减少膜的粘附。
在本发明方法中,使膜通过压纹辊和相对旋转的压辊之间。优选向压纹辊和压辊之间膜所施加的线压为20-80N/mm,尤其是40-65N/mm。线压意指按膜宽度计的该辊对施加的压力。
该压辊的温度为0-60℃,优选10-40℃,即相对于压纹辊主动冷却。该压辊无或仅有小的粗糙度(Rz最大为10μm),并优选由具有橡胶或EPDM表面的金属芯体制成。该压辊表面的肖氏-A-硬度特别是60-75。该压辊将膜压向该压纹辊的结构化表面,并轻轻贴在压纹辊上。通过改变线压可改变该压纹区的面积和由此改变停留时间。其示意性示于图1,其中用a)表示待压纹的膜,用b)表示压纹辊和以c)表示压辊。除图中所示的膜围绕辊的导向外,还可让该膜不缠绕该辊通过该辊隙简单导向。
通过选用工艺参数即线压力、膜温度和/或辊温度、辊速度和该膜幅在辊上的缠绕角度可在给定的压纹辊的粗糙深度下影响该膜压纹的粗糙度。
该压纹过程的品质也与膜的温度恒定性和由此与该冷辊、压辊和压纹辊有关。因此优选压纹辊和/或压辊的温度差横跨其宽度和周长上内调节到小于2℃,尤其小于1℃。
图2示意性示出本发明方法的一种变型方案。该膜的运行方向以双箭头表示。具有小粗糙度的膜(a)任选在辊对(d)上调温,并在压纹辊(e)和压辊(f)之间经单面压纹。(e)和(f)如所述进行调温。接着该经单面压纹过的膜的温度可在辊对(g)中经调节,从而固化该压纹。在图2中未示出的辊用于膜的导向。为改进温度调节,该辊对(d)和(g)也可被膜缠绕,以增加该膜在辊上的停留时间。
备选地,也可通过压纹间隙直接引导该膜而不缠绕该压纹辊或压辊。本发明的这种变型方案示于图3。其中d’和g’是用于膜调温的辊对,e’和f’是压辊或压纹辊。用于在压纹前的膜调温的第一对辊d’是任选的。
这种情况下,该膜也可通过调温辊的辊隙直接即无缠绕地导向。
作为部分缩醛化的聚乙烯醇尤其可使用聚乙烯醇缩丁醛(PVB)(其可呈交联形式或未交联形式),并总是与至少一种增塑剂、染料、颜料、调节粘附性的金属盐、有机添加剂和/或无机填料相混合。
一方面在现有技术中用作此目的的已知的增塑料均适用作为部分缩醛化的聚乙烯醇的增塑剂,特别是多元酸、多元醇或低聚醚二元醇的酯,如己二酸酯、癸二酸酯、或邻苯二甲酸酯,特别是二甘醇、三甘醇或四甘醇与线型或支化脂族羧酸的酯、己二酸二正己酯、癸二酸二丁酯、邻苯二甲酸二辛酯和这些酯的混合物。作为部分缩醛化的聚乙烯醇,特别是聚乙烯醇缩丁醛的标准增塑剂,优选使用脂族二元醇与长链脂族羧酸的酯,特别是三甘醇与含6-10碳原子的脂族羧酸如2-乙基丁酸(2-)或正庚酸的酯。特别优选是选自己二酸二正己酯(DHA)、癸二酸二丁酯(DBS)、邻苯二甲酸二辛酯(DOP)、二甘醇、三甘醇或四甘醇与线型或支化脂族羧酸的酯,特别是三甘醇-双-2-乙基丁酸酯(3GH)、三甘醇-双正庚酸酯(3G7)、三甘醇-双-2-乙基己酸酯(3G8)、四甘醇-双-正庚酸酯(4G7)的一种或多种增塑剂。
在本发明的一个特别的实施方案中,可进一步降低该膜在压纹工具上的粘附性,其中在该膜材料中加入减少粘附力的物质。
作为减少粘附性的有机添加剂可使用按总混合物计的如0.01-2重量%的式I的季戊四醇:
其中R1、R2、R3、R4各为相同的或不同地选自-CH2OH、-CH2OR5、-CH2OCOR5或-CH2OCOR6-COOR5的基,R5、R6为含1-26碳原子的饱和的或不饱和的、支化的或未支化的烃基。
作为任选添加剂所用的季戊四醇或其酯在使用部分缩醛化的聚乙烯醇作为聚合物质时也便于使用特殊增塑剂例如起改进膜隔音的作用的增塑剂,参见DE 19938159A1,其内容完全引此作参考。这类特殊增塑剂特别提及选自下列的增塑剂:
·通式如下的聚亚烷基二醇
HO-(R-O)n-H,其中R=亚烷基和n>5,
·通式如下的由乙二醇和丙二醇组成的嵌段共聚物
HO-(CH2-CH2-O)n-(CH2-CH(CH3)-O)m-H,其中n>2,m>3,(n+m)<25,
·通式如下的由乙二醇和丙二醇组成的嵌段共聚物的衍生物
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,(n+m)<25,和R1为有机基,
·通式如下的聚亚烷基二醇的衍生物
R1-O-(R2-O)n-H,其中R2=亚烷基和n≥2,该聚亚烷基二醇的两个终端羟基之一的氢由有机基R1取代,
通式如下的聚亚烷基二醇的衍生物R1-O-(R2-O)n-R3,其中R2=亚烷基和n>5,该聚亚烷基二醇的终端羟基的氢由有机基R1或R3取代。
在部分缩醛化的聚乙烯醇特别是PVB情况下,该特殊的增塑剂优选与一种或多种标准增塑剂组合使用,该特殊增塑剂的用量按增塑剂总量计为0.1-15重量%。
该增塑的部分缩醛化的聚乙烯醇树脂中的增塑剂量按100重量份树脂计优选为25-45重量%,特别优选为30-40重量%。
以已知的方法通过水解的聚乙烯基酯的缩醛化来制备部分缩醛化的聚乙烯醇。作为醛可使用如甲醛、乙醛、丙醛、丁醛等,优选使用丁醛。
该优选的聚乙烯醇缩丁醛树脂含10-25重量%,优选为17-23重量%,特别优选为19-21重量%的乙烯醇基和/或0-20重量%,优选为0.5-2.5重量%的乙酸酯基。
在另一方法变型方案中,作为聚合物使用WO 2004/063231A1中的与聚醛(特别是戊二醛)和氧代羧酸(特别是二羟乙酸)交联的PVB作为聚合物。与不交联的PVB类似物相比,这种交联的PVB的粘度增加10-50%。
该膜的水含量优选调节到0.15-0.8重量%,特别是0.3-0.5重量%。
按本发明制备的膜特别可用于制备由一层或多层塑料板和至少一层按本发明制备的结构化膜构成的层压件,其中该塑料膜(功能膜)位于按本发明制备的膜的未经压纹的面之间。
在最简单的情况下,这种层压件由五层组成,即玻璃/膜/功能膜/膜/玻璃,其中该膜的经压纹的面朝向玻璃,该膜的未经压纹的面朝向功能膜。
作为功能膜优选使用经任选涂金属的厚度为10-100μm的聚对苯二甲酸乙二醇酯膜(PET)。这种膜是例如由WO 97/03763已知的。如此制备的层压件可用作建筑领域的复合窗用玻璃或用作汽车或飞机的窗用玻璃。
在制备这种层压件时,首先通过压制、真空袋压或真空唇压由玻璃/塑料板和膜制备预复合件。通常该预复合层压件还会由于夹入空气而稍混浊。该层压件的最终制备如按WO 03/033583是在压热器(Autoklaven)中进行。
附图说明
图1示出通过改变线压力可以改变压纹区面积并由此改变膜在辊隙间的停留时间。
图2示意性示出了本发明方法的一种变型方案。
图3示意性示出了本发明方法的另一种变型方案。
具体实施方式
实施例:
使含钾盐和镁盐作为抗粘附剂的其两面粗糙度Rz≤5μm的由72.5重量%的PVB、25重量%的3G8组成的含增塑剂的PVB膜在图3的装置中经压纹。
装置参数:
压纹辊直径:245mm
橡胶辊硬度:70±5肖氏硬度-A
橡胶辊直径:255mm
压纹辊粗糙度:约80μm
表面涂层:PTFE
得到具有下列压纹特征的膜:
线速度(m/min) | 线压力(N/mm) | T压纹辊温度(℃) | T橡胶辊温度(℃) | Rz(μm)经压纹面 | Rz(μm)未经压纹面 |
2.75 | 60 | 120 | 10 | 45 | <5 |
该所得的两膜通过未压纹的面与厚度为50μm的PET膜叠在一起。
接着使膜叠层置于两玻璃板之间,并在200mbar绝对压力的真空炉中于95℃下经25分钟加工成几乎透明的预复合件。该预复合件在12bar的热压器中于125℃下经90分钟加工成复合玻璃。
Claims (10)
1. 一种制备基于部分缩醛化的聚乙烯醇膜的方法,该膜的第一面的粗糙度Rz=1-30μm,第二面的粗糙度Rz=20-100μm,该方法具有下列方法步骤:
a.制备其两面粗糙度Rz=1-30μm的基于部分缩醛化的聚乙烯醇的膜,和
b.在相应的温度为80-170℃的粗糙压纹辊和温度为0-60℃的压辊之间压纹该膜的一面,得到经压纹的表面的粗糙度Rz=20-100μm的膜,其特征在于,该压辊的肖氏-A-硬度为50-80。
2. 权利要求1的方法,其特征在于,向压纹辊和压辊之间的膜施加的线压为20-80N/mm。
3. 权利要求1或2的方法,其特征在于,所述压辊表面由橡胶或EPDM组成。
4. 权利要求1-3之一的方法,其特征在于,在横跨辊的宽度和周长上,该压纹辊的温差小于2℃。
5. 权利要求1-4之一的方法,其特征在于,在横跨辊的宽度和周长上,该压辊的温差小于2℃。
6. 权利要求1-5之一的方法,其特征在于,所述膜的压纹面的表面粗糙度Rz为20-80μm。
7. 权利要求1-6之一的方法,其特征在于,在方法步骤b)之前和/或之后,将该膜的温度调节到-10-+20℃。
8. 权利要求1-7之一的方法,其特征在于,所述膜的压纹面经冷却。
9. 权利要求1-7之一的方法,其特征在于,所述膜的未压纹面经冷却。
10. 一种由一层或多层塑料膜和至少两层按权利要求1-9之一的方法制备的膜组成的层压件,其中该塑料膜置于该膜的未经压纹的面之间。
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CN108859364B (zh) * | 2017-05-10 | 2021-09-28 | 可乐丽欧洲有限责任公司 | 具有遮阳带的夹层膜 |
CN113748020A (zh) * | 2019-04-18 | 2021-12-03 | 大日本印刷株式会社 | 透明性树脂膜、透明性树脂膜的制造方法和装饰材料 |
US11993063B2 (en) | 2019-04-18 | 2024-05-28 | Dai Nippon Printing Co., Ltd. | Transparent resin film, transparent resin film production method, and decorative material |
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EP1842647A1 (de) | 2007-10-10 |
MX2007003829A (es) | 2009-02-16 |
DE502006002816D1 (de) | 2009-03-26 |
EP1842647B1 (de) | 2009-02-11 |
JP5209894B2 (ja) | 2013-06-12 |
JP2007276474A (ja) | 2007-10-25 |
TW200804055A (en) | 2008-01-16 |
US20070231550A1 (en) | 2007-10-04 |
ES2321644T3 (es) | 2009-06-09 |
ATE422408T1 (de) | 2009-02-15 |
ZA200702637B (en) | 2008-07-30 |
RU2007111839A (ru) | 2008-10-10 |
KR20070099432A (ko) | 2007-10-09 |
CA2581791A1 (en) | 2007-10-03 |
PL1842647T3 (pl) | 2009-07-31 |
TWI403401B (zh) | 2013-08-01 |
KR101376061B1 (ko) | 2014-03-19 |
BRPI0701793A (pt) | 2008-02-19 |
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