CN1492908A - 红外吸收性聚乙烯醇缩丁醛组合物,由此制成的片材以及包含此片材的层合材料 - Google Patents

红外吸收性聚乙烯醇缩丁醛组合物,由此制成的片材以及包含此片材的层合材料 Download PDF

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CN1492908A
CN1492908A CNA018208347A CN01820834A CN1492908A CN 1492908 A CN1492908 A CN 1492908A CN A018208347 A CNA018208347 A CN A018208347A CN 01820834 A CN01820834 A CN 01820834A CN 1492908 A CN1492908 A CN 1492908A
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W·K·费施尔
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Abstract

公开了一种由含吸收红外有效量的六硼化镧或六硼化镧与锡氧化物和锑锡氧化物至少一种的混合物的聚乙烯醇缩丁醛树脂组成的聚乙烯醇缩丁醛组合物。还公开了一种吸收红外的聚乙烯醇缩丁醛片和一种具有置于两片玻璃之间的吸收红外的聚乙烯醇缩丁醛片的玻璃层合材料。

Description

红外吸收性聚乙烯醇缩丁醛组合物，由此 制成的片材以及包含此片材的层合材料
发明背景
技术领域
本发明涉及红外(IR)吸收性聚乙烯醇缩丁醛组合物，由此制成的片材以及包含此片材(作为夹层)的玻璃层合材料。尤其涉及聚乙烯醇缩丁醛组合物至少包含六硼化镧(LaB6)，更优选是既包含六硼化镧又包含铟锡氧化物(ITO)和锑锡氧化物(ATO)中的至少一种。
背景技术
聚乙烯醇缩丁醛(PVB)树脂片材用于包含一层或多层刚性层(如玻璃)的光透射层合材料中，供制造如汽车用和建筑用玻璃窗、橱窗和图片、文件等的防护玻璃。当车辆突然停止或是外来物体撞击层合玻璃外侧后，乘车人的头部撞击在层合玻璃窗的刚性层时，PVB片材会吸收能量而防止刚性层碎裂。
玻璃窗(包括层合玻璃窗)往往是传导热能的。这对于在有限区域如车辆的客舱或办公室内，由于空间有限而可能产生的过热会成为特别的难题。因此，为了控制通过玻璃窗的热传导已经开发了多种技术。
一种常规隔热、透明的复合材料可能包含一层很薄的、通过真空沉积或溅射技术沉积在透明基材上的反射性金属层如铝或银层。这种技术只能限于车辆或建筑物的窗上，因为这种薄膜的厚度必须极薄。此外，金属层也可能产生腐蚀问题。
大家都知道，各种无机氧化物的纳米级微粒分散在树脂粘合剂内可形成对特定的红外波长带产生反射，并允许透过较多的可见光的涂层。具体地说，美国专利5807511公开了掺杂有锑的氧化锡(ATO)对波长超过1400纳米的红外光透过率很低。美国专利5518810公开了包含掺杂有锡的氧化铟(ITO)微粒的涂层基本上能阻挡波长超过1000纳米的红外光，而且ITO结晶结构可改性成能阻挡波长降低至700-900纳米的红外光。
美国专利5830568公开了一种包含拥有官能性超细微粒的层间薄膜的层合玻璃，这种超细微粒具有隔热、吸收紫外光或足以保持无线电的传导的性能。优选的层间薄膜是聚乙烯醇缩丁醛或乙烯-醋酸乙烯酯共聚物。例证性的超细微粒包括锑锡氧化物和铟锡氧化物。
EP-A-1008564公开了包含ATO或ITO和金属六硼化物(如LaB6)的红外阻隔涂料组合物的用途。ATO或ITO能阻隔波长较长的红外光，而金属六硼化合物微粒能阻隔波长较短的光。该涂料可涂敷聚合物薄膜基材。然而，该专利申请未提出采用金属六硼化合物在PVB组合物(具体说是玻璃层合材料夹层片材)中的纳米级微粒分散体。
发明内容
本发明涉及包括含吸收IR有效量的六硼化镧的聚乙烯醇缩丁醛树脂的聚乙烯醇缩丁醛组合物。优选的聚乙烯醇缩丁醛树脂包含吸收IR有效量的六硼化镧与至少一种铟锡氧化物和锑锡氧化物的混合物。六硼化镧与任何一种铟锡氧化物和/或锑锡氧化物都是以细微粒形态存在的，即其粒度不会影响可见光透过由这类吸收IR的聚乙烯醇缩丁醛构成的片材。
本发明还涉及由本发明聚乙烯醇缩丁醛组合物制造的片材以及由两层玻璃与配置其间的本发明片材构成的玻璃层合材料。由本发明聚乙烯醇缩丁醛组合物制成的片材可用于吸热性玻璃以形成具有最佳的吸收太阳能特性的层合材料。本发明玻璃层合材料对降低IR透射是特别有效的，其效果不会随时间而下降。
附图的简要说明
图1表示LaB6对透明、拥有含0.45％锑锡氧化物的聚乙烯醇缩丁醛夹层的玻璃层合材料的透射光谱的影响。更具体地说，标有“LaB6”的曲线表示拥有含0.01％LaB6和0.45％锑锡氧化物的聚乙烯醇缩丁醛夹层的玻璃层合材料的透射光谱；标有“不含LaB6”的曲线表示拥有含0.45％锑锡氧化物的聚乙烯醇缩丁醛夹层的玻璃层合材料的透射光谱；标有“不含IR添加剂”的曲线表示拥有不含LaB6和不含锑锡氧化物的聚乙烯醇缩丁醛夹层的玻璃层合材料的透射光谱。
图2表示LaB6对透明的、拥有含0.2％铟锡氧化物的聚乙烯醇缩丁醛夹层的玻璃层合材料的透射光谱的影响。更具体地说，标有“0.01％LaB6”和“0.004％LaB6”的曲线表示拥有分别含(i)0.2％铟锡氧化物与“ 0.01％LaB6”及(ii)含0.2％铟锡氧化物与0.004％LaB6的聚乙烯醇缩丁醛夹层的玻璃层合材料的透射光谱；标有“不含LaB6”的曲线表示拥有含0.2％铟锡氧化物的聚乙烯醇缩丁醛夹层的玻璃层合材料的透射光谱；标有“不含IR添加剂”的曲线表示拥有不含LaB6和不含铟锡氧化物的聚乙烯醇缩丁醛夹层的玻璃层合材料的透射光谱。
具体实施方式
本发明的聚乙烯醇缩丁醛树脂或只含红外吸收有效量的六硼化镧或优选含六硼化镧与铟锡氧化物和掺杂的锡氧化物中的至少一种的结合物。如果单独采用六硼化镧作为IR吸收剂，则在聚乙烯醇缩丁醛树脂中的用量为约0.005％-约0.1％，优选为约0.01％-约0.05％，最优选为约0.01％-约0.04％(以组合物重量计)。
当以六硼化镧与铟锡氧化物或锑锡氧化物中的至少一种的结合物用作IR吸收剂时，则六硼化镧在聚乙烯醇缩丁醛树脂中的用量通常为约0.001％-约0.1％，优选为约0.004％-约0.05％，最优选为约0.006％-约0.02％(以组合物重量计)。
在优选的实施方案中，铟锡氧化物、锑锡氧化物或它们的混合物在聚乙烯醇缩丁醛组合物中用量为约0.05％-约2.0％，优选约0.1％-约1.0％，最优选约0.1％-约0.5％(以组合物重量计)。
当采用铟锡氧化物和锑锡氧化物的混合物时，铟锡氧化物与锑锡氧化物的重量比通常为约90∶10-约10∶90，优选约70∶30-约30∶70。
本发明的聚乙烯醇缩丁醛树脂组合物常用来制造目视透明的PBV片材和制造包含这类PVB片材(作为夹层)的目视透明的玻璃层合材料。因此，六硼化镧和任何铟锡氧化物与锑锡氧化物必须呈细小的微粒形态以致不会影响通过该片材的可见光透射性。这种微粒包括通常粒度小于200纳米，最优选是在5纳米-100纳米范围的纳米级微粒。
向PVB树脂添加六硼化镧、铟锡氧化物和锑锡氧化物的最好方式是先在与PVB相容的溶剂最优选为增塑剂中形成分散体。也可以在PVB形成前将这些微粒的溶剂分散体添加到PVOH与丁醛的反应性混合物中，而将IR吸收微粒混入PVB中。
虽然PVB是用于本发明的优选树脂，但必须认识到，其它可用于构成玻璃层合材料中的夹层的聚合物都可替代PVB。通常，PVB树脂的重均分子量高于70000，优选约100000-250000(采用小角激光散射的尺寸排阻色谱法测定)。PVB通常包含：15-25％，优选约16-19％按聚乙烯醇(PVOH)计算的羟基基团；0-10％，优选0-3％按聚乙烯酯如醋酸酯计算的残酯基团；其余为缩醛，优选为缩丁醛，但任选地包含少量除缩丁醛外的缩醛基团，例如美国专利5137954公开的2-乙基己缩醛。
PVB树脂是通过已知的水基型或溶剂型缩醛化方法，在酸催化剂存在下使PVOH与丁醛反应，接着经中和催化剂、分离、稳定化和树脂干燥而制得。这种PVB树脂可从Solutia Incorporated，St.Louis，Mo.商购如Butvar树脂。
优选的是，用于本发明片材中的PVB树脂是经增塑的PVB树脂。非临界厚度为约0.13-1.3毫米的经增塑PVB片材是通过使树脂与增塑剂相混合，优选(在工业系统中)使混合的配制物通过挤片模头挤塑，即：使熔融的、经增塑的PVB通过水平长度直立的基本上与所成形片材尺寸一致的窄狭模口。或者使从挤塑模头挤出的熔体聚合物流延在紧靠模头出口的模辊上，并将所要求的表面特征赋予聚合物一个侧面上。当模辊表面具有细小的峰和谷时，与模辊接触的片材的一个表面上就会形成相应的谷和峰的粗糙表面。片材另一表面的粗糙度通过挤塑模口的设计而获得，如美国专利4281980中图4所示。有关在挤塑片材上形成一面或两面粗糙表面的其它已知技术涉及确定和调整下述一项或多项参数：聚合物分子量分布、含水量及熔体温度。这些技术已公开在美国专利2904844、2909810、3994654、4575540和欧洲专利0185863中。挤塑模头压花的下游也能使片材表面变粗糙。正如大家所知，这种粗糙性是暂时性的以利层合过程中排出空气，排气后，在片材粘合到玻璃过程中采用的高温和高压会使片材熔融而变得光滑。PVB树脂片材层合在玻璃上的过程是按照通常已知的步骤实施的。
本发明的片材可任选地包含各种添加剂(除红外吸收剂外)以提高其性能，例如染料、颜料、紫外光稳定剂、抗氧化剂、粘合力调节剂等。
片材用PVB树脂通常是以每百份树脂用约20-80份，一般是用20-60份增塑剂增塑的。常用的增塑剂是多元酸的酯或多元醇。适用的增塑剂是三甘醇二(2-乙基丁酸酯)、三甘醇二(2-乙基己酸酯)、三甘醇二庚酸酯、四甘醇二庚酸酯、已二酸二己酯、己二酸二辛酯、环己基己二酸己酯、己二酸庚酯与壬酯的混合物、己二酸二异壬酯、己二酸庚基壬基酯、癸二酸二丁酯，聚合增塑剂如油改性的癸二酸醇酸树脂以及磷酸酯与己二酸酯的混合物(如美国专利3841890公开的)和己二酸酯(如美国专利4144217中公开的)。美国专利5013779中公开的也是由C4-C9烷醇和C4-C10环烷醇的己二酸酯的混合物。己二酸C6-C8烷基酯如己二酸己酯是优选的增塑剂。
本发明还涉及包含两层玻璃与夹在其间的本发明片材的玻璃层合材料。两层玻璃片间还可配置其它层，只要层合材料能保持所要求的光学性能。玻璃片材可以是任何类型的玻璃。特别优选的是采用至少一层是吸热性玻璃、能反射太阳光的玻璃、低e玻璃等。
通过下列实施例会对本发明有更好的了解。然而，技术人员都知道，所论述的特定方法和结果仅仅是说明性的，而不是限制性的。所有份额和百分比都是以重量表示的，除非另有说明。
实施例1
使19克三甘醇二-(2-乙基己酸酯)与0.32克2.2％六硼化镧纳米级微粒在甲苯中的分散体相混合，然后使该混合物与50克聚乙烯醇缩丁醛树脂相混合制成聚乙烯醇缩丁醛组合物。将得到的组合物在Brabender混合器中混和并压成30密耳厚的片材。然后将该片材层合在两片大小一样的透明玻璃片之间，加压成形为层合材料。所形成的层合材料的可见光透过率为80％，太阳光透过率为62％。相同的层合材料但不含六硼化镧的可见光透过率为87％。太阳光透过率为74％。这些结果表明，添加六硼化镧能明显地降低太阳光透过率，而仍保持高水平的可见光透过率。
实施例2
除了将1.56克20％锑锡氧化物在三甘醇二-(2-乙基己酸酯)中的分散体与六硼化镧一起加到树脂中外，其余按实施例1所述方法制备聚乙烯醇缩丁醛组合物。压制成片材后与透明的玻璃片制成层合材料。该层合材料的可见光透过率为70％，太阳光透过率为44％。
实施例3
除了使0.462克30％铟锡氧化物在三甘醇二-(2-乙基己酸酯)中的分散体与六硼化镧一起添加到树脂中外，其余按实施例1所述方法制备聚乙烯醇缩丁醛组合物。压制成片材后与透明的玻璃片制成层合材料，该层合材料的可见光透过率为78％，太阳光透过率为52％。
实施例4
按实施例3制备聚乙烯醇缩丁醛片材。将该片材层合在两片吸热性玻璃(所谓绿色玻璃)之间。该层合材料的可见光透过率为71％，太阳透过率为38％。
实施例5
除了将2克20％铟锡氧化物与锑锡氧化物(50∶50)的混合物分散体与六硼化镧一起添加到树脂中外，其余按实施例1所述方法制备聚乙烯醇缩丁醛组合物。制成具有优良IR吸收性的片材和层合材料。
实施例6
使5.11克6.3重量％的LaB6在三甘醇二(2-乙基己酸酯)增塑剂中的分散体与另外878.7克三甘醇二(2-乙基己酸酯)相混合以供制备聚乙烯醇缩丁醛组合物。将LaB6与增塑剂的混合物添加到2250克聚乙烯醇缩丁醛树脂中，采用1.25英寸挤塑机挤塑成片材。该片材包含0.01重量％LaB6。按同样步骤，由适当比例的LaB6在增塑剂中的分散体与另外增塑剂配制成LaB6含量分别为0.015％、0.02％、0.025％、0.03％的聚乙烯醇缩丁醛片材。分别将这些片材层合在两片2.3毫米厚的透明玻璃之间形成层合材料，这些层合材料的可见光透过率和太阳光透过率列于下表(太阳光透过率采用ISO 9050，以空气质量为1计算的)。
表10
LaB6重量％ 可见光透过率 太阳光透过率
0 89 70
0.01 79 52
0.015 72 44
0.02 67 38
0.025 62 32
0.03 57 28
实施例7
使5.11克6.3重量％的LaB6分散在三甘醇二-(2-乙基己酸酯)增塑剂中的分散体与21.47克30重量％铟锡氧化物在三甘醇二-(2-乙基己酸酯)中的分散体和另外863.7克三甘醇二-(2-乙基己酸酯)相混合以供制备聚乙烯醇缩丁醛组合物。将所得混合物添加到2250克聚乙烯醇缩丁醛树脂中，采用1.25英寸挤塑机挤塑成片材。该片材包含0.01重量％LaB6和0.2％铟锡氧化物。将该片材层合在两片2.3毫米厚的透明玻璃之间形成层合材料，这些层合材料的平均可见光透过率和平均太阳光透过率分别为77％(可见光透过率)和44％(太阳光透过率，太阳光透过率采用ISO 9050，以空气质量为1计算的)。
本发明可以有其它的变化和改变，这对技术人员来说是显而易见的。本发明除了下列权利要求所述以外，是不受其它限制的。

Claims (15)

1.一种包含聚乙烯醇缩丁醛树脂的聚乙烯醇缩丁醛组合物，该组合物包含吸收IR有效量的(i)六硼化镧或(ii)六硼化镧与铟锡氧化物和锑锡氧化物中至少一种的混合物。
2.根据权利要求1的聚乙烯醇缩丁醛组合物，该组合物包含六硼化镧与铟锡氧化物的混合物。
3.根据权利要求1的聚乙烯醇缩丁醛组合物，该组合物包含六硼化镧与锑锡氧化物的混合物。
4.根据权利要求1的聚乙烯醇缩丁醛组合物，该组合物包含六硼化镧、铟锡氧化物与锑锡氧化物的混合物。
5.一种聚乙烯醇缩丁醛片材，该片材包含吸收IR有效量的(i)六硼化镧或(ii)六硼化镧与铟锡氧化物和锑锡氧化物中至少一种的混合物。
6.根据权利要求5的聚乙烯醇缩丁醛片材，该片材包含六硼化镧与铟锡氧化物的混合物。
7.根据权利要求5的聚乙烯醇缩丁醛片材，该片材包含六硼化镧与锑锡氧化物的混合物。
8.根据权利要求5的聚乙烯醇缩丁醛片材，该片材包含六硼化镧、铟锡氧化物与锑锡氧化物的混合物。
9.一种包含两片玻璃片与夹在其间的片材的玻璃层合材料，其中夹在两玻璃片间的片材是由包含吸收IR有效量的(i)六硼化镧或(iii)六硼化镧与铟锡氧化物和锑锡氧化物中至少一种的混合物的聚乙烯醇缩丁醛树脂构成的。
10.根据权利要求9的玻璃层合材料，其中所述聚乙烯醇缩丁醛树脂包含六硼化镧和铟锡氧化物。
11.根据权利要求9的玻璃层合材料，其中所述聚乙烯醇缩丁醛树脂包含六硼化镧和锑锡氧化物。
12.根据权利要求9的玻璃层合材料，其中所述聚乙烯醇缩丁醛树脂包含六硼化镧、铟锡氧化物和锑锡氧化物。
13.根据权利要求9的玻璃层合材料，其中所述两层玻璃片中至少一层是吸热性玻璃。
14.根据权利要求9的玻璃层合材料，其中所述两层玻璃片中至少一层是反射太阳光的玻璃。
15.根据权利要求9的玻璃层合材料，其中所述两层玻璃片中至少一层是低e玻璃。
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JP2004518785A (ja) 2004-06-24
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BR0115342A (pt) 2003-08-26
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US6620872B2 (en) 2003-09-16
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