CN1209092A - 增塑聚乙烯醇缩丁醛及片材 - Google Patents

增塑聚乙烯醇缩丁醛及片材 Download PDF

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CN1209092A
CN1209092A CN96180142A CN96180142A CN1209092A CN 1209092 A CN1209092 A CN 1209092A CN 96180142 A CN96180142 A CN 96180142A CN 96180142 A CN96180142 A CN 96180142A CN 1209092 A CN1209092 A CN 1209092A
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pvb
sheet material
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polyvinyl butyral
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J·J·德埃里科
B·A·杰姆莫特
M·S·克拉赫
J·R·莫兰
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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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    • B32—LAYERED PRODUCTS
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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    • 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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    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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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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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
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Abstract

聚乙烯醇缩丁醛树脂及片材,其羟基含量为19.5%(重量)以下,优选为约17～19%(重量),按聚乙烯醇计算;并用可相容数量的三乙二醇二－2－乙基己酸酯增塑。

Description

增塑聚乙烯醇缩丁醛及片材
发明背景
本发明涉及增塑聚乙烯醇缩丁醛(PVB)，更具体地说，涉及含有相容增塑剂的PVB片材。
增塑PVB片材已应用于含有诸如玻璃的一个或多个硬质层的透光层压材料，其用途为例如建筑和运载工具窗、陈列柜、图画和资料防护玻璃等。诸如当运载工具突然停止后，车内容物的头撞击层压材料的硬质层的时候，或者外来物体撞击层压材料外侧的时候，增塑片材能吸收能量并防止碎裂。PVB树脂在聚合物链中含有羟基能促进其与玻璃粘结。
必须仔细选择增塑剂，以使层压材料性能平衡。增塑PVB作为具有重要工业性能的安全层压材料，在对其的评价中，价格/有益性能依旧是重要的。
发明概述
与现有技术的体系相比较，现已开发出的增塑PVB制剂改善了增塑剂与PVB的相容性(树脂和增塑剂彼此的亲和性)。
所以，本发明的主要目的是提供一种改善了增塑剂与PVB树脂相容性的增塑PVB制剂。
另一个目的是提供一种其中含有从易得的较廉价的起始材料合成的增塑剂的相容增塑PVB制剂。
这些目的是通过按照用可相容量的三乙二醇二-2-乙基己酸酯(3GEH)增塑的、按照聚乙烯醇计算羟基含量为19.5％(重量)以下、优选为约17～19％(重量)的聚乙烯醇缩丁醛树脂实现的。
还提供了一种由该组合物形成的片材。
附图简述
在全面叙述本发明时参阅了附图，该附图示出在PVB中不同聚乙烯醇(PVOH)含量下3GEH与PVB的相容性。
发明详述
在PVB制剂中三乙二醇二-2-乙基己酸酯增塑PVB树脂。其与树脂相容的有效量取决于层压材料应用场合中所需要的性能。一般每100份PVB树脂(PPHR)使用35～45份增塑剂。
当树脂应用于安全层压材料的玻璃之间的夹层时，树脂与增型剂的相容性对于夹层暴露于使用条件下可能遭遇的各种条件时，层压材料保持其完整性具有重要的意义。如果增塑剂从片材渗出损失过大，片材组合物玻璃化转变温度增加，且层压材料抗冲性能下降，片材性能就受到了不利影响。
PVB树脂重均分子量大于7000，优选为约100,000～250,000，其测量是通过使用小角激光散射的尺寸排阻色谱进行的。按重量计，按聚乙烯醇(PVOH)计算，PVB一般含有19.5％以下的羟基，优选约17～19％；含有0～10％，优选0～3％残余酯基，按照聚乙烯酯计算，例如其醋酸酯；剩余量为缩醛，优选丁醛缩醛，但任选包含少量除丁缩醛外的缩醛，例如1992年8月11日授权的美国专利5137954公开的2-乙基己醛的缩醛。
PVB树脂生产方法包括：采用已知的含水的或溶剂缩醛化反应，在酸催化剂存在下使PVOH与丁醛反应，随后中和催化剂，分离，稳定，再干燥树脂。可以Butvar商品名从盂山都(Monsanto)公司购得。
厚度为约0.13～1.3毫米(厚度并非关键)的片材形式的增塑PVB的制备方法是，使树脂和增塑剂混合，再优选(在商业化系统中)使混合配料经片材模头挤出，即：迫使熔融的增塑的PVB经过一个水平方向长而垂直方向窄的模头，其尺寸基本上与待形成的片材一致；或者，将从挤出模头流出的熔融聚合物流延到十分靠近模头出口的模头辊上，以赋于聚合物一侧所要求的表面特性。当辊表面有少量凸起和凹陷时，与辊接触的片材一侧则会具有通常与凹陷和凸起相对应的粗糙表面。另一侧的粗糙程度能够通过所示的挤出模头出口的不同设计而提供，例如：美国专利4281980中图4所示的模头出口。在挤出片材一侧或两侧产生粗糙表面的其他已知技术包括拟订或控制如下一项或多项技术条件：聚合物分子量分布、含水量和熔体温度。这些技术公开在美国专利2904844、2909810、3994654、4575540和欧洲专利0185863中。挤出模头的后续压花工序也能使片材表面粗糙。正如已知的那样，这种粗糙表面是暂时的，其作用是促使层合期间脱气，此后，在使片材与玻璃粘合期间，高温高压使其熔融平滑。对玻璃的层压按照一般已知工序进行。
任选本发明的片材含有添加剂，以便提高性能；例如：染料、颜料、紫外光稳定剂、抗氧剂和调节粘附力的盐等。
如下实例说明但不限制或约束本发明。其数量和百分率以重量计。
在实例中所报告的性能基本上按如下步骤进行测定。
PVB残余羟基(％PVOH)：ASTM 1396。
自渗(S.E.)度量在预计的极限操作温度和湿度的条件下的增塑剂-PVB树脂的相容性。采用以50转/分钟旋转的装有σ桨的Brabender混合机，在150℃下，将增塑剂和制得的PVB(就增塑剂的用量而言)混合8分钟，得玻璃化转变温度Tg 31±1℃。采用加热的液压机(149℃，5.5兆帕，5分钟)将增塑的PVB压制成0.76毫米厚的片材，切割成17.5×38毫米的样品，在干燥器中干燥5天，称量得干重。将样品置于保持不同温度的加温器(Wet dessicator，含有水的密闭室，相对温度100％)中7天。从样品表面轻轻擦去渗出的增塑剂，以便除去渗出的增塑剂，然后将样品在干燥器中干燥5天。计算初始增塑剂重量损失百分数，作为自渗。
实例1～5
将具有所述PVB残余羟基含量的PVB树脂与不同用量的液态3GEH增塑剂共混，成形为片材，采用自渗试验测定相容性。配制成Tg 31±1℃[增塑剂以每100份PVB树脂的份数计(PPHR)]。结果示于表1，(S.E.)示于图中。
                            表1 实例                     PPHR                       ％PVOH
1                        37.6                        17.1
2                        39.2                        18.1
3                        40.2                        18.6
4                        41.7                        19.4
5                        43.1                        19.9
图中，实例1～3与实例4、5比较，所示自渗结果说明3GEH增塑剂与PVB树脂系列的相容性，在PVOH为17.1～18.6％狭窄范围内呈现出意想不到的效果，这是就在PVB片材大规模应用中所遇到的全部相似温度和湿度范围内增塑剂损失小于1％而论。虽然由图中的图线能够看出，将实例4.5的组合物加热至如约95℃(35℃)的高温能够避免过量渗出，但是在工业实践中并不能实施，因为在这么高的温度下，在贮存时增塑片材的相邻层会彼此粘结(粘着)。认为损失3％以下是在PVOH小于19.5％下所产生的最高上限。优选PVOH量等于或小于19％，例如：约17～19％。
实例6～9
将用3GEH增塑的PVB各种制剂的片材，在片材含水量为约0.4～0.6％下，在50°F(10℃)的仓库中成卷贮存约9个月。片材配方为
  实例                    PPHR                     ％PVOH
  6                        41                        18.3
  7                        39.5                      18.6
  8                        44                        20.0
  9                        42                        20.3
当将这些卷展开，并目视观察时，实例8、9的片材与实例6、7比较，前者增塑剂的表面薄膜是不能接受的，而后者不是。这进一步证实了大规模应用中实例1～5的试验结果。
上述叙述仅仅用于说明，而没有限制的意思。本领域的技术人员可以提出各种改进和变通方案。所以，上述仅仅是示范性的，本发明的范围按下述权利要求确定。

Claims (4)

1.一种聚乙烯醇缩丁醛树脂，其羟基含量按聚乙烯醇计算为19.5％(重量)以下，并用可相容量的三乙二醇二-2-乙基己酸酯增塑。
2.权利要求1的增塑聚乙烯醇缩丁醛树脂，其中羟基含量为约17～19％聚乙烯醇。
3.一种由下述的聚乙烯醇缩丁醛树脂形成的片材，该树脂具有的羟基含量按聚乙烯醇计算为19.5％以下，并用可相容量的三乙二醇二-2-乙基己酸酯增塑。
4.权利要求3的片材，其中羟基含量为约17～19％聚乙烯醇。
CN96180142A 1995-12-29 1996-12-24 增塑聚乙烯醇缩丁醛及片材 Expired - Lifetime CN1106278C (zh)

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US6559212B1 (en) 2003-05-06
US20030144396A1 (en) 2003-07-31
CN1106278C (zh) 2003-04-23
EP0877665B1 (en) 2000-08-23
CZ299865B6 (cs) 2008-12-17
ATE195686T1 (de) 2000-09-15
KR19990076845A (ko) 1999-10-25
MX9805320A (es) 1998-10-31
DE69609992T2 (de) 2001-05-10
CZ200298A3 (cs) 1999-05-12
DE69609992D1 (de) 2000-09-28
PT877665E (pt) 2000-12-29
CA2241653A1 (en) 1997-07-10
EP0877665A1 (en) 1998-11-18
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JP3675841B2 (ja) 2005-07-27
JP2001515527A (ja) 2001-09-18

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