CN107266762A - 聚烯烃泡沫片材的生产方法及其制品 - Google Patents
聚烯烃泡沫片材的生产方法及其制品 Download PDFInfo
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- CN107266762A CN107266762A CN201710209322.0A CN201710209322A CN107266762A CN 107266762 A CN107266762 A CN 107266762A CN 201710209322 A CN201710209322 A CN 201710209322A CN 107266762 A CN107266762 A CN 107266762A
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- sheet
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及聚烯烃泡沫片材的生产方法及其制品。制造聚烯烃泡沫片材组合物的方法包括:挤出聚烯烃片材、照射挤出片材以获得物理交联的片材、利用热发泡该物理交联的片材以获得发泡层、并且刮削该发泡层以获得具有至少一个刮削表面的泡沫片材。该泡沫片材的刮削表面的表面粗糙度与未刮削表面的表面粗糙度不同。
Description
技术领域
本公开涉及连续生产交联闭孔聚烯烃泡沫片材的方法。本公开的一些方面涉及连续生产具有基本不同的主表面的交联闭孔聚烯烃泡沫片材的方法。还公开了包含该泡沫片材的制品。
背景技术
连续生产的交联闭孔聚烯烃泡沫片材可以通过将成分的共混物挤出成片、照射片材、然后使片材发泡而生产。然而,在设备能力和成本方面存在实际限制,这限制了在该三步生产方法中可获得的厚度和密度的组合的范围。例如,非常薄且非常轻的泡沫片材对于商业生产可是不实际的,因为(a)挤出薄片材上的困难性和(b)与获得非常轻的泡沫片材所需的高级别的昂贵的化学发泡剂相关的成本。因此,需要能够生产在过去或许是不可行的非常薄且非常轻的泡沫的方法和材料。
发明内容
本发明提供一种制造聚烯烃泡沫片材组合物的方法,该方法包含将发泡剂和至少一种选自由聚丙烯和聚乙烯构成的组的聚烯烃树脂挤出以获得未发泡的挤出片材;利用电离辐射照射挤出片材以获得物理交联的片材;利用热使该物理交联的片材发泡以获得发泡层;并且,刮削发泡层以获得具有至少一个刮削表面的泡沫片材。泡沫片材的刮削表面优选具有约20μm至约150μm的Sa和约250μm至约1000μm的Sz。
本发明还提供一种包含至少一种选自由聚丙烯和聚乙烯构成的组的聚烯烃树脂的交联的聚烯烃泡沫片材,其中交联的泡沫片材的表面被刮削以获得至少一个刮削表面。该交联的聚烯烃泡沫片材可以与地板垫层系统、垫片、泡沫胶带和窗玻璃装配(windowglazing)系统结合使用。
具体实施方式
本文公开的方法和材料能够生产非常薄且非常轻的泡沫,其在常规三步生产方法中是不可行的。此外,与目前可得的泡沫相比,该泡沫具有扩大的厚度和密度的组合的范围,其允许连续生产的交联闭孔聚烯烃泡沫片材在商业上可行并且成本比其它商业泡沫(例如非交联闭孔聚烯烃泡沫片材)的成本有竞争性。
此外,所述泡沫允许工厂制造能力和效率的提高。在典型的制造环境中,存在提高生产过程的效率和产出能力的推动力。扩展产出能力的一个方法是安装另一条生产线。然而,这对制造商而言通常是昂贵的,并被认为是当其他工程解决方案不可用时的“最后的手段”。
发明人已经发现了增加生产辐射交联闭孔聚烯烃泡沫片材的连续制造工艺的产出的独特方法,而不必安装另一条生产线。通过利用我们的包含刮削步骤的方法,可以将产出提高两倍、三倍或甚至更多倍。通过刮削连续生产的双倍(2x)于所需商业泡沫厚度的泡沫片材,生产产出基本上翻倍。同样地,通过刮削连续生产的三倍(3x)于所需商业泡沫厚度的泡沫片材,生产产出基本上是三倍。对于四倍、五倍或更多倍厚于所需商业泡沫厚度的泡沫片材,以此类推。作为刮削的结果,生产出具有基本不同的主表面的泡沫层。
连续生产具有不同主表面的交联闭孔聚烯烃泡沫片材的方法可以任选地包括以下步骤:(a)挤出、(b)照射、(c)发泡和(d)刮削。
在挤出步骤中,泡沫组合物的原料可以被供给到挤出机中。将成分供给到挤出机中的方法是基于挤出机的设计和可用的材料处理设备。如果有必要或有需要,可以进行泡沫组合物的成分的预混以便于它们的分散。如果进行预混,可以优选使用亨舍尔混合机(Henshel mixer)用于预混。任选地,所有成分可以被预混并通过挤出机中的一个端口进料。成分也可以通过针对每种成分的单独指定的端口独立进料。例如,如果交联剂或任何其它添加剂是液体,则可以通过挤出机上的一个进料口(或多个进料口)或通过挤出机上的排气口(如果配备有排气口)将交联剂和/或添加剂加入,而不是与固体成分预混。也可以采用“预混”和独立的成分端口进料的组合。示例性挤出技术也在Handbook of Polymeric Foamand Foam Technology(第二版,Daniel Klempner和Vahid Sendijarevic编辑)的第8章中公开,其主题通过引用并入本文。
供给到挤出机中的泡沫组合物的原料可以包括至少一种聚丙烯,其在230℃的熔体流动指数为约0.1克/10分钟至约25克/10分钟;和/或至少一种聚乙烯,其在190℃的熔体流动指数为约0.1克/10分钟至约25克/10分钟。在一些实施例中,聚丙烯和/或聚乙烯的熔体流动指数可优选地分别在230℃和在190℃为约0.3克/10分钟至约20克/10分钟,并且更优选地分别在230℃和在190℃为约0.5克/10分钟至约15克/10分钟。
任选地,所述泡沫组合物包含上述聚丙烯和上述聚乙烯的共混物。在共混物中,聚丙烯与聚乙烯的合适比例为30/70至90/10,或更优选为40/60至80/20。可替选地,所述泡沫组合物可以是100%聚乙烯或100%聚丙烯。
聚合物的“熔体流动指数”(MFI)值根据ASTM D1238来定义和测量,使用2.16千克的柱塞进行10分钟,对于聚丙烯和聚丙烯基材料在230℃,并且对于聚乙烯和聚乙烯基材料在190℃。对于相对高的熔体流动性的树脂,测试时间会减少。
MFI提供聚合物的流动特性的量度,并且是聚合物材料的分子量和可加工性的指示。如果MFI值太高,其对应于低粘度,则挤出会不能令人满意地进行。与过高的MFI值相关的问题包括挤出期间的低压力、设定厚度轮廓的问题、由于熔体粘度低引起的不均匀冷却轮廓、熔体强度差、机器问题或其组合。过低的MFI值的问题包括熔融加工期间的高压力、片材质量和轮廓问题以及导致发泡剂分解和活化的风险的较高的挤出温度。
上述MFI范围对于发泡过程也是重要的,因为它们反映了材料的粘度,并且粘度对发泡有影响。不受任何理论的约束,认为MFI值比其他值更有效存在一些原因。较低MFI的材料可以改善一些物理性质,因为分子链长度较大,当施加应力时,产生更多的链流动所需的能量。而且,分子链(MW)越长,链可以结晶的晶体实体越多,从而通过分子间连接提供更多的强度。然而,在过低的MFI下,粘度变得过高。另一方面,具有较高MFI值的聚合物具有较短的链。因此,在给定体积的具有较高MFI值的材料中,相对于具有较低MFI的聚合物,在微观水平上存在更多的链端,由于旋转所需的空间,该链端可以旋转并且产生自由体积(例如,高于聚合物的Tg或玻璃化转变温度发生的旋转)。这增加了自由体积并且允许在应力作用下的容易的流动。
具有合适MFI值的聚丙烯类可以包括但不限于聚丙烯、抗冲改性聚丙烯、聚丙烯-乙烯共聚物、茂金属聚丙烯、茂金属聚丙烯-乙烯共聚物、茂金属聚丙烯烯烃嵌段共聚物(具有受控的嵌段序列)、聚丙烯基聚烯烃塑性体、聚丙烯基聚烯烃弹性-塑性体、聚丙烯基聚烯烃弹性体、聚丙烯基热塑性聚烯烃共混物和聚丙烯基热塑性弹性体共混物。此外,聚丙烯可以用马来酸酐接枝。
具有合适MFI值的聚乙烯可以包括但不限于LDPE、LLDPE(均聚物、与丁烯或己烯或辛烯的共聚物、与丁烯和/或己烯和/或辛烯的三元共聚物)、VLDPE(均聚物、与丁烯或己烯或辛烯的共聚物、与丁烯和/或己烯和/或辛烯的三元共聚物)、VLLDPE(均聚物、与丁烯或己烯或辛烯的共聚物、与丁烯和/或己烯和/或辛烯的三元共聚物)、HDPE、聚乙烯-丙烯共聚物、茂金属聚乙烯、茂金属乙烯-丙烯共聚物和茂金属聚乙烯烯烃嵌段共聚物(具有受控的嵌段序列),其中,任一种可以含有接枝相容剂或含有乙酸酯和/或酯基团的共聚物。聚乙烯可以用马来酸酐接枝。聚乙烯还可以是含有乙酸酯和/或酯基团的共聚物和三元共聚物,并且可以是含有乙酸酯和/或酯基团的共聚物离聚物和三元共聚物离聚物。
因为用所公开的泡沫组合物可以产生宽范围的刮削泡沫层、制品和层压品,所以在泡沫组合物中可以采用宽范围的聚丙烯和聚乙烯,以满足刮削泡沫层、制品和层压品的各种最终用途要求。
任选地,供给到挤出机中的泡沫组合物的原料也可以含有与生产所公开的泡沫结构相容的添加剂。常用添加剂可以包括但不限于有机过氧化物、抗氧化剂、润滑剂、热稳定剂、着色剂、阻燃剂、抗静电剂、成核剂、增塑剂、抗菌剂、抗真菌剂、光稳定剂、UV吸收剂、防粘连剂、填料、除臭剂、增稠剂、孔尺寸稳定剂、金属钝化剂及其组合。
无论成分如何被供给到挤出机中,挤出机内的剪切力和混合必须足以产生基本均匀的结构。可选地,同向旋转和反向旋转的双螺杆挤出机可以提供通过挤出机料筒的足够的剪切力和混合以挤出具有均匀性质的结构。
比能是衡量成分挤出期间施加多少功以及挤出过程的密集程度的指标。比能定义为施加到被挤出机加工的材料的能量,标准化为每千克的基准。比能以每小时每千克供给的总物料施加能量的千瓦数为单位进行量化。比能量根据下式计算:
其中:
比能用于定量挤出机内成分的剪切和混合的量。挤出机优选能够产生至少约0.090KW·hr/kg、优选至少约0.105kW·10kg、并且更优选至少约0.120kW·hr/kg的比能。
泡沫组合物可以包括各种不同的化学发泡剂。化学发泡剂的实例可以包括但不限于偶氮化合物、肼化合物、卡巴肼、四唑、亚硝基化合物和碳酸酯。此外,化学发泡剂可以单独使用或以任何组合使用。
在一些实施例中可以使用的一种化学发泡剂是偶氮二甲酰胺(“ADCA”)。泡沫组合物中ADCA的合适的量可以小于或等于约40%PPHR。ADCA的热分解通常在约190℃至约230℃的温度下发生。为了防止ADCA在挤出机中热分解,挤出温度可以保持在约190℃或低于约190℃。在一些实施例中可以使用的另一种化学发泡剂是对甲苯磺酰肼(“TSH”)。泡沫组合物中TSH的合适的量可以小于或等于约77%PPHR。在一些实施例中可以使用的另一种化学发泡剂是对甲苯磺酰氨基脲(“TSS”)。泡沫组合物中TSS的合适的量可以小于或等于约63%PPHR。化学发泡剂的量没有特别限制,并且可以尤其取决于未发泡的片材厚度、所需的泡沫厚度、所需的泡沫密度、被挤出的材料、交联百分数、化学发泡剂的类型(不同的发泡剂可以显著地产生不同量的气体)。发泡剂的合适的量通常可以小于约80%PPHR。
结构的挤出温度优选低于化学发泡剂的热分解起始温度至少10℃。如果挤出温度超过发泡剂的热分解温度,则发泡剂倾向于分解,导致不期望的“预发泡”。合适的挤出温度也可以低于化学发泡剂的热分解起始温度至少15℃,并且甚至更优选低于化学发泡剂的热分解起始温度至少20℃。
如果可热分解发泡剂的分解温度与熔点最高的聚合物的熔点之间的差异大,则可以使用发泡剂分解用催化剂。示例性催化剂可以包括但不限于锌氧化物、镁氧化物、硬脂酸钙、甘油和尿素。
用于挤出的较低温度限值是熔点最高的聚合物的熔点温度。用于挤出的合适的较低温度限值可以高于熔点最高的聚合物的熔点至少5℃,并且更优选高于熔点最高的聚合物的熔点至少10℃。
如果挤出温度低于熔点最高的聚合物的熔融温度,则在挤出片材中出现不期望的“未熔物”。在发泡时,在低于该较低温度限值下挤出的片材将呈现不均匀的厚度、不均匀的泡孔(cell)结构、泡孔塌陷穴(pocket)及其它不期望的性质。
通常,合适的挤出温度范围可以是约138℃至约190℃,优选约143℃至约185℃,并且更优选约148℃至约180℃。
挤出片材的厚度可以是约0.1mm至约30mm,优选约0.2mm至约25mm,更优选约0.3mm至约20mm,并且甚至更优选约0.4mm至约15mm。
在挤出期间挤出片材不应发泡。挤出未发泡的片材不同于挤出已发泡的片材,挤出已发泡的片材通常被称为“挤出发泡(extrusion foaming)”。典型的挤出发泡产生具有未刮削表面的聚烯烃泡沫,其比通过首先挤出未发泡的片材的方法(其中发泡在挤出后发生)产生的同等泡沫显著更粗糙。与通过首先挤出未发泡的片材的方法产生的泡沫相比,挤出发泡的片材的更粗糙的表面通常是由较大尺寸的泡孔的存在引起的。虽然泡沫片材的泡孔尺寸和尺寸分布在一些商业应用中可能不是关键的,但是由于表面粗糙度是泡孔尺寸的函数,对于使用光滑泡沫表面的应用,具有较大泡孔的泡沫会不如具有较小泡孔的泡沫片材令人满意。
通过挤出机生产片材之后,可以将挤出片材进行电离辐射照射以交联挤出片材的组合物,从而获得经照射的物理交联的片材。示例性照射技术在Handbook of PolymericFoam and Foam Technology(第二版,Daniel Klempner和Vahid Sendijarevic编辑)的第8章中公开。
电离辐射通常不能在聚丙烯、聚丙烯基材料、一些聚乙烯和一些聚乙烯基材料上产生足够程度的交联。因此,交联剂可以任选地加入到供给到挤出机的泡沫组合物中以促进交联。
电离辐射的实例可以包括但不限于α射线、β射线(电子束)和γ射线。其中优选使用具有均匀能量的电子束来制备交联结构。暴露时间、照射频率和用电子束照射时的加速电压可以根据预期的交联度和挤出结构的厚度而广泛变化。然而,电离辐射通常应该为约10kGy至约500kGy,优选约20kGy至约300kGy,并且更优选约20kGy至约200kGy。如果暴露太少,则发泡时会不能维持泡孔的稳定性。如果暴露太多,则所得泡沫结构的可塑性会较差。当泡沫结构用于热成型应用时,可塑性是所需的性质。并且,当暴露于电子束辐射时,放热的热释放可以使结构软化,这样当暴露太多时,结构会变形。此外,聚合物组分也会由过度的聚合物链断裂而降解。
挤出片材可以最多照射单独的四次或单独的三次,但优选不超过两次,并且更优选仅一次。如果照射频率多于约四次,则聚合物组分会发生降解,使得当发泡时,例如在所得泡沫中不会产生均匀的泡孔。
电离辐射的穿透深度是以kV为单位测量的加速电压的函数。当电离辐射是β射线(电子束)时,典型的商业电子束照射机可以穿透约15mm的挤出片材(约3000kV)且具有良好的均匀性。当挤出片材的厚度大于约15mm时,用β射线(电子束)照射轮廓的每个主表面是优选的,以使主表面和内层的交联度更均匀。
用电子束照射提供了一个优点,即通过控制电子的加速电压可以有效地交联具有各种厚度的挤出片材。加速电压通常为约200kV至约3000kV,优选为约400kV至约2000kV,并且更优选为约600kV至约1000kV。如果加速电压小于约200kV,则辐射不能到达挤出片材的内部。结果,内部的泡孔在发泡时会是粗糙的和不均匀的。此外,对于给定的厚度轮廓,加速电压太低将引起电弧,导致泡沫结构中的“针孔”或“孔洞(tunnels)”。不管选择的电离辐射的类型,进行交联使得挤出片材交联约20%至约75%,优选约30%至约60%,如通过“TORAYTM Gel Fraction Method”测量的。
根据“TORAYTM Gel Fraction Method”,使用四氢化萘溶剂溶解组合物中的非交联组分。原则上,将非交联材料溶解在四氢化萘中并且交联度表示为整个组合物中交联材料的重量百分数。
用于确定“TORAYTM Gel Fraction Method”中聚合物交联百分数的装置可以包括:100目(0.0045英寸线的直径);304型不锈钢袋;编号的线和夹子;Miyamoto恒温油浴装置;分析天平;通风橱;气体燃烧器;高温炉;防静电枪和三个带盖的3.5升宽口不锈钢容器。使用的试剂和材料包括四氢化萘高分子量溶剂、丙酮和硅油。具体地,称重一个空的丝网袋并记录重量。对于每个样品,称取100毫克±5毫克样品并转移到丝网袋中。记录丝网袋和样品(通常为泡沫切割的形式)的重量。每个袋子都绑到相应的编号的线和夹子上。当溶剂温度达到130℃时,将束(袋子和样品)浸入溶剂中。样品上下摇动约五次或六次以释放任何气泡并充分润湿样品。将样品附到搅拌器并搅拌三(3)小时,使溶剂可以溶解泡沫。然后将样品在通风橱中冷却。通过在第一丙酮的容器中上下摇动约七次或八次洗涤样品。样品在第二丙酮液中第二次洗涤。洗涤后的样品在如上所述的现配丙酮的第三容器中再洗涤一次。然后将样品悬挂在通风橱中约1分钟至约5分钟以蒸发丙酮。然后将样品在干燥箱中在120℃下干燥约1小时。将样品冷却最少约15分钟。将丝网袋在分析天平上称重,并记录重量。
然后使用公式100*(C-A)/(B-A)计算交联,其中A=空丝网袋重量;B=丝网袋重量+浸入四氢化萘前的泡沫样品的重量;和C=丝网袋重量+浸入四氢化萘后溶解的样品的重量。
合适的交联剂可以包括但不限于市售的二官能度的、三官能度的、四官能度的、五官能度的和更高官能度的单体。这种交联单体可以以液体、固体、丸和粉末形式获得。实例包括但不限于丙烯酸酯或甲基丙烯酸酯,例如1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、四羟甲基甲烷三丙烯酸酯、1,9-壬二醇二甲基丙烯酸酯和1,10-癸二醇二甲基丙烯酸酯;羧酸烯丙酯(例如偏苯三酸三烯丙酯、均苯四甲酸三烯丙酯和草酸二烯丙酯);氰尿酸(cyanulicacid)烯丙酯或异氰尿酸烯丙酯,例如氰尿酸三烯丙酯和异氰脲酸三烯丙酯;马来酰亚胺化合物,例如N-苯基马来酰亚胺和N,N'-间亚苯基双马来酰亚胺;具有至少两个三键的化合物,例如邻苯二甲酸二丙炔(dipropagyl)和马来酸二丙炔;以及二乙烯基苯。此外,这种交联剂可以单独使用或以任何组合使用。双官能液体交联单体二乙烯基苯(DVB)可以用作交联剂,并以不大于约4%PPHR的水平加入到挤出机中。
可以使用各种不同技术产生交联,并且可以在不同的聚合物的分子间以及单一聚合物分子部分的分子内形成交联。这种技术包括但不限于提供与聚合物链分离的交联剂以及提供包含含有能够形成交联或被活化以形成交联的官能团的交联剂的聚合物链。
挤出片材应该是“物理交联的”。物理交联不同于化学交联。在化学交联中,交联可以用交联促进剂产生,但不使用电离辐射。无论化学交联过程如何,化学交联的泡沫片材通常表现出比通过物理交联产生的同等泡沫片材明显更粗糙的表面。与通过使用物理交联产生的泡沫相比,化学交联泡沫片材的更粗糙的表面通常由较大尺寸的泡孔引起。虽然泡沫片材的泡孔尺寸和尺寸分布在一些商业应用中可能不是关键的,但是由于表面粗糙度是泡孔尺寸的函数,故对于使用光滑泡沫表面的应用,具有较大泡孔的泡沫会不如具有较小泡孔的泡沫片材令人满意。
在照射挤出片材之后,可以通过将交联的片材加热到高于可热分解发泡剂的分解温度的温度来实现发泡。对于可热分解发泡剂偶氮二甲酰胺,在连续工艺中,在约200℃至约260℃、优选约220℃约240℃下进行发泡。对于生产连续泡沫片材,连续发泡工艺优于分批工艺。
通常通过用熔融盐、辐射加热器、立式热风炉、卧式热风炉、超声波能量、微波能量或这些方法的组合加热交联片材来进行发泡。也可以在使用例如高压釜中的氮的浸渍工艺中进行发泡,然后通过熔融盐、辐射加热器、立式热风炉、卧式热风炉、微波能量或这些方法的组合进行自由发泡。示例性发泡技术在Handbook of Polymeric Foam and FoamTechnology(第二版,Daniel Klempner和Vahid Sendijarevic编辑)的第8章中公开。
任选地,在发泡之前,交联片材可以通过预热而软化。这有助于在发泡时稳定片材的膨胀。可以通过将交联片材浸入热水中或将交联片材暴露于辐射热来进行预热。
在交联片材发泡之后,可以通过将连续发泡片材连续切割或切片成两层或更多层来实现刮削。可以使用机械刀片作为切割器。刀片可以是可移动的或固定的。当刮削机使得刀片是可移动的时,刀片运动可以是单向的、循环的或往复的。不管刀片是可移动的还是固定的,刀片可以被定位成使得切割平行于主表面,优选地,在切割刀片处没有泡沫片材振动或聚束。
合适的刮削速度(即加工速度、输入速度或输出速度)可以为约0.0米/分钟至约30.0米/分钟。刀片速度可以为约1.7米/秒至约5.0米/秒。
刮削的泡沫片材具有两个相对的主表面(例如,上表面和下表面)并且该两个主表面中的一者或两者会被刮削。如果发泡片材的其中一个表面没有被刮削,那么未刮削表面具有泡沫层的表面特性。例如,未刮削表面会具有在发泡期间由于暴露于辐射加热器或与熔融盐接触而带来的表面特性。刮削表面通常具有与同一泡沫层的未刮削表面不同的表面性质。
表面性质可以通过使用非接触式轮廓仪(例如NANOVEATM ST400轮廓仪)的轴向色差技术来测量。泡沫片材表面的算术平均高度(Sa)是由以下表达式确定的平均表面粗糙度:
也可以测量最大高度(Sz)或者最高峰与最深谷之间的高度。
泡沫片材的刮削表面的Sa可以是约20μm至约150μm,更优选约40μm至约130μm,并且甚至更优选约50μm至约120μm。泡沫片材的刮削表面的Sz可以是约250μm至约1000μm,更优选约300μm至约750μm。
未刮削的层的表面粗糙度将取决于表面在加工期间暴露的条件,例如,在发泡期间未刮削表面是否面向辐射加热器、在发泡期间是否接触熔融盐、在发泡期间是否接触加热炉中的皮带、或在表面固化之前是否接触空转轮或冷却滚筒。通常,泡沫片材的未刮削表面的Sa可以为约5μm至约30μm,更优选约9μm至约26μm。泡沫片材的未刮削表面的Sz可以为约90μm至约350μm,更优选约100μm至约135μm。更具体地,在发泡期间暴露于辐射加热器的泡沫片材的未刮削表面的Sa可以为约9μm至约11μm,并且Sz可以为约110μm至约130μm。在发泡期间接触熔融盐的泡沫片材的未刮削表面的Sa可以为约9μm至约26μm,并且Sz可以为约112μm至约350μm。
通常,在泡沫片材既具有未刮削表面又具有刮削表面时,泡沫片材的刮削表面的表面粗糙度会大于泡沫片材的未刮削表面的表面粗糙度。例如,泡沫片材的刮削表面的Sa可以是未刮削表面的Sa的至少约2.5倍或甚至至少约3倍。同样地,泡沫片材的刮削表面的Sz可以是未刮削表面的Sz的至少约1.5倍或甚至至少约2倍。如果未刮削表面是在发泡期间暴露于辐射加热和冷却滚筒的表面,则刮削表面的Sa可以是未刮削表面的Sa的至少约3倍或甚至至少约5倍。同样地,泡沫片材的刮削表面的Sz可以是在发泡期间暴露于辐射加热和冷却滚筒的未刮削表面的Sz的至少约2倍或甚至至少约3倍。如果未刮削表面是在发泡期间接触熔融盐浴的表面,则刮削表面的Sa可以是未刮削表面的Sa的至少约2.5倍,并且泡沫片材的刮削表面的Sz可以是暴露于熔融盐浴的未刮削表面的Sz的至少约1.5倍。
如根据JIS K6767所测量的,使用截面密度或“总体”密度而不是“芯”密度来定义和测量任何刮削泡沫层的密度。使用上述方法生产的刮削泡沫层优选产生具有约0.015g/cm3至约0.250g/cm3、优选约0.030g/cm3至约0.175g/cm3的截面密度或“总体”密度的泡沫。截面密度可以通过发泡剂的量和挤出结构的厚度来控制。如果刮削泡沫层的密度小于约0.015g/cm3,则由于获得该密度所需的大量化学发泡剂,照射的结构不会有效地发泡。此外,如果刮削泡沫层的密度小于约0.015g/cm3,则在发泡步骤期间照射结构的膨胀变得越来越难以控制。此外,如果刮削泡沫层的密度小于约0.015g/cm3,则泡沫结构在发泡步骤期间变得越来越容易发生泡孔塌陷。因此,难以以小于约0.015g/cm3的密度生产具有均匀截面密度和厚度的刮削泡沫层。
刮削泡沫层不限于约0.250g/cm3或更小的截面密度。也可以生产约0.350g/cm3或更小、约0.450g/cm3或更小或约0.550g/cm3或更小的刮削泡沫层。然而,优选地是,刮削泡沫层的密度小于约0.250g/cm3,因为当其与可以在给定应用中使用的其它材料相比时,较大的密度通常成本过高。
使用以上方法生产的刮削泡沫层可以具有闭孔。优选地,至少约90%的泡孔具有未损坏的泡孔壁,优选地至少约95%,并且更优选地大于约98%。平均泡孔尺寸为约0.05mm至约1.0mm,并且优选地约0.1mm至约0.7mm。如果平均泡孔尺寸低于约0.05mm,则刮削泡沫层的密度通常大于约0.250g/cm3。如果平均泡孔尺寸大于约1mm,则未刮削的泡沫表面会过度不均匀,和/或刮削的泡沫表面会过度不均匀。如果在刮削泡沫层中的泡孔群不具有合适的平均泡孔尺寸,则还存在刮削泡沫层被不合需要地撕裂的可能性。这会发生在当刮削泡沫层被拉伸或者当其部分进行二次加工时。当泡沫层具有一个刮削表面和一个未刮削表面时,泡沫层中的泡孔尺寸可以具有双峰分布,该双峰分布表示在大部分泡沫层中相对圆形的泡孔群,以及表示在未刮削表面中相对平坦、薄和/或椭圆形的泡孔群。
刮削泡沫层的厚度为约0.2mm至约125mm,优选约0.4mm至约50mm,更优选约0.6mm至约25mm,并且甚至更优选约0.8mm至约12mm,或者更优选约0.8mm至约3.2mm。如果厚度小于约0.2mm,则发泡步骤由于主表面的显著气体损失而不是有效的。如果厚度大于约125mm,则在发泡步骤期间的膨胀变得越来越难以控制。因此,生产具有均匀的截面密度和厚度的刮削泡沫层越来越困难。
刮削泡沫层允许生产具有基本不同的主表面的交联闭孔聚烯烃泡沫片材。
刮削泡沫层可用于各种应用。一个应用是泡沫胶带和垫片。闭孔泡沫胶带通常用于诸如窗玻璃装配的区域,其中泡沫胶带的条带被放置在两个窗格之间以密封玻璃之间的空气。这改善了窗户的隔热性能。泡沫也用作缓冲物使玻璃窗格免受由于每日的和季节性的温度变化引起的建筑物和窗框架的热膨胀和收缩的影响。同样,闭孔泡沫垫片通常用于密封和缓冲。手持电子设备和家用电器是可包含泡沫垫片的两个示例。软的、柔性刮削泡沫层通常适合作为胶带或垫片。
当将刮削泡沫层用作胶带或垫片时,压敏粘合剂层可以设置在一个主表面或两个主表面的至少一部分上。可以使用本领域已知的任何压敏粘合剂。这种压敏粘合剂的实例可以包括但不限于丙烯酸类聚合物、聚氨酯、热塑性弹性体、嵌段共聚物、聚烯烃、硅酮、橡胶基粘合剂、丙烯酸乙基己酯和丙烯酸的共聚物、丙烯酸异辛酯和丙烯酸的共聚物、丙烯酸粘合剂和橡胶基粘合剂的共混物以及前述的组合。
刮削泡沫层也可以热成型。为了使刮削层热成型,将泡沫加热至聚烯烃共混物的熔点。如果该共混物具有不混溶的聚合物,则该共混物可以表现出多于一个的熔点。在这种情况下,当将泡沫加热至泡沫组合物的最低熔点和最高熔点之间的中间温度时,刮削泡沫层通常可以热成型。
热成型制品的一个实例是汽车通风管。闭孔刮削泡沫层特别适合于此应用,因为其较轻重量(当与固体塑料相比时),其绝缘性能有助于保持通过通风管流动的空气的温度,以及其抗振动性(相对于固体塑料)。坚实的刮削泡沫层适合于汽车通风管。
在一些实施例中,刮削泡沫结构是含有刮削泡沫第一层和第二层的层压件。在这些层压件中,刮削泡沫层可以例如与薄膜和/或箔组合。用于这种层的合适材料的实例包括但不限于聚氯乙烯(PVC);热塑性聚烯烃(TPO);热塑性聚氨酯(TPU);织物,例如聚酯、聚丙烯、布和其它织物;皮革和/或纤维层,例如无纺布。可以使用本领域技术人员熟知的标准技术制造这样的层。重要的是,本公开的刮削泡沫层可以在一侧或两侧层压有这些材料,并且可以包括多层。
在这些层压件中,层可以通过化学结合(chemical bonds)、机械方式和/或这些的组合连接到相邻层。相邻的层压层也可以通过其他方式彼此固定,包括使用具有相反电磁荷的材料之间的吸引力或存在于主要具有疏水特性或主要具有亲水特性的两种材料之间的吸引力。
在一些实施例中,刮削泡沫层或层压品用于汽车内部部件,例如门板、门辊、门嵌板、门填充件、行李箱填充件、扶手、中央控制台、座垫、座椅靠背、头枕、座椅后板、仪表板、膝垫、顶篷等。这些刮削泡沫层或层压品也可用于家具(例如商业、办公室和住宅家具),例如椅垫、椅背、沙发垫、沙发装饰、躺椅垫、躺椅装饰、长沙发垫、长沙发装饰、卧铺垫、卧铺装饰等。这些刮削泡沫层或层压件也可用于墙壁,例如模块化墙壁、可移动墙壁、墙板、模块化面板、办公系统面板、室内分隔件、便携式隔板等。这些刮削泡沫层或层压件也可用于移动的或静止的储存箱(例如,商业、办公室和住宅)。刮削泡沫层或层压件也可用于行李箱。此外,刮削泡沫层或层压件还可用于覆盖物,例如椅垫覆盖物、椅背覆盖物、扶手覆盖物、沙发覆盖物、沙发垫覆盖物、躺椅垫覆盖物、躺椅覆盖物、长沙发垫覆盖物、长沙发覆盖物、卧铺垫覆盖物、卧铺覆盖物、墙壁覆盖物、建筑覆盖物等。
一些实施例包括所公开的刮削泡沫的第一层和选自由实心硬木地板面板、工程木地板面板、层压地板面板、乙烯基地砖、陶瓷地砖、瓷质(porcelain)地砖、石地砖、石英地砖、水泥地砖和混凝土地砖构成的组的第二层。
在这些实施例中,第一层可以通过化学结合、机械方式和/或这些的组合连接到相邻面板或砖。相邻的层压层也可以通过其他方式彼此固定,包括使用具有相反电磁荷的材料之间的吸引力或存在于主要具有疏水特性或主要具有亲水特性的两种材料之间的吸引力。
将刮削泡沫层附着到地板面板(特别是实心硬木地板面板、工程木地板面板和层压地板面板)的合适方法是通过设置在泡沫表面和/或面板表面的至少一部分上的压敏粘合剂层。可以使用本领域已知的任何压敏粘合剂。这种压敏粘合剂的实例是丙烯酸类聚合物、聚氨酯、热塑性弹性体、嵌段共聚物、聚烯烃、硅酮、橡胶基粘合剂、丙烯酸乙基己酯和丙烯酸的共聚物、丙烯酸异辛酯和丙烯酸的共聚物、丙烯酸粘合剂和橡胶基粘合剂的共混物以及前述的组合。
附接到地板面板,特别是实心硬木地板面板、工程木地板面板和层压地板面板的刮削泡沫层,用于多种目的。当面板受到冲击时,例如当靴子或高跟鞋在面板上行走时,刮削泡沫可以减少反射的声级。刮削泡沫还可以作为面板和地板底层之间的湿气隔离层,且可以有助于在多个面板之间提供更均匀的铺设,因为地板底层上的任何不平坦、隆起或尖峰(例如突出的钉头)将会通过刮削泡沫缓冲。这些地板面板和地砖通常安装在住宅、办公楼和其他商业建筑物中。
发明人还提供一种地板系统,包括:地板顶层、地板底层以及一个或更多个垫层,其中至少一层垫层包含设置在地板底层和地板顶层之间的刮削泡沫层。
在该系统中,刮削泡沫层可以连接到或可以不连接到任何相邻层,该相邻层包括地板底层或地板顶层。当所公开的系统中的任何层连接时,该连接可以通过化学结合、机械方式和/或这些的组合来进行。相邻层也可以通过任何其他方式彼此固定,包括使用具有相反电磁荷的材料之间的吸引力或存在于主要具有疏水性或主要具有亲水特性的两种材料之间的吸引力。
如果任何层被附接,则合适的附接方法是使用单组分聚氨酯粘合剂、双组分聚氨酯粘合剂、单组分丙烯酸类粘合剂或双组分丙烯酸类粘合剂。粘合剂通常在将该系统安装在住宅、办公楼和商业建筑物期间被应用。
该系统中的刮削泡沫层用于若干目的。当地板顶层受到冲击时,例如当靴子或高跟鞋在面板上行走时,泡沫可以减少反射的声级。泡沫也可以作为面板和地板底层之间的湿气隔离层并有助于在多个面板之间提供更均匀的铺设,因为在地板底层上的任何不平坦、隆起或尖峰(例如突出的钉头)将通过泡沫缓冲。对于地板顶层由砂浆连接的陶瓷地砖、瓷质地砖、石地砖、石英地砖、水泥地砖和混凝土地砖组成以及地板系统中的所有层被连接的情况,刮削泡沫可以通过缓冲该地板系统中不同层的不同热膨胀和收缩来帮助减少砂浆压裂。
为了满足上述任何一种应用的要求,可以对刮削泡沫层进行各种二次加工,包括但不限于压花、电晕或等离子体处理、表面粗糙化、表面平滑化、穿孔或微穿孔、拼接、切片、另外的刮削、分层、粘合和打孔。
实施例
使用Nanovea ST400 3D轮廓仪测试实施例的表面特征。探头规格和测量参数可见于下表1和表2中。
实施例1:
实施例1是80/20聚丙烯/聚乙烯共混物,其配制和发泡以产生如表3所示的0.155g/cm3至0.175g/cm3的泡沫层。发泡方法包括通过熔融盐和辐射加热器加热交联的未发泡片材。实施例1用光笔P1-OP1200C测量。当交联的发泡片材在包含单向带锯型刀片作为切割机构的机器中刮削一次时,基本上产生两种不同的表面:
较光滑(未刮削)表面: Sa=10μm Sz=110μm至130μm
较粗糙(刮削)表面: Sa=50μm至70μm Sz=340μm至390μm
实施例2
实施例2也是80/20聚丙烯/聚乙烯共混物,但是其配制和发泡以产生显著更轻的如表3所示的0.030g/cm3至0.050g/cm3的泡沫层。实施例2用光笔P1-OP1200C测量。当交联的发泡片材在包含单向带锯型刀片作为切割机构的机器中刮削一次时,基本上产生三个不同的表面:
最光滑(未刮削表面,其中当发泡时材料面向辐射加热器)
Sa=10μm Sz=130μm
中间(未刮削表面,其中当发泡时材料接触熔融盐)
Sa=20μm Sz=220μm
最粗糙(刮削)表面
Sa=60μm至90μm Sz=400μm至570μm
实施例3
实施例3是如表3所示的40/60聚丙烯/聚乙烯共混物,其配制和发泡以产生相比实施例1和实施例2甚至更轻的泡沫层(0.025g/cm3至0.045g/cm3)。实施例3用光笔P1-OP1200C测量。当交联的发泡片材在包含单向带锯型刀片作为切割机构的机器中刮削一次时,基本上产生三个不同的表面:
最光滑(未刮削表面,其中当发泡时材料面向辐射加热器)
Sa=10μm Sz=110μm
中间(未刮削表面,其中当发泡时材料接触熔融盐)
Sa=30μm Sz=350μm
最粗糙(刮削)表面
Sa=80μm Sz=550μm至670μm
实施例4
实施例4与实施例2相似,因为它是80/20聚丙烯/聚乙烯共混物,其配制和发泡以产生如表3所示的0.030g/cm3至0.050g/cm3的泡沫层。然而,不同于实施例1至实施例3,实施例4的发泡方法包括通过在卧式炉中的热风和辐射加热器加热交联的未发泡片材。实施例4用光笔P1-OP3500C测量。当交联的发泡片材在包含单向带锯型刀片作为切割机构的机器中刮削两次时,产生三个基本上不同的表面:
最光滑(未刮削表面,其中当发泡时材料面向热风)
Sa=10μm Sz=110μm
中间(未刮削表面,其中材料接触炉带)
Sa=20μm Sz=150μm
最粗糙(刮削)表面
Sa=110μm至120μm Sz=620μm至720μm
实施例5
实施例5与实施例1、实施例2、实施例4相似,因为它是如表3所示的80/20聚丙烯/聚乙烯共混物。然而,配制和发泡该材料以产生0.045g/cm3至0.065g/cm3的泡沫层。不同于实施例1至实施例4,实施例5的发泡方法包括通过在立式炉中的热风和辐射加热器加热交联的未发泡片材。实施例5用光笔P1-OP1200C测量。当交联的发泡片材在包含单向带锯型刀片作为切割机构的机器中刮削一次时,基本上产生两个不同的表面:
较光滑(未刮削)表面: Sa=10μm Sz=110μm
较粗糙(刮削)表面: Sa=60μm Sz=390μm至410μm
实施例6
实施例6说明与挤出后发泡相比挤出发泡对未刮削表面的表面性质的影响。将聚乙烯挤出发泡片材(从Gladon Company(Oak Creek,WI)商购的0.025g/cm3至0.026g/cm3的池衬壁泡沫(“38064blue Gladon”))与两种0.025g/cm3至0.026g/cm3的聚乙烯泡沫片材比较。第一片材是由东丽株式会社(Toray Industries,Inc.,Shiga,日本)商业化生产的40100-AG00。40100-AG00通过用热风加热辐射交联的片材而发泡。第二片材是由东丽塑料公司(Toray Plastics,Inc.,美国)生产的40064LCE-STD。40064LCE-STD通过在一个表面上用熔融盐加热辐射交联片材并在另一个表面上辐射加热来发泡。使用Nanovea ST400 3D轮廓仪测试片材的表面特性。无论加热方法如何,挤出发泡材料(38064blue Gladon)(显示出83.9μm的平均表面粗糙度(Sa)和706μm的最大高度(最高峰和最深谷之间的高度)(Sz))比挤出然后发泡的片材(40100-AG00&40064LCE-STD)(表现出20.7μm至65.2μm的平均表面粗糙度(Sa)和237μm至592μm的最大高度(Sz))明显地更粗糙。
实施例7
实施例7说明物理交联和化学交联对未刮削表面的表面性质的影响。将0.067g/cm3的化学交联的聚烯烃泡沫片材(由Trocellen Group of Companies商业生产的ProGameTM XC-Cut 7010)的表面与两种0.067g/cm3的物理交联的聚丙烯/聚乙烯共混物泡沫片材(15030AC17-STD和15030SR18-STD)比较。化学交联的泡沫和物理交联的泡沫都在挤出后工艺中发泡。化学交联的泡沫(XC-Cut 7010)显示出89.5μm的平均表面粗糙度(Sa)和856μm的最大高度(Sz)。物理交联的泡沫显示出7.63μm至23.9μm的平均表面粗糙度(Sa)和81.0μm至273μm的最大高度(Sz)。因此,与化学交联的泡沫相比,物理交联的泡沫表现出显著更平滑的表面。
Claims (33)
1.一种制造聚烯烃泡沫片材组合物的方法,所述方法包含:
a)将发泡剂和至少一种选自由聚丙烯和聚乙烯构成的组的聚烯烃树脂挤出以获得未发泡的挤出片材;
b)利用电离辐射照射所述挤出片材以获得物理交联的片材;
c)利用热发泡所述物理交联的片材以获得发泡层;以及
d)刮削所述发泡层以获得具有至少一个刮削表面的泡沫片材,
其中,所述泡沫片材的所述刮削表面的Sa为约20μm至约150μm并且Sz为约250μm至约1000μm。
2.根据权利要求1所述的方法,其中,所述泡沫片材的厚度为约0.8mm至约3.2mm。
3.根据权利要求1所述的方法,其中,所述泡沫片材的密度为约0.015g/cm3至约0.250g/cm3。
4.根据权利要求1所述的方法,其中,所述泡沫片材的两个表面被刮削。
5.根据权利要求1所述的方法,其中,所述泡沫片材具有未刮削表面。
6.根据权利要求5所述的方法,其中,所述泡沫片材的所述刮削表面的表面粗糙度大于所述未刮削表面的表面粗糙度。
7.根据权利要求5所述的方法,其中,所述刮削表面的Sa为所述未刮削表面的Sa的至少约2.5倍。
8.根据权利要求5所述的方法,其中,所述泡沫片材的所述未刮削表面的Sa为约5μm至约30μm,且Sz为约90μm至约350μm。
9.根据权利要求1所述的方法,其中,所述电离辐射选自由α射线、β射线和γ射线构成的组。
10.根据权利要求1所述的方法,其中,所述聚丙烯在230℃的熔体流动指数为约0.1克/10分钟至约25克/10分钟,以及所述聚乙烯在190℃的熔体流动指数为约0.1克/10分钟至约25克/10分钟。
11.根据权利要求1所述的方法,其中,所述泡沫片材的至少约90%的泡孔具有未损坏的泡孔壁。
12.根据权利要求1所述的方法,其中,所述泡沫片材的平均泡孔尺寸为约0.05mm至约1.0mm。
13.根据权利要求1所述的方法,其中,所述挤出以至少约0.090kW·hr/kg的比能进行。
14.根据权利要求1所述的方法,其中,所述交联的片材被交联约20%至约75%。
15.根据权利要求1所述的方法,其中,所述聚烯烃树脂是聚乙烯。
16.根据权利要求1所述的方法,其中,所述聚烯烃树脂是所述聚丙烯和所述聚乙烯的共混物。
17.根据权利要求16所述的方法,其中,在所述聚烯烃树脂中,所述聚丙烯与所述聚乙烯的比例为约30/70至约90/10。
18.根据权利要求1所述的方法,其中,所述发泡剂的量为小于约80%PPHR。
19.一种物理交联的聚烯烃泡沫片材,其包含至少一种选自由聚丙烯和聚乙烯构成的组的聚烯烃树脂,其中,所述物理交联的聚烯烃泡沫片材的表面被刮削以获得至少一个刮削表面,并且所述泡沫片材的所述刮削表面的Sa为约20μm至约150μm以及Sz为约250μm至约1000μm。
20.根据权利要求19所述的交联的聚烯烃泡沫片材,其中,所述泡沫片材具有未刮削表面,并且所述泡沫片材的所述刮削表面的表面粗糙度大于所述未刮削表面的表面粗糙度。
21.根据权利要求20所述的交联的聚烯烃泡沫片材,其中,所述刮削表面的Sa比所述未刮削表面的Sa大至少约2.5倍。
22.根据权利要求20所述的交联的聚烯烃泡沫片材,其中,所述未刮削表面的Sa为约5μm至约30μm并且Sz为约90μm至约350μm。
23.根据权利要求19所述的交联的聚烯烃泡沫片材,其中,所述泡沫片材的密度为约0.015g/cm3至约0.250g/cm3。
24.根据权利要求19所述的交联的聚烯烃泡沫片材,其中,所述聚丙烯在230℃的熔体流动指数为约0.1克/10分钟至约25克/10分钟,以及所述聚乙烯在190℃的熔体流动指数为约0.1克/10分钟至约25克/10分钟。
25.根据权利要求19所述的交联的聚烯烃泡沫片材,其中,所述泡沫片材的所述刮削表面的Sa为约20μm至约150μm并且Sz为约250μm至约1000μm。
26.根据权利要求19所述的交联的聚烯烃泡沫片材,其中,所述聚烯烃树脂是聚乙烯。
27.根据权利要求19所述的交联的聚烯烃泡沫片材,其中,两个表面被刮削。
28.根据权利要求19所述的交联的聚烯烃泡沫片材,其中,在所述聚烯烃泡沫片材中,所述聚丙烯与所述聚乙烯的比例为约30/70至约90/10。
29.一种地板垫层,所述地板垫层包含根据权利要求19所述的交联的泡沫片材。
30.一种地板垫层系统,所述地板垫层系统包含根据权利要求19所述的交联的泡沫片材。
31.一种垫片,所述垫片包含根据权利要求19所述的交联的泡沫片材。
32.一种泡沫胶带,所述泡沫胶带包含根据权利要求19所述的交联的泡沫片材。
33.一种窗玻璃装配系统,所述窗玻璃装配系统包含根据权利要求19所述的交联的泡沫片材。
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US20170282430A1 (en) | 2017-10-05 |
CA2925823C (en) | 2023-08-15 |
EP3225374B1 (en) | 2022-03-02 |
ES2910702T3 (es) | 2022-05-13 |
MX2017004166A (es) | 2018-08-16 |
CA2925823A1 (en) | 2017-09-30 |
EP3225374A1 (en) | 2017-10-04 |
US11738492B2 (en) | 2023-08-29 |
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