CN1031345A - 双层泡沫模制品的制法 - Google Patents

双层泡沫模制品的制法 Download PDF

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CN1031345A
CN1031345A CN88106208A CN88106208A CN1031345A CN 1031345 A CN1031345 A CN 1031345A CN 88106208 A CN88106208 A CN 88106208A CN 88106208 A CN88106208 A CN 88106208A CN 1031345 A CN1031345 A CN 1031345A
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foam
polyolefin
molded articles
fabric
foam molded
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CN1013089B (zh
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金子勝利
小林俊雄
渡充
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Prime Polymer Co Ltd
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Mitsui Petrochemical Industries Ltd
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    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
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    • B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
    • B29C51/145—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets having at least one layer of textile or fibrous material combined with at least one plastics layer
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    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0854—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns in the form of a non-woven mat
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

一种制造双层泡沫模制品的方法，其特征在于把 一块处于尚未发泡的可发泡聚烯烃板材加热生成一 泡沫聚烯烃层，把一层纤维织物整体层合在仍处于熔 化和软化状态下的所得的泡沫聚烯烃层的一面上以 生成一层合物并同时使所得层合物拉伸成双层泡沫 模制品的形状。

Description

本发明涉及双层泡沫模制品的制法，尤其是涉及泡沫聚烯烃的制法。该泡沫聚烯烃是双层泡沫模制品的基层，该模制品用作汽车内部装饰和装璜等的材料。
双层泡沫模制品包括一层纤维织物，如一层聚酯、锦纶等的无纺纤维织物和被载于所说纤维织物的背面的一层泡沫聚烯烃，如泡沫聚烯层。该模制品被广泛应用在汽车中，作为用于行李间、柱子、车门内装饰物、车身地板垫、尾部杂物箱等的材料。
以前制造如上所指的这种双层泡沫模制品都是把一层纤维织物，如无纺纤维织物和一块泡沫板材并使用一种粘合剂经整体层压以获得一种泡沫背层的纤维织物，然后把这种纤维织物进行拉伸模制，同时泡沫材料因受热而软化。然而，当以上述方法制造双层泡沫模制品时，如所用的加热温度较低，上述泡沫背层的纤维织物的拉伸生成性能变差，尤其困难的是要通过把有较厚和较薄部分的泡沫背层纤维织物进行深度拉伸使该双层泡沫模制品形成任意所希望的形状。另一方面，如果所用的加热温度过高，尽管泡沫背面纤维织物的拉伸生成（工艺）可以很好地实施，但得不到高质量的双层泡沫模制品，因为发生了泡沫的崩溃。当以上述方法用一块泡沫板材和一层纤维织物如一种无纺纤维织物制造各种形状的双层泡沫模制品时，需要精确地控制所用的加热温度，这形成在使泡沫背层的纤维织物拉伸生成一定形状中的困难。
还有，在按上述方法制造双层泡沫模制品时，当泡沫背层的纤维织物经受拉伸成形时，所用的纤维织物，如一种无纺纤维织物也被直接加热。因此纤维织物的绒毛通常会脱落使所得双层泡沫模制品的外观变差。
还有，在按上述方法制造双层泡沫模制品时，还存在一个问题，即必须使用粘合剂来使泡沫材料和如无纺纤维织物那样的纤维织物密切层合。
本发明打算解决如上所述的与已有技术有关的这些问题。本发明的一个目的是提供一种包括一层纤维织物，如无纺纤维织物和一泡沫聚烯烃层的双层泡沫模制品的制造方法，其中泡沫背层的纤维织物，即使它有较厚的部分，也有较薄的部分，也容易用深度拉伸法拉伸成所要的各种形状，所说的泡沫背层纤维织物是经把一层纤维织物，如无纺纤维织物和一泡沫聚烯烃层整体层压而获得的，并不使用粘合剂，还有，所得双层泡沫模制品的外观也不会因由不适当的过度加热引起的纤维织物;如无纺纤维织物的绒毛的脱落而变差。
本发明的双层泡沫模制品的制法的特征在于可以把一可发泡化的聚烯烃板材在其还未发泡时通过加热使其发泡并随后马上使一层纤维织物整体层合于所生成的泡沫聚烯烃层的一面上，同时把所生成的泡沫背层的纤维织物拉伸成一定形状。
根据本发明的制造双层泡沫模制品的方法，因为可发泡的聚烯烃板材在其未发泡时可经加热使其发泡，并随后马上使该纤维织物整体层合于所得泡沫聚烯烃层的一面上并同时立即把所得泡沫背层的纤维织物拉伸生成一定形状，该泡沫背层的纤维织物即使是既有较厚的部分也有较薄的部分也容易拉伸成形，例如，用深度拉伸法成形。并且，该纤维织物，如一种无纺纤维织物和该泡沫聚烯烃层能不使用粘合剂而互相整体层合，且所得双层泡沫模制品的外观不会因该纤维织物，如一种无纺纤维织物的绒毛的脱落而变差。
图1是本发明的双层泡沫模制品的横截面图。
图2、3、4和5依次分别说明本发明的双层泡沫模制品的制造过程中涉及的各步。
下面详细说明本发明的双层泡沫模制品的制造方法。
如图1的横面图所示在本发明中制造的双层泡沫模制品包括一层纤维织物2，如一层无纺纤维织物和载于该纤维织物2的背面上的一泡沫聚烯烃层。
作为纤维织物2的有用物质通常包括聚酯、锦纶、聚丙烯酸酯、聚丙烯等的无纺纤维织物。举出这些只是为了说明而不是为了限制。任何物质，只要是可以方便地用作双层泡沫模制品的表面材料的，都可被用作纤维织物2。
作为背层材料的泡沫聚烯烃层3可经加热可发泡的聚烯烃板材而制得。
如上所指的这样一种可发泡的聚烯烃层3可通过把其模制成一种可发泡性聚烯烃组合物的板材形式，该组合物包括（A）聚烯烃，（B）一种交联剂，（C）一种发泡剂和（D）一种有机过氧化物，并在既不使发泡剂（C）也不使有机过氧化物（D）分解的温度下进行制造。
作为聚烯烃（A）主要用聚乙烯或聚丙烯。
（ⅰ）有用的聚乙烯包括一种低密度聚乙烯LDPE[例如：MFR＝7.2克/10分，D＝0.917克/（厘米）3]，其熔融流动速率（MFR）为0.5～50克/10分和一种高密度聚乙烯（HOPE）[例如：MFR＝1.2克/10分，D＝0.9555克/（厘米）3]。在某些情况下，也可以用含小量（如小于该组合物的30%重量的）醋酸乙烯的乙烯/醋酸乙烯共聚物或含有小量丙烯和非共轭二烯的乙烯/丙烯/非共轭二烯共聚物。
（ⅱ）有用的聚丙烯包括丙烯的均聚物和丙烯与所占摩尔百分比小于15%的其它α-烯烃，如乙烯、1-丁烯、4-甲基-1-戊烯、1-己烯、1-辛烯、1-癸烯等的共聚物，它们都具有0.1-50克/10分的熔融流动速率，更好的是在0.5-20克/10分。
还有，也可以把上面所述的聚丙烯与一种选自1-丁烯聚合物且其1-丁烯含量在70%摩尔以上的α-烯烃树脂和丙烯与4～20个碳原子的α-烯烃的无规共聚物并用，所说无规共聚物含丙烯55～85%摩尔。
使用交联剂（B）来交联作为上面提到的聚烯烃的聚乙烯比较好，虽然并不总是需要它。有用的交联剂包括不饱和化合物、肟化合物、亚硝基化合物或马来酰亚胺化合物，它们都有一个、两个或更多的双键。这种交联剂（B）就是由于它和一种聚合物基团的反应，使它具有这样一种功能，交联剂（B）可以在该聚合物基团发生裂解反应之前稳定住它，同时也就提高了交联效率;上述聚合物基团是在前述有机过氧化物（17）的有在下从前述聚烯烃（A）中拉出氢原子后生成的。
交联剂（B）的具体实例包括氰尿酸三烯丙酯、异氰尿酸三烯丙酯、乙二醇二甲基丙烯酸酯、三甲基丙烯酸三羟甲基丙酯、三丙烯酸季戊四醇酯，二丙烯酸新戊二醇酯、二甲基丙烯酸1，6-己二醇酯、肟类化合物如醌二肟、苯醌二肟、对亚硝基苯酚和N，N-间苯撑双马来酰亚胺以及上述化合物中的两种或更多种化合物的混合物。在上面所举的化合物中，较好的是二丙烯酸新戊二醇酯、二甲基丙烯酸1，6-己二醇酯或它们的混和物。
就重量而言，当前述的聚烯烃（A）有100份时，这种交联剂（B）的总量以0.1-1份的量存在为好。
用于可发泡组合物中的发泡剂（C）是一种在室温下为液态或固态并在加热至气态时分解的化学物质。只要上述化学物质的分解温度高于前述聚烯烃（A）的熔点，对它们就没有特别的限制。
上面提到的这种发泡剂（C）包括偶氮二酰胺、偶氮二羧酸钡、N，N-二亚硝基-五亚甲基四胺、4，4-氧化双苯磺酰基酰肼、二苯砜-3，3-二磺酰基酰肼、对-甲苯磺酰基氨基脲、三肼基三嗪、联二脲和碳酸锌。考虚到它以高产率放出气体并且气体释放的结束温度足够低使聚烯烃（A）的热损耗不致开始，在以上所例举的这些化合物中，以偶氮二酰胺、N，N′-二亚硝基-五亚甲基四胺和三肼基三嗪特别好。
就重量而言，当前述的聚烯烃（A）有100份时，这种发泡剂的总量以5-20份的量存在为好。
用来交联可发泡组合物的有机过氧化物（D）主要包括有机过氧化物和有机过氧酯。为了达到分解半衰期为1分钟，这种有机过氧化物的分解温度最好高于前述聚烯烃（A）的熔点。
上面提到的有机过氧化物（D）的具体实例有：3，3，5-三甲基己酰基过氧化物（1）、辛酰基过氧化物（2）、癸酰基过氧化物（3）、月桂酰基过氧化物（4）、过氧化琥珀酸（5）、乙酰基过氧化物（6）、特丁基过氧化2-己酸乙酯（7）、间甲苯酰基过氧化物（8）、苯甲酰基过氧化物（9）、特丁基过氧化异丁酸酯（10）、1，1-双过氧化特丁基-3，5，5-三甲基环己烷（11）、1，1-双过氧化特丁基环己烷（12）、特丁基过氧化马来酸（14）、特丁基过氧化-3，5，5-三甲基环己酸酯（15）、环己酮过氧化物（16）、特丁基过氧化碳酸异丙酯（17）、2，5-二甲基-2，5-二过氧化苯酰基己烷（18），特丁基过氧化醋酸酯（19）、2，2-双过氧化特丁基丁烷（20）、特丁基过氧化苯甲酸酯（21）、正-丁基-4，4-双过氧化特丁基戊酸酯（22）、二特丁基过氧化间苯二甲酸酯（23）、丙酮过氧化物（24）、α，α-双特丁基过氧化异丙基苯（25）、过氧化二异丙苯（26）、2，5-二甲基-2，5-二过氧化特丁基己烷（27）、过氧化特丁基二异丙苯（28）、二异丙苯氢过氧化物（29）、二特丁基过氧化物（30）、对 烷氢过氧化物（31）、2，5-二甲基-2，5-二过氧化特丁基己炔-3（32）、1，1，3，3-四甲基丁基氢过氧化物（33）、2，5-二甲基己烷-2，5-二氢过氧化物（34）、异丙苯氢过氧化物（35）和特丁基氢过氧化物（36）。
在上面举例的化合物中，以化合物（12）-（36）为宜。
以每100份重量的上面所说的聚烯烃（A）为准，这种自由基形成剂最好以0.01～2.0份重量的量存在。
本发明的可发泡组合物除了含有上面所指出的组份外还可含有各种添加剂。例如，当所说可发泡组合物的组份被捏和时，最好掺入含30个碳原子以上的酚型热稳定剂。
下面接着说明应用上面指出的这样的可发泡聚烯烃组合物来制造双层泡沫模制品的方法。
为了将可发泡聚烯烃组合物制成板材，可以应用这样的方法，一种方法是用一台布拉本德（Brabender）混合器或其它类似机器将含有上述组份的可发泡聚烯烃组合物捏和，然后用压延辊使之形成板材;一种是使用压模机将所说组合物制成板材的方法;一种方法是用一台挤压机捏和所说组合物并通过一个T型或圆形模口使之形成板材。在上述方法中，最后一种方法较好，即把所说组合物捏和并然后在低于发泡剂（C）或其它助剂的分解温度下通过一T型模口挤出成板材形，因为在这个方法中，无论是能量消耗还是时间的需要都小，而且所得板材在平直度和挤出后的结构方面均十分出色。
当将可发泡聚烯烃组合物加工制成板材时，有必要应用在此温度下，如上所指出的那样发泡剂（C）不会发生分解的板材生成温度。然而，具体地说，当聚乙烯用作聚烯烃以及以偶氮二酰胺作发泡剂时，可发泡聚乙烯组合物最好在110-160℃温度下进行制板，更好地是在约120～160℃下进行。还有，当聚丙烯用作聚烯烃及偶氮二酰胺用作发泡剂时，最好在150～190℃，更好地在约160～180℃温度下将可发泡聚丙烯组合物进行制板。
作为制造好的可发泡聚烯烃组合物，其厚度最好为约0.5～5mm。
接着，可以把这样获得的可发泡聚烯烃板材4在它还未发泡前通过利用一真空模塑机的一陶瓷加热器5或其它类似加热器加热而发泡以生成发泡聚烯烃层3（如图2和图3、4及5中所示），一层纤维织物2，如一层无纺纤维织物在其仍然熔化和软化时被整体层合到该可发泡聚烯烃层3的一面上以获得一泡沫背层的纤维织物并同时立即用压模机上配置的阳模和阴模6a和6b制造所要形状的双层泡沫模制品1。
当将尚未发泡的可发泡聚烯烃组合物发泡时，所用的加热温度必须高于发泡剂（C）的分解温度。然而，具体地说，当以偶氮二酰胺被用作发泡剂时所用的加热温度最好高于200℃。
还有，当对泡沫聚烯烃板材4进行压模时，最好将压模保持在冷却状态而不加热，并使所得模制泡沫聚烯烃板材4冷却而硬化。在那种情况下，所用的加压时间约0.1～3分钟，而所得双层泡沫模制品最好用空气喷雾器等进行冷却。
在根据本发明得到的双层泡沫模制品中，泡沫聚烯烃层3的厚度约1-50mm，而发泡率最好为约2-40倍。
当泡沫聚烯烃层含有泡沫聚丙烯时，该泡沫层的密度约0.1～0.5g/cm3，并得到重量轻、且是硬质的双层泡沫模制品。另一方面，当该泡沫聚烯烃层含有泡沫聚乙烯时，该泡沫层密度为约0.02～0.5g/cm3，并因此得到重量轻且是软性的双层泡沫模制品。
在如上所述制造本发明的双层泡沫模制品的方法中，因为纤维织物2，如一层无纺纤维织物，是叠合在仍为熔化和软化的泡沫聚烯烃层3的一面上并随后进行压模的，纤维织物2，如一层无纺纤维织物是渗透入该泡沫聚烯烃层3的表面层中的，并因此该泡沫聚烯烃层3和该纤维织物2能不用粘合剂而互相整体结合在一起，而且更进一步地，这样获得的泡沫背层的纤维织物即使当所说泡沫背层纤维织物既有厚的部分也有薄的部分时也是易于进行加工的。
还有，在制造本发明的双层泡沫模制品的方法中，因为纤维织物2，如一层无纺纤维织物，和泡沫聚烯烃层3能在不使纤维织物2暴露直接加热情况下互相整体层合，所得双层泡沫模制品的纤维织物2（如无纺纤维织物）将不会由于所说织物的绒毛的脱落而损伤其外观。
在制造本发明的双层泡沫模制品的方法中，因为聚烯烃泡沫板材是在它尚未发泡时能用加热进行发泡并随后立即使一层纤维织物整体层合到所得泡沫聚烯烃层的一面上并同时立即对所得泡沫背层的纤维织物施行拉伸模制，该泡沫背层的纤维织物即使在它有较厚的部分也有较薄的部分时容易进行拉伸模制成各种形状，尤其是，如无纺纤维织物那样的一层纤维织物和一泡沫聚烯烃层的整体层合而毋须使用粘合剂。此外，所得双层泡沫模制品的如无纺纤维那样的纤维织物不会因所说纤维织物的绒毛的脱落而损伤其外观。
下面参考实施例说明本发明，但应当认作本发明并不限于这些实施例。
实施例1
把具有下列配方的一种可发泡聚丙烯组合物用一架亨斯切尔（Henschel）混合机充分混合并用直径65mm的挤压机造粒以制成颗粒料。此时所用的树脂温度为170℃。
聚丙烯树脂……80份重量
（密度0.91g/cm3，MFR2.0g/10min）
聚丁烯-1树脂……20份重量
（密度0.915g/cm3，MFR0.03g/10min）
交联剂……1.0份重量
（异氰尿酸三烯丙酯）
发泡剂……3份重量
（偶氮二酰胺）
有机过氧化物……0.1份重量
（二异丙苯过氧化物）
把这样得到的粒料加入一制板机中（65mm直径挤压机，具有一宽度550mm厚2.0mm的模口）并进行板材如可发泡聚丙烯板材的制造。所用的板材生成温度为170℃，且在那时未观察到树脂的起泡。这样得到的板材厚1.5mm。
将上面得到的可发泡聚丙烯板材用真空模塑机的一陶瓷加热器加热约2分钟以生成泡沫聚丙烯层。在那种情况下，陶瓷加热器的现场温度为400℃，而可发泡聚丙烯板材的表面温度是210℃。在泡沫聚丙烯层生成的同时，一层无纺纤维织物被敷在所说泡沫聚丙烯层的一个表面上。对已经敷上该无纺纤维织物的泡沫聚丙烯层使用一配置的阳模和阴模模具压制成形。那时，当压制有效时，该压力模具被在通常温度下应用而不被过热。加压时间约1分钟，在加压模制完成后，把双层泡沫模制品从模具中取出并用空气喷雾器使之冷却约30分钟。
这样获得的双层泡沫模制品的泡沫聚丙烯层厚度约6mm，密度0.2g/cm3，发泡率约4倍。
实施例2
聚烯烃……聚丙烯    80份重量的无定型聚合物
实质上含20份重量的70mol%的丙烯和30mol%1-丁烯
MFR（230℃）＝6g/10min
D＝0.89g/cm3
交联剂……三甲基丙烯酸三羟甲基丙酯0.5pbw
发泡剂……偶氮二酰胺    2pbw
有机过氧化物……2.5-二甲基-2，5-二过氧化特丁基己烷0.05pbw
把上述各组份加料入一亨斯切尔型混合机中，并然后在室温下混合生成一组合物。
把该组合物如例1中所描述的那样在170℃树脂温度下加料到一带通风的板材生成机中以制造可发泡板材。
该板材在未发泡状态下厚约1.2mm。用真空模塑机的一陶瓷加热器把该板材加热约90秒钟以生成一厚度约5mm的泡沫聚丙烯层，其发泡率约4倍。余下的操作和条件类同例1中的。

Claims (4)

1、一种制造双层泡沫模制品的方法，其特征在于把一块处于尚未发泡的可发泡聚烯烃板材加热生成一泡沫聚烯烃层，把一层纤维织物整体层合在仍处于熔化和软化状态下的所得的泡沫聚烯烃层的一面上以生成一层合物并同时使所得层合物拉伸成双层泡沫模制品的形状。
2、如权利要求1所说方法，其特征在于该可发泡聚烯烃板材是由一组合物生成的，该组合物包括（A）聚烯烃，（B）一种交联剂，（C）一种发泡剂（D）一种有机过氧化物。
3、如权利要求1所说方法，其特征在于该聚烯烃是聚乙烯或聚丙烯。
4、如权利要求1所说方法，其特征在于该纤维织物是一种无纺纤维织物。
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CN102548804B (zh) * 2009-08-31 2015-04-01 标致·雪铁龙汽车公司 用于车辆,尤其是汽车,的乘员室的隔音装置
CN109153192A (zh) * 2016-05-25 2019-01-04 伯杰橡胶金属有限责任公司 由纤维复合材料制造部件的方法
US10730248B2 (en) 2016-05-25 2020-08-04 Boge Elastmetall Gmbh Method for producing a component from a fiber-composite material
CN109153192B (zh) * 2016-05-25 2021-01-26 伯杰橡胶金属有限责任公司 由纤维复合材料制造部件的方法

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JPS6449623A (en) 1989-02-27
EP0304301B1 (en) 1992-12-02
KR890003532A (ko) 1989-04-15
KR900005081B1 (ko) 1990-07-19
US4878972A (en) 1989-11-07
EP0304301A3 (en) 1990-08-16
CA1297394C (en) 1992-03-17
DE3876337T2 (de) 1993-04-01
CN1013089B (zh) 1991-07-10
JPH0710535B2 (ja) 1995-02-08
EP0304301A2 (en) 1989-02-22
DE3876337D1 (de) 1993-01-14

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