CN1328347C - 制鞋用热塑性加固材料及其生产方法 - Google Patents

制鞋用热塑性加固材料及其生产方法 Download PDF

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CN1328347C
CN1328347C CNB2004800005353A CN200480000535A CN1328347C CN 1328347 C CN1328347 C CN 1328347C CN B2004800005353 A CNB2004800005353 A CN B2004800005353A CN 200480000535 A CN200480000535 A CN 200480000535A CN 1328347 C CN1328347 C CN 1328347C
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melt adhesive
filler
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埃米尔·维尔丁
马库斯·法特
斯特凡·弗赖
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Renault Shoe Material Co ltd
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Abstract

本发明涉及制鞋(部件)的新型热塑性加固材料，以及在该材料的生产中一种对环境无害的生产方法。本发明的材料为热熔性粘合剂/填料复合物的形式，其特征在于由一种或多种热溶性粘合剂和一种或多种填料组成，填料的量为50-15重量%且不溶于热溶性粘合剂中。所述热熔性粘合剂/填料复合物同时满足以下参数：1.MVR值为2-6cm3/10min，优选3-5cm3/10min，2.根据DIN EN 14610，在65℃下测量的表面粘性值为至少10N/2cm，优选15N/2cm，最优选20N/2cm，3.采用DIN 53357测量的对鞋面材料或衬里的粘合值/抗剥强度至少为30N/5cm，4.在90℃的温度下测量的纵向伸长率最大为25%，优选小于20%。

Description

制鞋用热塑性加固材料及其生产方法
本发明涉及制鞋(部件)的新型热塑性加固材料，以及在该材料的生产中一种对环境无害的生产方法。
鞋用加固或增强材料包括鞋头和后帮隆起(puff)、防火鞋底、侧面增强材料和滑动带、后跟增强材料和多种罩面(cap)组合。现代制鞋方法习惯使用这些组分，从而提供鞋的方便成型性和穿着稳定性以及在最终除去支架鞋楦之后的回弹性。
热塑性鞋加固材料可在生产过程中施用，在所谓的活化方法中使用热和压力将这些材料粘合/胶合到鞋面(例如皮革)或织物内衬上，然后使它们与鞋楦的形状保持一致。
DE 26 21 195 C描述了片状加固材料的生产方法，其中用包含附加填料的可熔性粉状聚合物材料包覆支撑材料。在这些可熔性聚合物中包括聚乙烯、乙烯与醋酸乙烯酯或丙烯酸甲酯的共聚物。
本发明的目的在于寻找在粉状聚合物和填料材料的混合物中增大填料材料量而仍能得到材料的合适稳定性的方法。这一问题的解决办法基于以下的发现：如果两种材料的粒子大小分布保持可比性，则相对于可溶性粉状聚合物材料的量，填料量有可能增加到100体积％。只有这样，熔融的聚合物材料才能完全包覆填料粒子，使其完全具有聚合物性质，并然后如真正的聚合物那样起作用。典型的填料粒子的例子为木粉和白垩。
然而，这种加固材料在通常的制鞋温度下不能够粘合或胶合，因此需要附加的胶合或粘合过程或使用粘合剂材料。
EP 183 192 B2描述了具有直接粘合或胶合性质的鞋加固材料。其使用惰性填料，所述惰性填料完全由结合有可熔性粘合剂材料的聚合物组成或完全由结合有可熔性粘合剂材料的聚合物包覆，所述可熔性粘合剂材料如聚己酸内酯，其在约60℃的相对低的熔点温度下是可熔的。粘合剂材料对填料的比为：粘合剂占70-20重量％，填料占30-80重量％。填料的粒子大小分布为50-500μm。
本发明的根本特征体现于以下事实中：填料包括惰性聚合物，所述惰性聚合物不溶于处于活化状态下的熔融聚合物粘合剂材料中，即，所述惰性聚合物在粘合剂的熔融温度范围内不溶。最适合的填料为聚氯乙烯或PVC，前提条件是仍然需要粒子大小贡献的可比性，以建立良好的混合物内部粘合。本文所述粘合剂的其它例子为聚氨酯和改性聚乙烯-乙酸乙烯酯。为实现生产过程的充分稳定性，还需要使用支撑材料(通常为无纺织物、纺织材料离型纸)。在生产过程中需要这些支撑材料。本文描述的加固材料不再需要另外的粘合剂或粘合材料，并且可适当地选择使用相对于包覆材料的总量最多为80重量％的填料。即使当进行切削或切片操作时，这些包覆层表现出与非切削的“完整”材料同样好的热塑性和粘合征。本文中所述的热熔性粘合剂的熔融温度为50-80℃，并通过粘合于填料粒子表面上而与填料粒子结合。
制鞋用增强和加固材料在一系列的其它专利文献中有所描述。其示例性例子包括申请人同为Texon UK的WO 00/41585 A1和WO00/53416，因为这些文献不是较近地涉及本发明的主题，所以这些文献在本文中只是示例性的，不作进一步的评价。
施用EP 183 192的这些加固材料优选的方法为在手动定位到鞋轴(shoe shaft)之前预热加固材料，包括粘合剂的热塑成型或熔融。在定位鞋轴之后，在胶合或粘合的同时对其进行热压或冷压成形。
可通过接触式加热实现预热或活化。为了在热状态操作下提供充分的机械稳定性和可控的表面粘合性，为这些产品提供支撑纺织材料。这些纺织材料可以是开孔的织物、薄纱或无纺织物，以表面性地覆盖两侧。通过施用这一方法，可获得充分的机械稳定性并控制和降低表面粘性。在生产过程中，粘合剂在压力下冲压织物覆盖物。然而，这一方法的主要缺点在于纺织材料的成本高，更重要的是织物支撑材料部分不能再循环使用。必需指出的是，最终材料/片材的切削和切片获得的“废料”可占原始材料重量的30％。
在热状态下通过手工定位到鞋轴的具有良好的粘合性和良好的粘着或稳定性的任务需要50-100℃的生产方法温度范围并且不易于调整适当的表面粘性。迄今为止，如上所述，还不能满足这些需要，就使得有必要使用纺织物或包覆层的多层组合，以提供适合的和备用(ready-for-use)的加固材料。这一生产方法的主要缺点在于成本高和材料不可能再循环使用。
本发明的目的在于寻找适合用于任何生产方法的热熔性粘合剂/填料组合或混合物，该方法完全满足了上述参数而无需采用多层材料组合，并另外确保了经过切削和切片产生的生产废料可作为原料进行100％的再循环使用。
本发明的另一个目的在于选择热塑性聚合物，使其与天然存在的填料以及惰性无机填料组合实现刚性和粘合性的预期值，所述天然存在的填料如木材、木粉或软木产品，惰性无机填料如白垩、高岭土等。
令人惊讶地，发现可通过热塑性加固材料解决上述问题，所述热塑性加固材料为以下物质组成的热熔性粘合剂/填料复合物：
1.一种或多种热熔性粘合剂，其量为50-95重量％，MVR值/熔体体积流动速率(根据German DIN ISO 1133，在100℃、21.6kg条件下测量)为2-300cm3/10min，优选10-20cm3/10min
2.一种或多种填料，其量为50-5重量％，其在热熔性粘合剂中不溶解，并且热熔性粘合剂/填料复合物同时满足以下参数：
1.MVR值为2-6cm3/10min，优选3-5cm3/10min，
2.根据European standard DIN EN 14610，在65℃下测量的表面粘性为至少10N到最大为60N，优选15N，最优选30N，
3.采用German standard DIN 53357测量的对皮革或衬里对表面材料的粘合值/抗剥强度至少为30N/5cm，
4.在90℃的烘箱中保存5分钟后测量的纵向伸长率最大为25％，优选小于20％。
本发明的热熔性粘合剂/填料复合物形式的制鞋用热塑性加固材料的特征在于组分a热熔性粘合剂是由以下物质组成的混合物：
1.线型聚酯，其量为75-95重量％和/或热塑性聚氨酯，其量为75-95重量％，和2.乙烯-醋酸乙烯酯共聚物，其量为0-25重量％，其中醋酸乙烯酯的量为10-40重量％，优选25-30重量％，和填料，其选自无机和矿物填料、植物来源或植物性的有机填料、聚合物及其混合物，该填料为球状多边粒子，粒子大小分布为10-1000μm，优选45-500μm，或为纤维状粒子，长度为45-1000μm，优选45-500μm。优选的填料为粒子大小分布为45-500μm的木粉。填料还可以是白垩，特别是工业用白垩，其粒子大小分布为10-45μm，或聚合物如聚对苯二甲酸乙二醇酯(PET)，其粒子大小分布为45-500μm。
根据DIN EN 14510在65℃的温度下测量的热熔性粘合剂/填料复合物的表面粘性值为至少10N(最大为60N)，优选15N，特别是30N。大于60N的较高粘性值使材料的操作性显著最小化。
纵向伸长率表示活化状态材料的稳定性，其在90℃的烘箱中测量。在加热5分钟之后从烘箱取出悬挂的宽度为2cm和长度为10cm及厚度为0.95mm的试验带，测量长度的变化。测量样品相对于原来样品长度的长度并表示为百分数。在90℃下表现出最大为20％纵向伸长率的热熔性粘合剂/填料复合物为最适合的材料，条件是满足权利要求1的其它参数。
本发明提供了热熔性粘合剂/填料复合物形式的适于制鞋用热塑性加固材料的生产方法，其特征在于：热熔性粘合剂在最高220℃的温度下熔化和在搅拌或捏和条件下通过计量器将填料掺杂到热熔性粘合剂中，通过脱气设备排出水分和放出的气体，对可延展物质进行真空除气。然后可延展物质准备用于确定的鞋加固过程的其它处理。
表1包括本发明的热熔性粘合剂/填料复合物混合物。测定值表明该混合物适合用作鞋加固材料。
表1
组成   粘性在90℃+5下对微纤维人造革冷压[N/5cm]   纵向伸长率[％](热稳定性)   在100℃/21.6kg下的MVR/粘性/[cm3/10cm]   圆形试样2cm的表面粘性[N]   混合物分离的主要形式   材料合格
    1     79     14     3.6     39.8     NC/CF   是
    2     65     25     6.3     32.2     NC   是/否
    3     55     19     3.8     21.5     NC   是
    4     57     13     1.8     10.1     NC   否
    5     88     10     5.2     19.2     NC   是
    6     22     12     2.3     ＜5     NC   否
    7     49     ≥25     8.2     35.2     NC/CF   否
    8     59     ＜25     2.1     14.8     NC   是/否
    9     n.n.     27     2.8     18.3     NC   否
    10     n.n.(1)     n.n.(1)     16.2     36.4     CF   否
    11     n.n.(1)     n.n.(1)     67.7     37.6     CF   否
    12     n.n.(1)     n.g(1)     319.6     31.6     CF   否
    13     0     n.g     n.g     0   否
    14     n.g     ＞5     n.n.(2)     25     NC   否
组成1-14包含以下组分。
1.70重量％的平均分子量为80,000g/mol的聚ε-己内酯，和30重量％的粒子大小分布为50-500μm的木粉或木纤维(松木的)。
2.80重量％的平均分子量为80,000g/mol的聚ε-己内酯，和20重量％的粒子大小分布为150-500μm的木粉或木纤维。
3.70重量％的平均分子量为80,000g/mol的聚ε-己内酯，和30重量％的粒子大小分布为150-500μm的木粉或木纤维。
4.60重量％的平均分子量为80,000g/mol的聚ε-己内酯，和40重量％的粒子大小分布为150-500μm的木粉或木纤维。
5.65重量％的平均分子量为80,000g/mol的聚ε-己内酯，5重量％的EVA/乙烯-醋酸乙烯酯，和30重量％的粒子大小分布为150-500μm的木粉或木纤维。
6.70重量％的热塑性聚氨酯，其在190℃、10kg负载下测量的MVR值为20-35cm3/10min，和30重量％的粒子大小分布为150-500μm的木粉或木纤维。
7.70重量％的平均分子量为80,000g/mol的聚ε-己内酯，和30重量％的得自Omya的平均粒度为45μm的市售白垩。
8.70重量％的平均分子量为80,000g/mol的聚ε-己内酯，和30重量％的粒子大小分布为150-500μm的研磨聚对苯二甲酸乙二醇酯(PET)作为填料。
9.热塑性聚氨酯，其在190℃、10kg的负载下测量的MFFR值为20-35cm3/10min。
10.聚ε-己内酯，其平均分子量为80,000g/mol。
11.聚ε-己内酯，其平均分子量为40,000g/mol。
12.乙烯-醋酸乙烯酯共聚物，其具有28重量％的乙酸酯，和在190℃/2.16kg的条件下测量的熔体流动指数为150g/10min。
13.DE 26 21 195 C的材料
14.EP183192 C1实施例2的材料
表中使用以下缩写：
n.n.(1)：因为材料不够稳定而不可检测、不可测定。不可能使其活化，如不能进行热状态下的处理。
n.n.(2)：由于织物支撑不可测定。
n.g.：未测定。
NC：不完全的渐增温材料，沿混合物和表面材料(皮革)之间的胶条分离。
CF：内聚破坏一是指混合物内发生分离。
结果简述
实施例1、3、5和8的本发明材料的特征在于它们满足全部4个参数，它们保留在所谓的“产品窗口”之内，然而EP 183 192和DE 26 21 195的原料、产品9，10，11和12，以及材料13和14至少有一个参数发生偏离，从而被认为是不适合的，并从而位于产品窗口之外。此外，表1说明一些聚合物的适用性也受到限制。然而，由于它们光滑的表面，它们表现出低的粘合力。
生产方法
将平均分子量为80,000g/mol的热熔性粘合剂在180℃熔化。通过计量器将粒子大小分布为150-500μm的填料(木粉纤维混合物)以5-30重量％的量在搅拌和捏和下加入到热熔性粘合剂中，并通过脱气装置排出水分和气体。然后通过真空脱气对可延展物质进一步脱气。
将可延展物质加入到多级砑光机，砑光机表现出渐减的温度梯度，从40℃开始到20℃结束。在砑光机中，平稳地辊压可延展物质，在冷却之后，将片材从砑光机中取下。这一扁平的片材可根据确定的鞋头隆起和后帮的生产方法进行切削和切片。收集切削和切片处理产生的废料，并在碾磨工序之后将这一磨碎的物质再次用于所述方法中或可以在加固材料生产用粉末技术中以粉末形式用作原料。
热熔性粘合剂/填料复合物还可以制成粒子状，并且这种粒子可再次熔融并通过挤出或压延成为扁平薄片或片。
本发明的热溶性粘合剂/填料复合物的另一个生产方法为注射成型技术。
本发明的热熔性粘合剂/填料复合物还可以作为粒子大小分布为50-1000μm的细粉使用，和用于生产加固部件制造中使用的扁平薄片。
此外还可以在粉末涂层技术中使用热熔性粘合剂/填料粉末复合物，生产三维加固元件或部件。
本发明的包含这种热熔性粘合剂/填料复合物或根据不同的方法制造的加固材料或加固部件的鞋有特别好的耐磨性。

Claims (12)

1.热熔性粘合剂/填料复合物形式的制鞋用热塑性加固材料，其特征在于其包括以下物质：
a.50-95重量％的一种或多种热熔性粘合剂，其MVR值根据DINISO1133，在100℃、21.6kg条件下测量为2-300cm3/10min，和
b.50-5重量％的一种或多种填料，其不溶于热熔性粘合剂，且热熔性粘合剂/填料复合物同时满足以下参数：
1.MVR值为2-6cm3/10min，
2.根据DIN EN 14610，在65℃的温度下测量的表面粘性值为至少10N到最大为60N，
3.根据German DIN 53357标准测量的对表面材料的粘合值/抗剥强度至少为30N/5cm，
4.混合物在90℃的烘箱中保存5分钟后测量的最大纵向伸长率为25％。
2.权利要求1的热熔性粘合剂/填料复合物形式的制鞋用热塑性加固材料，其特征在于，
组分a热熔性粘合剂是由以下物质组成的混合物：1.75-95重量％的线型聚酯和/或75-95重量％的热塑性聚氨酯；和2.0-25重量％的乙烯-醋酸乙烯酯共聚物，其中醋酸乙烯酯的含量为10-40重量％；以及
50-5重量％的填料选自无机和矿物填料、植物来源或植物性有机填料、聚合物及其混合物，该填料为球状多边粒子，其粒子大小分布为45-1000μm，或为纤维状粒子，其长度为45-1000μm。
3.权利要求1的加固材料，其特征在于填料是粒子大小分布为45-500μm的木粉。
4.权利要求1的加固材料，其特征在于填料是粒子大小为45μm的白垩。
5.权利要求1的加固材料，其特征在于热熔性粘合剂/填料复合物的表面粘性值是25-45N。
6.权利要求1的加固材料，其特征在于热熔性粘合剂/填料复合物在90℃的温度下测量的纵向伸长率小于20％。
7.生产权利要求1的热熔性粘合剂/填料复合物形式的制鞋用热塑性加固材料的方法，其特征在于将热熔性粘合剂熔融，并在搅拌和捏和条件下通过计量器将填料加入到热熔性粘合剂中，同时通过脱气设备排出水分和放出的气体，然后对得到的可延展物质进行真空脱气，用于后续加工。
8.生产权利要求1的热熔性粘合剂/填料复合物形式的制鞋用热塑性加固材料的方法，其特征在于热熔性粘合剂被制成粒状，和该粒子经过再次熔融、然后通过挤出或压延被进一步加工成为扁平薄片。
9.生产权利要求1的热熔性粘合剂/填料复合物形式的制鞋用热塑性加固材料的方法，其特征在于使用注射成型机从热熔性粘合剂/填料复合物原料生产加固部件。
10.权利要求1的热熔性粘合剂/填料复合物在生产用于制造加固部件的扁平薄片中的应用，所述热熔性粘合剂/填料复合物为粒子大小分布为50-1000μm的细粉形式。
11.权利要求1的热熔性粘合剂/填料复合物在生产三维加固部件中的应用，所述热熔性粘合剂/填料复合物为粒子大小分布为50-1000μm的细粉。
12.包含权利要求1到11所述加固材料的鞋。
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