CN1496385A - 适于改进尼龙涂料的粘合力的涂料溶液及其用法 - Google Patents

适于改进尼龙涂料的粘合力的涂料溶液及其用法 Download PDF

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CN1496385A
CN1496385A CNA028064631A CN02806463A CN1496385A CN 1496385 A CN1496385 A CN 1496385A CN A028064631 A CNA028064631 A CN A028064631A CN 02806463 A CN02806463 A CN 02806463A CN 1496385 A CN1496385 A CN 1496385A
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coating solution
nylon
polymeric amide
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R·U·帕吉拉甘
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Abstract

公开了改进与尼龙、聚酯或它们的混合物形成的基材的要求的粘合性的新颖的涂料溶液。这些涂料溶液包括具有特定溶解度的尼龙和选择的甲醛树脂及树脂混合物。该溶液提供了优异的粘合性，因而对于丝应用以及形成的结构具有吸引力。

Description

适于改进尼龙涂料的粘合力的涂料溶液及其用法
                        发明领域
本发明涉及改进尼龙涂料在尼龙和聚酯的基材上的粘合力。更具体地，本发明涉及使用选择的高亚氨基含量的甲醛树脂或其部分烷基化的或非烷基化的衍生物，以改进混和的尼龙聚合物与由尼龙和聚酯制成的丝、薄膜、零件等的粘合力的方法。
                        发明背景
尼龙“多元聚合物”是由尼龙形成单体的混合物制成的尼龙，使得尼龙聚合物含有至少两种尼龙结构单元的混合物。此类尼龙作为各种涂料和粘合剂应用而销售。通常这些尼龙容易溶解在有机溶剂中，一般作为溶液应用。参见例如E.I.DuPont de Nemours and Company，Inc.出版的标题为“Elvamide_Nylon Multipolymer Resins，Propertiesand Uses”(1977年9月)和“Elvamide_Nylon Multipolymer Resinsfor Thread Bonding”(1977年10月)的小册子。
一般用聚合材料(而且大部分情况下都加入润滑剂)涂覆缝纫线，在缝纫操作期间保护其不受磨损。此外，对于双绞式多丝缝纫线，聚合物涂料(也称为丝粘合剂)还防止单股丝的绽裂和散开(解开)。一般参见1990年11月的DuPont小册子和Kohan，M.I.的“NylonPlastics Handbook”，Hansen/Gardner Publications，Inc.(1995)第283-290页。
尼龙多元聚合物已用作丝粘合剂达几十年。然而，对于改进涂料与丝的粘合力的需要在增加，例如在高要求的现代应用中。这对于依靠紧密的纺织品的应用，例如在行李箱和汽车安全气囊、皮革等的应用也是最重要的。在这种应用中，丝的磨损很大，而且缝纫针的运行温度比诸如服装中所用的更疏松的纺织品要高得多。涂料的粘性差会在涂料从丝表面脱落的地方产生“蛇皮”效果。这样会导致涂料疏松，从而阻碍了要求操作中止的针。此外，在检查纤维表面时看见的涂料疏松也使美学效果很差。
在缝纫丝和纤维的情况下，尼龙共聚物、三元共聚物，以及更高的多元聚合物被用作涂料。这些聚合物通常都可溶于有机溶剂，尤其是醇中。尼龙涂料一般通过将丝浸入尼龙多元聚合物溶液中，接着使丝穿过干燥箱，然后送入温度一般高于尼龙混和的聚合物的熔点的熔融箱中来涂覆。尼龙多元聚合物涂料在丝上的熔融改进了粘合力。尼龙混和的聚合物通常适于这种用法，因为它们具有韧性、良好的耐磨性，且易溶于溶剂中。与尼龙混和的聚合物相关的这些方法和益处的更多信息参见上述Elvamide_(1977年10月)小册子和“Nylon PlasticsHandbook”。
上述小册子描述了诸如环氧树脂、酚醛树脂和蜜胺-甲醛树脂的热固性树脂与尼龙多元聚合物交联并改进涂料粘合力的能力。尼龙低聚物与这些热固性树脂反应形成热固性-热塑性组合物。
US 4992515描述了用Cytek Industries，Inc.提供的全烷基化蜜胺-甲醛树脂Cymel_1135，与强酸催化剂一起交联尼龙6/66/69、尼龙6/66/610和尼龙6/66/612三元共聚物的方法。达到的交联程度通过交联后的涂料在原有溶剂中的不溶度测量。交联的尼龙涂料变得不溶于溶剂中。然而，对于粘合力和耐剥离性改进了多少，未提供任何数据。
在Cytec提供的标题为“High Solids Amino CrosslinkingAgents”(1994年9月)的小册子中公开了甲醛衍生的交联剂的不同类型和反应性。例如，用于下文描述的几个实施例中的Cymel_325具有1.0重量％的游离甲醛。其他等级的Cymel_可含有多达3.5重量％的游离甲醛，可用于实施本发明。这些和其他交联剂通过由羟甲基取代胺官能团上的氢导致的胺官能团与甲醛的反应来制备。羟甲基官能团与醇反应，将羟基官能团转化为烷氧基。依反应程度不同，可制备这些交联剂的许多种类。例如，有可商购的蜜胺-甲醛交联树脂类型。蜜胺(以下结构1)中的氨基官能团的部分反应
                 
Figure A0280646300041
                          结构1导致结构2。
                   
                        结构2
其中仅有一些氢已被羟甲基取代。结构2与醇的烷基化反应使羟基转化为结构3中所示的烷氧基。
                 
Figure A0280646300052
                        结构3
含有结构3所示类型官能团的蜜胺-甲醛树脂归类为高亚氨基型树脂。蜜胺甲醛的完全取代反应以及随后的部分烷基化导致了结构4。
           
Figure A0280646300053
                        结构4
含有此类官能团的树脂归类为部分烷基化树脂。如果与醇的反应允许达到完全反应，就得到全烷基化的衍生物(结构5)。
              
Figure A0280646300061
                            结构5
本领域普通技术人员很容易理解的是，可将不同类的官能团(例如氨基或烷氧基)设计到分子中。每种类型的化学性质不同，并具有不同的特性和反应性。诸如Cymel_1135的完全烷基化树脂要求通过强酸催化而引发它们的反应。
长期需要一种技术，以改进尼龙涂料与尼龙和聚酯的基材的总粘合力。这种粘合力的改进将更好地促进所形成制品的美学质量，并提供由于最终产物的不均匀性而废弃的材料减少带来的经济效益。
本发明的目的是开发一种加工技术和涂料溶液，以改进尼龙涂料与尼龙、聚酯及其混合物的粘合力。这种开发不仅应用于丝(thread)，通常还应用于要求这种粘合力的任何基材。本发明的另一个目的是提供一种适应性强，并可用于包括单丝、多丝、薄膜、管材、成型部件等的各种应用的技术和溶液。本发明的特征是粘合剂粘合本身的耐久性，使其能适用于对材料进行大范围的处理和操作的苛刻的应用。本发明的优点是该方法可利用任何不同溶剂。本发明的这些和其他目的、特征和优点将参考本发明的以下描述而得到更好地理解。
                        发明概述
本文公开了促进聚酰胺与聚酰胺、聚酯或它们的混合物的基材的粘合力的涂料溶液。这些溶液包含：
(a)在选择的有机溶剂中的溶解度至少为0.5重量％的聚酰胺，和
(b)以聚酰胺的重量计为1-100重量％的高亚氨基、部分烷基化或非烷基化的甲醛树脂，所述甲醛树脂选自蜜胺-甲醛、甘脲(glycoluril)-甲醛、苯并胍胺-甲醛及其混合物。
任选的可添加以甲醛树脂重量计为0-20重量％的催化剂。此外，可加入全烷基化的蜜胺-甲醛、甘脲-甲醛或苯并胍胺-甲醛树脂。树脂(b)起粘合促进剂作用。树脂(b)优选以酰胺重量的1-40重量％(最优选1-20重量％)的量加入。
本文还公开了用本发明的涂料溶液涂覆这些基材的方法。这种方法很容易被本领域普通技术人员理解。参见例如本文描述的丝涂覆方法。
                        发明详述
对本发明目的而言适于作为涂覆材料的尼龙是衍生自含有6-12个碳原子的内酰胺的聚酰胺、衍生自2-12碳的二胺和6-12碳的二酸的聚酰胺、衍生自聚丙二醇二胺或聚乙二醇二胺和6-12碳原子二酸的聚酰胺，以及上述聚酰胺的混合聚合物，条件是这些聚酰胺必须在醇、酚、甲酚或这些溶剂的混合物中具有至少0.5重量％的溶解度。优选适合作为涂料的聚酰胺是诸如6/66共聚物或6/66/X的多元聚合物，其中X为衍生自含有7-12个碳原子的内酰胺的聚酰胺，或衍生自2-12碳的二胺和6-12碳的二酸的聚酰胺。
本发明合适的溶剂是甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、糠醇、苄醇、苯酚和间甲酚，或这些溶剂的混合物。所选溶剂或溶剂混合物可含有水。此外，可加入氯化的溶剂作为稀释剂。合适溶剂的选择还在于本领域普通技术人员理解的几个因素，例如基材的几何形状、制品的厚度等。
适合作为本文的单丝、多丝、薄膜或管材的基材的聚酰胺的实例是衍生自4-12碳的二胺和6-12碳的二酸、带有6-12个碳原子的内酰胺和上述单体的混和聚合物的聚酰胺。适合于单丝、多丝、薄膜或管材的聚酯的实例是聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯或聚对苯二甲酸丁二醇酯，以及它们的共聚物。本领域普通技术人员知道，聚合物之间的粘合力和相容性在这两种聚合物为相同种类或类型时较好，如极性聚合物与其他极性聚合物的粘合性往往较好。因此尼龙与其他尼龙间的粘合性本来就比其与聚酯间的粘合性更好。
适于本发明的蜜胺-甲醛树脂是诸如Cymel_325、1158、385、1172和1123的含有亚氨基和羟甲基部分的那些。它们是由CytekIndustries，Inc.提供的商品级材料。带有或不带有催化剂的蜜胺-甲醛树脂优选的加入尼龙多元聚合物溶液中并作为单一溶液涂覆到基材上。然而，具有可比的效果，可将带有或不带有催化剂的蜜胺-甲醛树脂预涂覆到基材上。
合适的催化剂是诸如磷酸的无机酸、诸如对甲苯磺酸、乙酸、草酸和邻苯二甲酸的有机酸。
除了诸如单丝的丝、管材、纺织品、薄膜和其他挤出或成型制品的材料外，在很多情况下，也能涂覆尼龙聚合物以增强表面性能。这些性能包括例如耐磨性、防护性能或诸如聚酯的表面改性，使其表面对于后续操作而言更具极性，使改性的表面更容易处理。
本文还公开和要求了已涂覆了本发明的涂料溶液的制品。首先提供了包含聚酰胺、聚酯或它们的混合物的基材的涂覆制品。然后涂覆涂料溶液，以形成预涂的基材。涂料溶液含有至少0.5重量％高亚氨基、部分烷基化的或非烷基化的甲醛树脂，所述甲醛树脂选自蜜胺-甲醛树脂、甘脲-甲醛树脂、苯并胍胺-甲醛树脂及其混合物。最后将在所选有机溶剂中具有至少0.5重量％的溶解度的聚酰胺涂覆到预涂基材上。
本发明将通过参考以下实施例更好地理解和掌握。
                         实施例
丝涂覆方法
丝的涂覆以实验室涂覆单元进行，与上文提及的有关Elvamide_的DuPont小册子(1977年10月)和“Nylon Plastics Handbook”中描述的相似。干燥和熔融部分用通过管式电加热器加热的热氮气加热，该加热器装有控制器，使两部分的温度可独立控制。在典型的涂覆试验中，使丝穿过通过将涂料溶液从滴定管中连续滴到沙罩上而饱和了涂料溶液的沙罩之间。丝在干燥部分的停留时间为6秒钟，在熔融部分也停留6秒钟。停留时间通过卷绕电机的提升速度控制。为了提供精确比较的基准，往往从同一卷中选择特定的丝。
耐磨性和股间粘合性
丝涂覆后，在测试前将其在相对湿度(RH)50％的室中调理6天。丝的一端与由电机驱动(以44圈/分钟的速度)的往复摆动的臂连接，另一端与230.0g的重量连接(使丝与尼龙66单丝摩擦)。丝以0.025-0.030英寸的直径悬挂尼龙66单丝。记录圈数。在测试期间，通过50倍的放大镜观察丝的外观。观察涂料磨损点作为圈数。圈数增加反映了耐磨性增加。
试样的股间粘合性通过以和原缠绕方向相反的方向拧带涂层的丝来进行定量比较。采用从0到3的定量分级体系。当每股相互间完全分离时为0；当每股都分离但某些部分股仍互相粘合时为1；当仅有少部分股相互分离时为2；当未发现股分离时为3。严格来讲采用0.5的分级单位(例如“1.5”和“2.5”)。
实施例1和2
在装有磁性搅拌器和冷凝器的烧瓶中加热Elvamide_8061和甲醇，制备11.0重量％的Elvamide_8061溶液。所需溶液的量取决于需涂覆的丝的量。在典型的试验中，通过加热11.0g Elvamide_8061和89.0g甲醇来制备100g溶液。
用上述方法以干燥部分停留6秒和熔融部分停留6秒来涂覆210旦的3股尼龙丝。结果示于下表中。
实施例       干燥温   熔融温    Wt％涂料  磨擦圈数  股间粘
             度℃     度℃                           合性
比较例1      80       120         4.5        24       3
比较例2      120      170          4.7       53       3
实施例3和4
用实施例1的方法制备含有11.0重量％Elvamide_8061、2.0重量％Cymel_1135和0.2重量％对甲苯磺酸的甲醇溶液。用实施例1的方法用该溶液涂覆210旦的3股尼龙丝。该实施例根据US 4992515用完全烷基化的蜜胺-甲醛交联剂和强酸催化剂进行。
实施例   WT.％CYMEL_ Wt％对  干燥温 熔融温 Wt％   摩擦     股间粘
                      甲苯    度℃   度℃   涂料   圈数     合性
                      磺酸
比较例3  2％Cymel(R)   0.2    80     120    3.7    32         2
         1135
比较例4  2％Cymel(R)   0.2    120    170    4.1    ＞200      1
         1135
结果表明，在较低熔融温度下(实施例3)，耐磨性与Elvamide_8061本身(实施例1)没有明显差别。较高熔融温度(实施例4)下的耐磨性有显著改进，但股间粘合性很差。
实施例5到16
用上述实施例中的方法，用浓度为11.0重量％的Elvamide_8061与不同Cymel_交联剂混和制备涂料溶液。以实施例1的方法用这些溶液涂覆210旦的3股尼龙丝。
实施例   WT.％CYMEL_       Wt％对   干燥温   熔融温   Wt％    摩擦    股间
                            甲苯     度℃     度℃     涂料    圈数    粘合性
                            磺酸
比较例5  2％Cymel(R)303      0.2     80       120      3.4     53      2.5
比较例6  2％Cymel(R)303      0.2     120      170      4.4     ＞200   0.5
7        2％Cymel(R)325      0.2     80       120      4.1     20      3
8        2％Cymel(R)325      0.2     120      170      5.6     ＞200   2
9        2％Cymel(R)325      0       80       120      2.9     148     3
10       2％Cymel(R)325      0       120      170      4.9     75      3
11       2％Cymel(R)385      0.2     80       120      3.4     28      3
12       2％Cymel(R)385      0.2     120      170      4.4     ＞200   1.5
13       2％Cymel(R)385      0       80       120      4.4     42      3
14       2％Cymel(R)385      0       120      170      4.7     45      3
15       2％of 1/1 Cymel(R)  0       80       120      4       74      3
         303/325
16       2％of 1/1 Cymel(R)  0       120      170      1.2     150     3
         303/325
比较例5和6说明了根据US 4992515的另一种全烷基化蜜胺-甲醛树脂的用途。在较低熔融温度下(比较实施例5)，耐磨性比仅有Elvamide_8061(比较实施例1)稍好，并具有良好的股间粘合性。然而，在较高熔融温度下，尽管耐磨性得到改善，但股间粘合性差(比较实施例6)。另一方面，采用高亚氨基交联剂Cymel_325(实施例7到10)和部分烷基化的交联剂Cymel_385(实施例11到14)，以及全烷基化的Cymel_303(实施例15和16)的混合物都提供了良好的耐磨性和股间粘合性。
实施例17到36
根据上述实施例中的方法，用浓度为11.0重量％的Elvamide_8061与不同Cymel_交联剂混和制备涂料溶液。然后以比较实施例1的方法用这些溶液涂覆220旦的3股聚对苯二甲酸乙二醇酯丝。
实施例        WT.％      Wt％     干燥温  熔融温 Wt％涂料  摩擦圈数    股间粘合性
          CYMEL_      催化剂       度℃   度℃
比较例17      0          0          80     120    3.2        14             2
比较例18      0          0          120    170    0.6        14             2
比较例20      1.1％      0.11％     80     120    3.2        23             2
          Cymel(R)1135  PTSA
比较例20      1.1％      0.11％     120    170    1.9        9              2
          Cymel(R)1135  PTSA
比较例21      1.1％      0.11％     80     120    1.9        25             1.5
          Cymel(R)303   PTSA
比较例22      1.1％      0.11％     120    170    2.9        8              2
          Cymel(R)303   PTSA
23            1.1％      0.11％     80     120    2.8        40             2
          Cymel(R)325   PTSA
24            1.1％      0.11％     120    170    0.4        14             2.5
          Cymel(R)325   PTSA
25            1.1％      0.11％Ac   80     120    4.6        55             2
          Cymel(R)325   ACID
26            1.1％      0.11％Ac   120    170    2.5        46             2
          Cymel(R)325   ACID
27            0.5％      0          80     120    4.6        37             2.5
          Cymel(R)325
2B            0.5％      0          120    170    0.2        48             2.5
          Cymel(R)325
29            1.0％      0          80     120    2.2        47             2.5
          Cymel(R)325
30            1.0％      0          120    170    0.9        57             2
          Cymel(R)325
31            4.0％      0          80     120    6.4        ＞200          2
          Cymel(R)325
32            4.0％      0          120    170    2.9        109            2.5
          Cymel(R)325
33            2.2％      0          80     120    5          44             2.5
          Cymel(R)1158
34            2.2％      0          120    170    2.23       44             2.5
          Cymel(R)1158
35            2.2％      0.022％    80     120    4.6        66             2.5
          Cymel(R)1158   PTSA
36            2.2％      0.022％    120    170    1.9        39             2
          Cymel(R)1158   PTSA
PTSA＝对甲苯磺酸 Ac ACID＝乙酸
仅用Elvamide_8061的比较实施例17和18表现出仅为14的耐磨性，比比较实施例1和2用尼龙丝获得的耐磨性低得多。这种耐磨性的差别说明了诸如尼龙与聚酯的不同聚合物间固有的低粘合力。股间粘合性仍然相当好。用US 4992515中描述的诸如Cymel_1135或303的全烷基化蜜胺-甲醛交联剂和对甲苯磺酸催化剂未获得耐磨性的明显改善(比较实施例19到22)。另一方面，用诸如Cymel_325和1158的高亚氨基蜜胺-甲醛交联剂在耐磨性和股间粘合性上均得到显著改善。
实施例37到40
用6.0重量％Cymel_350和1.0重量％对甲苯磺酸催化剂的甲醇溶液，在80℃的干燥部分停留6秒和170℃的熔融部分停留6秒，来预涂覆220支的3股聚对苯二甲酸乙二醇酯丝。然后用11.0重量％的Elvamide_8061甲醇溶液而不用其他催化剂(实施例37和38)，以及用11.0重量％Elvamide_8061及1.0重量％对甲苯磺酸的甲醇溶液(实施例39和40)，以实施例1的方法涂覆已预涂的丝。
  实施例   Wt％对甲苯磺酸   干燥温度℃   熔融温度℃   Wt％涂料   摩擦圈数   股间粘合性
    37     0     80   120     5.5     41     2.5
    38     0     120   170     4.3 超过80     2.5
    39     1.0     80   120     6.9     54     2
    40     1.0     120   170     3.4 超过100     2.5
结果表明，与比较实施例19到22相反，用全烷基化树脂Cymel_350预涂覆的聚酯丝提供了很好的耐磨性和股间粘合性。在用Elvamide_8061的后续涂覆中存在催化剂未发现有明显的负面或正面影响。

Claims (10)

1、适于粘合至聚酰胺与聚酰胺、聚酯或它们的混合物的基材的涂料溶液，包含：
(a)在选择的有机溶剂中的溶解度至少为0.5重量％的聚酰胺，和
(b)以聚酰胺的重量计为1-100重量％的高亚氨基，部分烷基化或非烷基化的甲醛树脂，所述甲醛树脂选自蜜胺-甲醛、甘脲-甲醛、苯并胍胺-甲醛及其混合物。
2、权利要求1的涂料溶液，还含有以甲醛树脂重量计最多为20重量％的催化剂。
3、权利要求2的涂料溶液，其中所述催化剂为无机酸。
4、权利要求1的涂料溶液，其中所述溶剂选自甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、糠醇、苄醇、苯酚和间甲酚，和它们的混合物。
5、权利要求1的涂料溶液，其中所述树脂(b)以聚酰胺重量的1-40重量％的量存在。
6、权利要求1的涂料溶液，其中所述树脂(b)以聚酰胺重量的1-20重量％的量存在。
7、权利要求1的涂料溶液，其中任何所述树脂(b)为高亚氨基或部分烷基化的。
8、尼龙或聚酯的成型结构，其涂覆了权利要求1的涂料溶液。
9、涂覆制品，包含(I)聚酰胺、聚酯或它们的混合物的基材，(II)涂覆涂料溶液形成预涂的基材，所述涂料溶液含有至少0.5重量％高亚氨基、部分烷基化或非烷基化的甲醛树脂，所述甲醛树脂选自蜜胺-甲醛树脂、甘脲-甲醛树脂、苯并胍胺-甲醛树脂及其混合物，和(III)涂覆到所述预涂基材上的在所选有机溶剂中具有至少0.5重量％溶解度的聚酰胺。
10、权利要求9的涂覆制品，其中所述涂料溶液(II)还含有以甲醛树脂重量计最多20重量％的催化剂。
CNA028064631A 2001-03-14 2002-03-14 适于改进尼龙涂料的粘合力的涂料溶液及其用法 Pending CN1496385A (zh)

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CN103476984A (zh) * 2011-04-13 2013-12-25 小松精练株式会社 纤维布帛的制造方法以及纤维布帛

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CN101670672B (zh) * 2009-08-14 2012-03-21 天津市天锻压力机有限公司 可调节行程的组合框架无拉杆式玻璃钢制品液压机

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CN103476984A (zh) * 2011-04-13 2013-12-25 小松精练株式会社 纤维布帛的制造方法以及纤维布帛
CN103476984B (zh) * 2011-04-13 2016-06-29 小松精练株式会社 纤维布帛的制造方法以及纤维布帛
CN102220065A (zh) * 2011-04-26 2011-10-19 安徽汇联机械工业有限公司 汽车轮毂用闪光白色漆

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JP4163000B2 (ja) 2008-10-08
ATE393793T1 (de) 2008-05-15
US20020198330A1 (en) 2002-12-26
EP1373371B1 (en) 2008-04-30
WO2002072673A2 (en) 2002-09-19
JP2004535518A (ja) 2004-11-25
EP1373371A2 (en) 2004-01-02
DE60226315T2 (de) 2009-06-25
US6805969B2 (en) 2004-10-19
WO2002072673A3 (en) 2003-02-13
DE60226315D1 (de) 2008-06-12

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