CN1051790C - 一种涂覆的基材 - Google Patents

一种涂覆的基材 Download PDF

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CN1051790C
CN1051790C CN91112773A CN91112773A CN1051790C CN 1051790 C CN1051790 C CN 1051790C CN 91112773 A CN91112773 A CN 91112773A CN 91112773 A CN91112773 A CN 91112773A CN 1051790 C CN1051790 C CN 1051790C
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H·P·坦南包姆
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Abstract

本发明涉及涂层体系，特别是涂覆的基材。该基材包括基底和多层不沾涂层；涂层包括底涂层、面涂层和一层或多层中间涂层，基底无妨碍涂层粘附的污物；底涂层以水分散体形式施于基底，该分散体包括含有50-90%熔融粘度至少1010泊的聚四氟乙烯第一树脂和50-10%第二树脂的全氟碳树脂和至少一种聚酰胺-酰亚胺和聚醚砜树脂，所述第二树脂选自熔融粘度在103-108泊的六氟丙烯与四氟乙烯的全氟化共聚物和熔融粘度在103-105泊范围内的全氟烷基乙烯基醚与四氟乙烯的全氟共聚物;以及面涂层和中间涂层包括全氟碳树脂。

Description

一种涂覆的基材
本发明涉及涂层体系，例如用以减少粘附而用于烹调器具的涂层体系尤其是本发明涉及一种涂覆的基材，一种多层涂层体系被直接施于光滑的，未经处理的基底表面，而且在涂层内具有浓度梯度。
在本技术领域中，一般说来，金属或玻璃基底在涂覆第一层涂层之前，先用某些方法粗糙化，以便机械结合力帮助化学粘结力将涂层保持在基底上。典型的粗糙化方式包括酸蚀，喷砂，吹砂和在基底上烘焙一层玻璃、陶瓷或搪瓷熔接物粗糙层。不沾涂料与基底的粘接问题常由于涂料的性质而恶化。如果涂料是最适合用于防止与食物颗粒的粘连，则为了在烹饪后便于清洗或延长使用期，或为了便于降低滑动接触摩擦，几乎可以肯定，将涂料很牢固地粘附在基底上是很困难的。
基底可以是金属的，通常用于烹调或工业上的如铝或不锈钢基底。基底也可以是玻璃或陶瓷的，甚至可以是塑料的(用于微波炉的烘盘)，或是一种工业制品，例如用碳钢制作的锯。无论何种基材或如何应用，如果必须将基底粗糙化以使涂层粘附牢固，则至少要增加成本并因此引起其它的麻烦，包括造成粗糙的表面(可以透过涂层而突出或显露出来)，对于表面特意要求平滑的场合，例如锯：蒸汽熨斗和复印辊，特别不希望出现这种情形。处理刻蚀材料的环保费用可能会很大。有时候，特别是对于玻璃和陶瓷基底，粗糙化会引起基材的强度降低或脆性，这是不能接受的。
增强不粘涂料对基底的粘附性的方法，在以下专利中已有说明。
美国专利4049863-Vassiliou(1977)讲授了一种底层涂料，它含有氟聚合物，例如聚四氟乙烯(PTFE)，胶态硅石和一种聚酰胺-酰亚胺(PAI)，以及其它组分，用各种技术将此涂料涂覆到-基底上，该基底最好是经喷砂火焰喷涂预处理的金属或金属氧化物或熔接物涂层，或将涂料涂覆到磷酸盐化和铬酸盐化的金属上。PTFE∶PAI的比率可以是1∶9。底涂层涂覆厚度一般为大约2～15微米(μm)干膜厚度(DFT)。干燥后，在底涂层上再外涂一层普通的氟聚合物熔接物并烘焙之。(本文中的份数，百分比和比例，除非另有说明，均按重量计算)。
美国专利4087394-Concannon(1987)公开了含水浓度梯度的氟聚合物涂层，它由20～80％的一种氟化乙烯丙烯(FEP)的均聚物或共聚物(由5-100％的四氟乙烯(TFE)与95-5％的六氟丙烯(HFP)制成)和80-20％的一种成膜聚合物(可以是PAI)组成。涂层用喷涂法涂覆到铝板或各种基底上。提到了其它一些应用技术。没有讲基底的予处理。尽管把PTFE和FEP看作是连续的介质，但没有提议使用例如50％的PTFE和50％的FEP的配料。
美国专利3928675和3857852(均为Tieszen)，讲授了在涂层中使用高粘度(＞1010)和低粘度(104泊)(109和103巴秒)PTFE以及聚亚芳基硫化物，例如聚亚苯基硫醚(PPS)的方法。
本发明，包括其实施例，提供一涂料物系，它包括一带有多层不沾涂层的基底，涂层包括一底涂层，一外涂层和在底涂层与外涂层之间的一层或多层中间涂层，其中：
基底没有妨碍涂层粘附力的玷污物，
底涂层以一种水分散体的形式涂覆到基底上，其中所述水分散体包括全氟碳树脂和至少一种聚酰胺酰亚胺和聚醚砜树脂，其中全氟碳树脂含有50-90％(重量)的第一树脂(熔融粘度至少为大约1010泊的聚四氟乙烯)和50-10％的第二树脂全氟烷基乙烯基醚、优选全氟丙基乙烯基醚与四氟乙烯的全氟化共聚物(PFA)，其熔融粘度在103-105泊的范围内，以及
外涂层和任何中间层涂层包含有全氟碳树脂。
本发明不仅由于不用对基底表面进行粗糙化处理而降低了费用，而且还保持了涂覆层表面较为光滑，这有利于烹调器的防粘性能和蒸汽熨斗底板的滑动性能。本发明也可以取消对已涂覆的复印辊表面所进行的昂贵的抛光工序，而用盘绕涂覆和滚压涂覆的技术进行PTFE涂层的分散。
本发明的各实施例均涉及在底涂层或外涂层使用至少两种具有不同熔融粘度的PTFE树脂。一对树脂具有较高和较低的熔融粘度，另一对树脂具有较低和更低的熔融粘度。
高熔融粘度氟聚合物涂层对各种类型的金属基底、特别是对平滑的金属的粘附力可以在底层中通过化学诱导分层或形成浓度梯度而得到明显地改进。
将低熔融粘度(MV)[在103-108泊(102-107巴秒)的范围内]的全氟碳聚合物加入到底涂层物系中，该物系由高MV[1011泊(1010巴秒)]的PTFE和一种聚合物粘结剂(例如聚酰胺-酰亚胺或聚亚苯基硫醚)组成，产生叠加效果，其中氟聚合物从基底的交界面分层，而聚合物粘结剂在基底面处获得较高的浓度和固化度，从而提高粘附力。为这种分层作用所要求的固化温度可以通过选择氟聚合物来调整。
全氟聚合物的熔融粘度可以用已知技术进行测定，例如Gangal等人的美国专利4636549(1987)，参见第4栏25-63行。
使用本发明的涂料，只需对平滑的基底进行冲洗去除油脂及可能妨碍粘附的任何其它污物，本发明的涂层物系就可提供良好的食品防粘性能和对普通耐久测试的良好耐久性，普通耐久测试包括，例如“虎爪”滥抓炊具测试，它包括在测试炊具时用装有多个圆珠笔轴的有一定重量的夹持器在一个平底煎锅内表面转动。该测试在美国专利4252859-Concannon和Vary(1981)第二栏，14-24行中概述。
在一般先有技术中，为了增强不粘涂层的粘附力，表面的处理包括：腐蚀或喷砂以产生表面粗糙度。粗糙度用R760型表面粗糙度测试仪(意大利、米兰、Alpa公司制造)以微英寸平均值进行测量。一般的辊轧铝板经清洗去油和去除沾污物后，其粗糙度为16～24微英寸(0.6～0.96μm)。钢表面的粗糙度变化范围更宽一些，但一般要小于50微英寸(2μm)。钢和铝，二者在被涂覆不粘涂层之前，一般要使其粗糙度增加到100微英寸(4μm)以上，对于某些用途的铝则优选180-220微英寸(7。2-8.8μm)的粗糙度。因此，本发明特别适用于粗糙度小于100，最好小于50微英寸(小于4μm，最好小于2μm)钢或铝基底。
使用一种低MV(至少为106泊或105巴秒)PTFE与一种更低MV(103-105泊或102-104巴秒)的PTFE可获得相似的效果。为获得分层作用，要求这两种PTFE的MV值至少相差102泊。
本发明的底涂层也可以用于以本技术领域已知的各种方法进行粗糙化处理的基底上，从而使涂层体系比不应用这样的底涂层效果更好这样可以把改进的化学粘附力性能与机械作用结合起来，生产出超凡的产品。
在下文的实例中，聚酰胺-酰亚胺、胶态硅石和分散体是本技术领域中已知的，优选美国专利4049863-Vassiliou(1977)中公开的那些物质；PFA是美国专利4253859-Concannon和Vary(1981)所概述的那种物质，但其熔融粘度的范围为2-4×104泊，最好是粉碎过的粉料或干燥的分散体形式，不论哪一种形式，其平均颗粒尺寸都在20-25μm范围内；群青色是美国专利4425448-Concannon和Rummel(1984)中公开的哪种。
下面的实施例和测试数据证明，将氟聚合物外涂层用作底涂层时对粘附性能的改进。氟聚合物以在水中60％的分散体形式提供。如通常那样，在表中列出分散体中的固体成分。这些成分接通用的技术相掺混，然后喷涂到光滑的，去除了油污的铝质基底上。
实施例1：FEP/PTFE-多层涂料体系
            表1
配方：40％ FEP/60％底涂层PTFE
    重量百分比
    0.007         氧化锌
0.050      “Afflair 153”产自
            EM Industries的，二氧化钛涂覆
            的云母
6.497       群青色颜料
6.750      “T-30”PTFE产自杜邦公司
0.972      “Ludox AM”胶态硅石，产自杜邦公司
4.153      “TE 9075”FEP，产自杜邦公司
4.641       AI-10。聚酰胺-酰亚胺树脂
            产自Amoco
67.628      去离子水
0.630      “Triton X-100”辛基苯酚聚醚
            醇非离子表面活性剂，产自
            Rohm and Haas
0.655       二乙基乙醇胺
1.309       三乙胺
3.614       糠醇总计100.00
            表2         外涂层
重量百分比：
0.790      “Afflair 153”
0.389       槽法碳黑颜料
0.172       群青色颜料
0.195       硅酸铝
40.704     “T-30”PTFE
0.442             辛酸铈
0.054             聚萘磺酸钠
1.834             乙二醇单丁基醚
0.928             油酸
33.772            去离子水
3.480             三乙醇胺
2.246             烃溶剂
2.914            “Triton  X-100”
12.080            丙烯酸胶乳，39重量份的甲基丙烯酸甲酯
总计100.00        三元共聚物/57份丙烯酸乙酯/4份甲基
                  丙烯酸，在水中40％固体的分散体，平均
                  颗粒尺寸0.2sm应用：
此体系包括用于底涂层的PTFE，FEP和聚酰胺-酰亚胺，其涂覆到金属表面的干膜厚度(DFT)为5-10sm(金属表面已经冲洗去除了油污)，底漆风干后，再涂外层漆，外涂层可为单层(15-17.5sm DFF)或为多层(每层厚度为12.5-17.5sm DFT)外涂层配方与表2所示配方相类似。漆膜先在150℃烘焙10分钟，然后在415℃以上的高温烘焙3分钟。测试：
在光滑的除去油污的铝基底面(粗糙度为12)上涂覆单层涂层，然后在不同的条件下固化，涂覆后的基底在沸水中浸泡20分钟。从基底刮下涂层，然后让一个人设法用其手指甲将涂层拉开。在下表中，P表示涂料层未变松，F表示拉开至少1厘米。
表3        在光滑铝面上的手指甲粘附性
           固化(温度℃/时间-分钟)
780/3     429/5            432/10
  P         P                P对于没有FEP的涂层，测试结果均不行。
用两种不同性质的FEP和PTFE作为平滑铝炊具的底涂层和一层外涂层，将该炊具进行如前所述的虎爪滥抓测试。确定涂层损坏的值标定为5次，记录标准炊具测试周期数并列于下表，同时列出与用喷砂处理基底后的涂覆商品炊具对比的百分数。结果是比许多优良的商品炊具还要好。
                   表4
  带有FEP/PTFE底漆的炊具性能
                        烹饪标定为5涂料系统        DFT        范围    平均值    与商品炊
                                         具的％40％ FEP     1.0-1.1      80-120    95       114/60％ PTFE30％ FEP     1.0-1.1      80-120    103      124/70％ PTFE
实施例2.FEP/PTFE-多层涂料系统
      表1配方：40％ FEP/60％ PTFE底漆
重量酚比
0.007         氧化锌
0.050        “Afflair 153”，由产自
              EM Indusrries的二氧化钛涂覆的云母
6.497         群青色颜料
6.750        “T-30”PTFE，产自杜邦
0.972        “Ludox AM”胶体硅石，产自杜邦
4.153        “TE 9075”FEP产自杜邦
4.641         AI-10聚酰胺-酰亚胺树脂产自Amoco
67.628        去离子水
0.630        “Triton X-100”辛基苯酚聚醚
              醇非离子表面活性剂产自Rohm和Haas
0.655         二乙基乙醇胺
1.309         三乙胺
3.614         糠醇
总计100.00

Claims (7)

1.一种涂覆的基材，包括基底和多层不沾涂层，涂层包括一层底涂层，一层面涂层，和在底涂层和面涂层之间的一层或多层中间涂料层，其中：
基底上没有妨碍涂层粘附的污物，
底涂层是以水的分散体形式施于基底的，该分散体包括全氟碳树脂和至少一种聚酰胺-酰亚胺和聚醚砜树脂，其中全氟碳树脂含有50-90％的第一树脂和50-10％第二树脂，所述的第一树脂是熔融粘度至少为1010泊的聚四氟乙烯，而第二树脂选自熔融粘度在103-108泊范围内的六氟丙烯与四氟乙烯的全氟化共聚物和熔融粘度在103-105泊范围内的全氟烷基乙烯基醚与四氟乙烯的全氟共聚物，以及
面涂层和中间涂层包括全氟碳树脂。
2.根据权利要求1的涂覆基材，其中所说第一树脂的熔融粘度至少为1011泊，所说第二树脂是熔融粘度在103-105泊范围内的全氟烷基乙烯基醚与四氟乙烯的全氟共聚物。
3.根据权利要求1的涂覆基材，其中所选择的共聚物是六氟丙烯与四氟乙烯的共聚物。
4.根据权利要求1的涂覆基材，其中基底选自铝，不锈钢和碳钢。
5.根据权利要求4的涂覆基材，其中基底在涂覆前的表面粗糙度小于4微米。
6.根据权利要求4的涂覆基材，其中基底在涂覆前的表面粗糙度小于2微米。
7.根据权利要求1的涂覆基材，其中由所说的水分散体形成的底涂层沿其厚度方向的组成是不均匀的，并且聚四氟乙烯的浓度在与基底交界面处的值要比在另一相对交界面处的值低。
CN91112773A 1990-12-12 1991-12-12 一种涂覆的基材 Expired - Fee Related CN1051790C (zh)

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US07/626,491 US5230961A (en) 1990-12-12 1990-12-12 Non-stick coating system with PTFE-FEP for concentration gradient
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US07/762,068 US5240775A (en) 1991-09-23 1991-09-23 Non-stick coating system with PTFE-PFA for concentration gradient
US762,068 1991-09-23

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