CN1038968A - 氟树脂涂覆物 - Google Patents
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Abstract
本发明涉及能提高设备耐磨性的氟树脂涂覆物。这种氟树脂的特征是在氟树脂中分散有聚酰胺酰亚胺树脂,聚酰亚胺树脂、聚亚苯基硫醚树脂、聚醚砜树脂或它们的混合物,以及云母。这种能显著提高其耐磨性的氟树脂涂覆物可广泛用于要求高温下具有耐磨性的诸如平底锅和电热平板等厨房用具以及食品工业、电器工业、机械工业领域中。
Description
本发明是关于能迅速提高诸如厨房用具等耐磨性的氟树脂涂覆物。
氟树脂由于其优良的不粘性和耐化学试剂性而被广泛地用于厨房用具(如带把平底锅、锅、电热平板、开口保温饭盒、烧热水锅等)食品工业、电器工业、机械工业等。
为了在铝等金属基材上涂覆氟树脂,通常,广泛采用的方法是首先在经过喷砂处理而使其表面粗糙化的基材上涂上底漆。由其产生粘着作用而使氟树脂表涂层牢固地粘着的方法(例如,特公昭62-5466号记载的打底法)。
另外,还采用如下的机械粘着的方法,即在基材表面设计成“蛸壶”形的细微凹凸状,使氟树脂嵌入凹凸中,由于“投锚”的效果而使氟树脂与基材进行机械粘附的方法(例如,特公昭56-35516号记载的腐蚀法)。
然而,由于这样得到的氟树脂涂覆物其本身对金属等的耐磨性很小,因此,对于象带把平底锅、电热平板、锅等要求具有耐磨性的用途方面还存在着一定的问题。为了改善该性能已采用了多种方法。作为这些方法有:在氟树脂中掺入陶瓷粉和金属粉的涂覆方法;在铝底基上熔融喷射金属粉和陶瓷粉,并且使铝表面硬化之后再涂敷氟树脂的方法;还有通过蚀浸使铝表面粗糙化之后,通过对其表面进行阳极氧化处理并使其硬质化,最后在该表面上涂覆氟树脂的方法等。
但是,即使采用上述方法也存在高温耐磨性差的问题。
鉴于上述原因,为了解决这些问题而开发了本发明。
也就是说,本发明的氟树脂涂覆物的特征是,在氟树脂中含有聚酰胺酰亚胺(PAI)树脂聚酰亚胺(PI)树脂、聚亚苯基硫醚(PPS)树脂或聚醚砜(PES)树脂、或者它们的混合物以及云母,并且它们各自相对于氟树脂的量为0.5(重量)%以上,同时将该组合物涂覆在金属基材表面上。
另外,关于本发明至少含有如下一些所优选的实施情况:
a).本发明的氟树脂涂覆物,其特征在于将氟树脂中含有聚酰胺酰亚胺树脂和云母,并且各自相对于氟树脂的含量为0.5(重量)%以上10(重量)%以下的组合物涂覆到金属基材上。
b).按a)中所述的氟树脂涂覆物,其特征在于将氟树脂中含有聚酰胺酰亚胺树脂和云母,并且相对于氟树脂各自的含量为1(重量)%以上10(重量)%以下的组合物涂覆到金属基材上。
c).按a)中所述的氟树脂涂覆物,其特征在于将氟树脂中含有聚酰胺酰亚胺树脂和云母,并且相对于氟树脂各自的含量为3(重量)%以上7(重量)%以下的组合物涂覆到金属基材上。
d).按a)中所述的氟树脂涂覆物,其特征在于将氟树脂中含有聚酰胺酰亚胺树脂和云母,并且各自相对于氟树脂的含量为4(重量)%以上6(重量)%以下的组合物涂覆到金属基材上。
e).按a)中所述的氟树脂涂覆物,其特征在于氟树脂是四氟乙烯树脂。
f).本发明的氟树脂涂覆物,其特征在于金属基材是铝和铝合金。
g).上述f)中所说的氟树脂涂覆物;其特征在于基材表面上设置有通过电化学的或化学的蚀浸形成的微细的凹凸状。
以下通过实施例详细地说明本发明。
本发明人为了解决上述问题进行了深刻地研究,其结果完成了本发明。本发明的特征为:将聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物和云母分散在氟树脂中。
由于聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物与云母的协同效应,所以与氟树脂中只分散云母的情况,和氟树脂中仅仅分散聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物的情况相比较,其在更高温度下的耐磨性都有显著地提高。
另外,在氟树脂中,聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物和云母各自相对于氟树脂的含量心须为0.5(重量)%以上。
聚酰胺酰亚胺树脂,聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂,或者它们的混合物和云母各自相对于氟树脂的含量优先选用0.5(重量)%以上10(重量)%以下,较优选3(重量)%以上7(重量)%以下,最优选4(重量)%以上6(重量)%以下。
这当中最好在氟树脂中含有的聚酰胺酰亚胺树脂和云母各自相对于氟树脂的含量为1(重量)%以上10(重量)%以下,较好的是3(重量)%以上7(重量)%以下,最好的是4(重量)%以上6(重量)%以下的各种情况下,其高温耐磨性提高的更显著。
再有,要求不粘性方面的用途,最好在该涂覆层上再涂覆上一层基本上不含有填充剂的第二层氟树脂层。
在本发明中使用的氟树脂,例如有聚四氟乙烯(PTFE)、四氟乙烯-六氟丙烯共聚物(FEP)、四氟乙烯-全-氟代烷基乙烯醚(PFA)、乙烯-四氟乙烯共聚物(ETFE)、聚三氟氯乙烯(PCTFE)或者乙烯-三氟氯乙烯共聚物(ECTFE)等。
氟树脂不仅可以使用树脂粉末,而且还可以由乳液聚合法制得的水性氟树脂分散液;将氟树脂粉末分散在水性介质中的分散液;氟树脂的有机溶胶或有机溶胶在水中的乳浊液等形式使用。
另一方面,例如聚酰胺酰亚胺树脂,其特征在于在分子结构中既含有酰胺键又含有酰亚胺键,并且该树脂,例如是由分子内含有酰胺基的芳香族二胺和均苯四甲酸等芳香族四价羧酸反应、偏苯三酸酐等芳香族三价羧酸与4,4′-二氨基二苯醚等二胺反应、分子内含有芳香族酰亚胺环的二元酸与二胺反应而制备的。
另一方面,云母按其成份可有许多种,典型的云母的组成式有白云母K2Al4(Si3Al)2O20(OH)4、金云母K2Mg3(Si2Al)2O20(OH)4以及黑云母K2(MgFe.2+)4(Si3Al)2O20(OH)4等,它们都可以使用,最好使用长轴径20~200μm的云母。
为了提高高温耐磨性,仅仅含有云母还不能达到最初的目的。
另外,仅仅含有聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物也是不够的。
本发明最重要一点在于在氟树脂中既含有云母又含有聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物,由于这两方面的协同效应才能使高温耐磨性有显著的提高。这一点可由下面实施例所述的原因中得出。
下面叙述本发明的实施例。
使用厚度为2毫米的铝板材(神户制钢社制得的ASB材)。首先将铝板放在氯化钠水溶液中用60Q/α的电量进行电化学蚀浸,使其表面形成细微的凹凸状。再将该表面放在15%硫酸中用15伏的电压进行5分钟的阳极氧化处理,以便在蚀浸过的表面上设置一硬化层。
所用的树脂组合物如下所述:
1).氟树脂:聚四氟乙烯(PTFE)ダイキン公司制得的EK-630 OCR-H;
2).聚酰胺酰亚胺树脂(PAI)三菱化成公司制品Torion;
3).云母:白云母メルクジヤペン制的ィリォジン163。
上述三成份按表1的比率进行配制,并将其涂敷在设置有硬质层的浸蚀处理面上,涂敷厚度为35微米的树脂层、干燥之后在380℃下烧结15分钟,为了评价由此获得的涂敷板的高温耐磨性,在200℃下进行不锈钢刷子旋转磨损试验。
该试验方法如下:由涂覆板上冲切下一块100mmφ的试验片。将该涂敷表面在200℃下加热并在2公斤荷重下将不锈钢刷子(商品名称:ハイビ ロンジャボ タ シキ 60)压在该涂覆面上。然后以200转/分的转数进行旋转磨损试验,记录露出有金属光泽的铝表面时的磨损转数。
其结果如表1所示,汇总这些结果可以清楚地看到:
在PTFE中仅仅分散PAI的情况下的高温耐磨性(比较例1-1)、和在PTFE中仅仅分散云母的情况下的高温耐磨损性(比较例1-2)都比在PTFE中同时分散PAI和云母的情况下的高温耐磨性低下。
这可以推断出云母与PTFE之间的牢固粘附是通过PAI而达到的。
另外,改变在PTFE中分散的PAI量和云母量再进行同样的试验,其结果汇总在表2中。
由试验结果可知,相对于PTFE的PAI含量为0.5(重量)%以上,云母的含量为0.5(重量)%以上是适宜的。
然后,用PI(三菱化成制品Polyimide 2080)、PPS(菲利浦Petroleum制品ラィトンR)、PES(ICI制品PES 200P)以及它们的混合物代替PAI进行同样的试验。
其结果汇总在表3和表4中。
由表3和表4可知,既含有云母又含有聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物的情况下其高温耐磨性优良。另外,相对于PTFE的聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂,或者它们的混合物的含量为0.5(重量)%以上,云母的含量为0.5(重量)%以上为适宜的。还有优选的情况是在氟树脂中的聚酰胺酰亚胺树脂和云母各自相对于氟树脂的含量在1(重量)%以上,10%以下时其高温耐磨性提高显著。
根据本发明,并由实施例可知,通过使用氟树脂中分散有聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物以及云母的涂覆物,可以使其高温耐磨性显著的提高,所以可有效地将它们用于诸如带把平底锅、锅和电热平板等在高温下要求具有耐磨性的领域中。再有,对于不粘性有严格要求的使用领域中,最好在这些涂覆层上再涂上基本上不含有填充剂的第二层氟树脂。
附图的简要说明:
图1为本发明涂覆物的断面图。
1)……铝基材;
2)……阳极氧化皮膜;
3)……氟树脂;
4)……在氟树脂中分散的聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物。
5)……在氟树脂中分散的云母。
Claims (11)
1、一种氟树脂涂覆物,其特征在于将在氟树脂中含有聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物和云母,并且各自相对于氟树脂的含量为0.5(重量)%以上的组合物涂覆在金属基材上。
2、按照权利要求1的氟树脂涂覆物,其特征在于将氟树脂中含有聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物和云母,并且各自相对于氟树脂的含量为0.5(重量)%以上10(重量)%以下的组合物涂覆到金属基材上。
3、按照权利要求2的氟树脂涂覆物,其特征在于将氟树脂中含有聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物和云母,并且各自相对于氟树脂的含量为3(重量)%以上7(重量)%以下的组合物涂覆到金属基材上。
4、按照权利要求2的氟树脂涂覆物,其特征在于将氟树脂中含有聚酰胺酰亚胺树脂、聚酰亚胺树脂、聚亚苯基硫醚树脂或聚醚砜树脂、或者它们的混合物和云母,并且各自相对于氟树脂的含量为4(重量)%以上6(重量)%以下的组合物涂覆到金属基材上。
5、按照权利要求2的氟树脂涂覆物,其特征在于将在氟树脂中含有聚酰胺酰亚胺树脂和云母,并且各自相对于氟树脂的含量为0.5(重量)%以上10(重量)%以下的组合物涂覆到金属基材上。
6、按照权利要求5的氟树脂涂覆物,其特征在于将在氟树脂中含有聚酰胺酰亚胺树脂和云母、并且各自相对于氟树脂的含量为1(重量)%以上10(重量)%以下的组合物涂覆到金属基材上。
7、按照权利要求5的氟树脂涂覆物,其特征在于将在氟树脂中含有聚酰胺酰亚胺树脂和云母,并且各自相对于氟树脂的含量为3(重量)%以上7(重量)%以下的组合物涂覆到金属基材上。
8、按照权利要求5的氟树脂涂覆物,其特征在于将在氟树脂中含有聚酰胺酰亚胺树脂和云母、并且各自相对于氟树脂的含量为4(重量)%以上6(重量)%以下的组合物涂覆到金属基材上。
9、按照权利要求1的氟树脂涂覆物,其特征在于氟树脂是四氟乙烯树脂。
10、按照权利要求1的氟树脂涂覆物,其特征在于金属基材是铝和铝合金。
11、按照权利要求10的氟树脂涂覆物,其特征在于在基材表面上设置有通过电化学的或化学的蚀浸形成的微细的凹凸状。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP124466/88 | 1988-05-20 | ||
JP12446688 | 1988-05-20 |
Publications (2)
Publication Number | Publication Date |
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CN1038968A true CN1038968A (zh) | 1990-01-24 |
CN1019081B CN1019081B (zh) | 1992-11-18 |
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CN89104434A Expired CN1019081B (zh) | 1988-05-20 | 1989-05-20 | 氟树脂涂覆物 |
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US (1) | US5009959A (zh) |
EP (1) | EP0343015B1 (zh) |
JP (1) | JPH0289633A (zh) |
KR (1) | KR920003561B1 (zh) |
CN (1) | CN1019081B (zh) |
DE (1) | DE68905376T2 (zh) |
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- 1989-05-19 JP JP1126860A patent/JPH0289633A/ja active Granted
- 1989-05-20 CN CN89104434A patent/CN1019081B/zh not_active Expired
- 1989-05-20 KR KR1019890006797A patent/KR920003561B1/ko not_active IP Right Cessation
- 1989-05-22 EP EP89305135A patent/EP0343015B1/en not_active Revoked
- 1989-05-22 DE DE8989305135T patent/DE68905376T2/de not_active Revoked
- 1989-05-22 US US07/354,563 patent/US5009959A/en not_active Expired - Lifetime
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CN110305579A (zh) * | 2019-06-05 | 2019-10-08 | 浙江鹏孚隆科技股份有限公司 | 耐磨耐刮及使用寿命长的不粘涂层及其涂覆方法 |
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Also Published As
Publication number | Publication date |
---|---|
US5009959A (en) | 1991-04-23 |
JPH0289633A (ja) | 1990-03-29 |
DE68905376D1 (de) | 1993-04-22 |
EP0343015A3 (en) | 1990-06-20 |
EP0343015A2 (en) | 1989-11-23 |
JPH0565349B2 (zh) | 1993-09-17 |
DE68905376T2 (de) | 1993-09-02 |
CN1019081B (zh) | 1992-11-18 |
KR920003561B1 (ko) | 1992-05-04 |
EP0343015B1 (en) | 1993-03-17 |
KR900018413A (ko) | 1990-12-21 |
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