CN1086269A - 在金属表面形成耐蚀膜的处理方法 - Google Patents
在金属表面形成耐蚀膜的处理方法 Download PDFInfo
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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Abstract
一含有一种阳离子有机聚合物(或其盐)的磷酸
盐表面处理剂在金属(如铁，锌，铝，等等)表面形成高
耐蚀膜，该膜也是优异的涂料衬底漆，所述阳离子有
机聚合物含有至少一个阳离子性氮原子，分子量为
1,000—1,000,000，该膜优选其中由阳离子有机化
合物(或其盐)构成的树脂渗入磷酸盐粒的晶界，并且
同时形成磷酸盐/树脂复合体。
Description
本发明涉及一种新颖的在诸如铁，锌，铝等等金属的表面形成强耐蚀膜的处理方法。该耐蚀膜也是一优异的涂料衬底。
目前，涂有涂层的物体，如车体和建材，需要越来越高的耐蚀性。到目前为止，金属表面是采用磷酸盐，铬酸盐处理的。然而，现有的金属表面处理剂并不总是表现出令人满意的耐蚀性和涂料粘附力。
人们熟知的现有技术是，如果将有机膜，例如，涂料，粘结剂，等等，涂覆在金属，例如，铁，锌，铝等等的表面上，则用通常可应用的预处理方法在该金属表面上形成一层磷酸盐膜。在施用有机涂层（典型的是涂料）之前，通过在金属表面上形成一层磷酸盐膜的方法改进了耐蚀性和涂料粘附力。当要求更高的耐蚀性时，在涂覆涂料之前，要进行磷酸盐处理和后处理（例如，用铬酸等等封闭）或使用底漆两种处理。然而，这些后处理（例如，用铬酸等等封闭）仅仅起到一较小的作用。而且，尽管使用底漆改善了涂料的粘附力，但也增加了涂覆工艺，因此实际上损害了可操作性。
但是，施用底漆对于涂有涂层的物体例如车体和建材，目前还是需要的。对于车体来说，在金属表面形成磷酸锌膜，然后将其浸入水溶性涂料中以形成电沉积涂层。这种涂覆过程是涂覆底漆的一种类型，其目的是提高被涂层涂覆的表面的耐蚀性，以及确保车体内表面的耐蚀性，该车体是难以涂罩面漆的。在施用罩面涂层前也类似地将底漆涂覆应用于建材，以提高其耐蚀性。
在涂覆操作中施工效率和降低成本要求减少工艺过程，但这一目标的令人满意的方法还有待于开发。因此，当涂层本身不满足耐蚀性和涂层粘附力的要求时，仅用磷酸盐膜仍具有较差的耐蚀性。在需要较高的耐蚀性时，就要同时使用磷酸盐膜和底漆涂层。这就导致了高的生产成本，并需要较大的工作区域。因此，需要开发具有高耐蚀性和高涂层粘附力的金属表面处理剂。同时，也需要开发可不用底漆涂层的金属表面处理剂。
作为解决上述问题的方法，本发明的目的是提供一种金属表面处理剂，它能够使适于磷酸盐膜处理的金属（例如，铁，锌，铝，等等下略称为“金属”）具有高耐蚀性和涂层粘附力。本发明的进一步的目的是提供一种金属表面处理剂，它可在省略了底漆涂层时保持现有的耐蚀性。
为解决上述问题进行的广泛的研究的结果是，现已发现，用含有具有某些特性的有机聚合化合物（或其盐）的磷酸盐处理浴成膜，可获得高耐蚀性和涂层粘附力。本发明正是基于这一发现而开发的。
也就是说，具有上述较高的所需性质的耐蚀膜，可以通过采用处理金属表面而形成，该处理剂可在金属表面成膜，其中该处理剂的特征在于包含磷酸盐表面处理浴，其含有阳离子有机聚合物（或其盐）该聚合物含有至少1个阳离子氮原子，并且其分子量为1，000-1，000，000本发明的耐蚀膜优选的为复合膜，其中构成阳离子有机化合物（或其盐）的树脂已经渗入到磷酸盐晶粒的晶界同时形成磷酸盐晶粒/树脂复合体。
本发明的表面处理剂包含阳离子有机聚合物在磷酸盐处理溶液中的溶液或稳定分散液。该磷酸盐处理浴包括任何表面处理浴，其能够在金属（如，铁，锌，铝，等等）的表面形成磷酸盐耐蚀膜，既可处理一种金属的单体样品，也可同时处理上述金属的两个或多个样品的表面。通常，其基本成分是锌离子和磷酸根离子，但其可任意含有硝酸盐离子，其它金属离子（镍，锰，钙，等等），氟化物，以及各种氧化剂。但是，磷酸盐处理浴在本发明文本中并不作出明确的限定，本发明包含了所有已知的磷酸盐处理浴。
阳离子有机聚合物必须含有至少一个阳离子性氮原子，并且其分子量为1，000-1，000，000。虽然其结构在本发明的最宽的实施方案中不作限定，但是，特别优选具有树脂骨架结构的有机聚合物，其中含有至少一种选自环氧树脂，氨基甲酸乙酯树脂，聚丁二烯树脂，丙烯酸树脂，马来酸酐树脂，其中，这些树脂均含有含氮原子基团。
阳离子有机聚合物的盐包括它的无机盐和有机盐，无机盐的实例如为磷酸盐，硝酸盐，硫酸盐，等等，有机盐的实例如为乙酸盐，丙酸盐，葡糖酸盐，等等。可以使用一种或两种或多种阳离子有机聚合物（或其盐）的样品。在分子量小于1，000时，耐蚀性只能得到较小的改善，而在分子量超过1，000，000时，在磷酸锌盐浴中则难以得到溶液或稳定分散液。
进一步，涂料添加剂（如颜料，等等），其它种类的树脂，活化剂，等等也可在选择的基础上添加进去。
关于处理金属表面的技术，本发明可使用转化处理方法，如喷涂或者浸渍，以及电解的方法，本发明中的所有的处理剂并不受特定的处理方法的限制。
实施例
本发明的效果通过下面的实施例和比较例进行详细的解释。然而本发明并不仅仅局限于实施例，本实施例只描述了典型的预涂磷酸盐处理和典型的涂覆体系。在比较例中，与实施例中作了与实施例中相同的评价和处理，但是使用了本发明范围之外的有机聚合物并且省略了阳离子有机聚合物。
实施例和比较例的通常条件如下：
工件：冷轧钢板;电镀钢板（锌镀膜＝20g/m2）;铝板（JIS5052）。
表面处理剂：实施例中使用的阳离子有机聚合物和比较例中使用的聚合物示于表1。PARBONDTML3020用于车体的表面处理剂，日本磷酸盐处理有限公司出品，被用于无有机聚合物的磷酸盐表面处理浴。这是一种典型的磷酸盐表面处理浴。
处理顺序：
1）去油脂：2%的FINECLEANERTML4460（日本磷酸盐处理有限公司）溶液，于42℃喷洗120秒。
2）水洗：于室温喷洗30秒。
3）表面调理：0.1%的PARCOLENETMZN（日本磷酸盐处理有限公司）溶液，于室温喷洗20秒。
4）本发明的表面处理剂和比较例的表面处理剂均在下列条件中应用;于42℃浸渍120秒。
5）水洗：于室温喷洗30秒。
6）去离子水清洗（电导率，0.2微西门子/厘米），于室温喷洗20秒。
在上述步骤完成后，依下述步骤干燥，涂覆（涂底漆步骤有时省去，所下表所述）：
表1
处理方法 采用的有机聚合物的化学 分子量
性质
A HN(CH3)2与双酚A 8,800
环氧树脂的加合物
B 甲基丙烯酸甲酯与甲基丙烯酸 20,000
二甲基氨基乙酯的共聚物
C H2NCH2N(CH3)22,000
与马来酸酐树脂的加合物
a H2NCH2N(CH3)2800
与马来酸酐树脂的加合物
b 聚乙烯醇 3,000
1）底漆涂层：电沉积用ELECRONTM9410〔肯赛（Kansai）涂料株式会社出品〕进行电沉积涂覆以产生一薄膜膜厚＝20微米;于175℃焙烘30分钟。
2）中间涂层：KPX36（肯赛（Kansai）涂料株式会社出品）;膜厚＝30微米;于140℃焙烘30分钟。
3）罩面涂层：RUGABAKETMB531（肯赛涂料株式会社出品）;膜厚＝40微米;于140℃焙烘30分钟。
所有实施例和比较例的试样，均按上述步骤用相同的方式进行处理，只是采用的表面处理剂的化学性质不同（步骤4）。
性能评价：
1）耐水第二粘附力：已涂覆的片材于40℃浸渍于去离子水中240小时，锋利的刻刀划出100个正方形（2mm×2mm）的棋盘，划痕至基材。用玻璃纸剥离后，计算被剥离方块的数量。被剥离的面积越小，表明性能越好。
2）复合循环试验：在已涂覆的片材表面用尖锐的切刀画一十字并深入到基材，然后将片材由T1→T2循环（见下面）重复处理14次。试验后，从十字处测量一表面上最大的膜鼓泡的宽度，由此来评价性能。
T1：盐雾试验（JIS Z2371）：24小时
T2：润湿试验（50℃，70%RH）：216小时
表2，3，和4报道了由分别对冷轧钢板，电镀钢板，和铝板进行表面处理得到的膜涂料的粘附力和耐蚀性。这些表也包括了比较例的实验结果。
在采用本发明的用于形成复合膜的金属表面处理剂处理的情况下试验结果表明，与磷酸盐处理相比，耐蚀性和涂料粘附力有相当的提高。因此，即使省略了底漆涂层，本发明的效果也近似于在磷酸盐膜之上涂覆底漆涂层。
当使用不在本发明的范围内的有机聚合物时，或者实际上不产生效果，或者其性能事实上下降了。
综上所述，本发明的用于形成复合膜的金属表面处理剂提高了耐蚀性和涂料粘附力，并可省去底漆涂层。
表2
表3
表4
Claims (6)
1、用于金属表面的磷酸盐转化涂层处理组合物，其特征在于该组合物含有一种阳离子有机聚合物，或该阳离子有机聚合物的盐类，该聚合物含有至少1个阳离子性氮原子，并且分子量为1，000至1，000，000。
2、权利要求1的磷酸盐转化涂层处理组合物，其中阳离子有机聚合物具有一种树脂骨架结构，其包括至少一种选自环氧树脂，氨基甲酸乙酯树脂，聚丁二烯脂，两烯酸树脂，马来酸酐树脂的树脂。
3、一种在金属表面形成保护性涂层的方法，该方法是将金属与一种磷酸盐转化涂层溶液相接触，其特征在于该磷酸盐转化涂层溶液中含有权利要求1或2的组合物。
4、权利要求3的方法，其中金属是铁，锌，或铝。
5、权利要求4的方法，其中所形成的保护性涂层具有复合结构，其中含有阳离子有机化合物或其盐的树脂渗入磷酸盐晶粒的晶界中。
6、一种制品，该制器包括有机保护性涂层外表面，位于有机保护性膜下面的磷酸盐离子的中间膜，和位于中间涂层下的金属，其特征在于该中间涂层具有复合结构，其中含有具有阳离子氮原子的有机聚合物或其盐的树脂渗入磷酸盐晶粒的晶界。
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03308227A JP3139795B2 (ja) | 1991-10-29 | 1991-10-29 | 複合皮膜形成用金属表面処理剤 |
| AU28841/92A AU2884192A (en) | 1991-10-29 | 1992-10-22 | Treatment for the formation of a corrosion resistant film on metal surfaces |
| CA002121486A CA2121486A1 (en) | 1991-10-29 | 1992-10-22 | Treatment for the formation of a corrosion resistant film on metal surfaces |
| PCT/US1992/008811 WO1993009265A1 (en) | 1991-10-29 | 1992-10-22 | Treatment for the formation of a corrosion resistant film on metal surfaces |
| EP92922276A EP0610315A1 (en) | 1991-10-29 | 1992-10-22 | Treatment for the formation of a corrosion resistant film on metal surfaces |
| BR9206685A BR9206685A (pt) | 1991-10-29 | 1992-10-22 | Composição de tratamento de revistimento de conversão com fosfato para superfícies metálicas, processo para a formação de um revestimento protetor sobre um metal, e, produto manufaturado |
| MX9206223A MX9206223A (es) | 1991-10-29 | 1992-10-28 | Tratamiento para la formacion de una pelicula resistente a la corrosion sobre superficies de metal. |
| CN92112560A CN1086269A (zh) | 1991-10-29 | 1992-10-29 | 在金属表面形成耐蚀膜的处理方法 |
| ZA928377A ZA928377B (en) | 1991-10-29 | 1992-10-29 | Treatment for the formation of a corrosion resistant film on metal surfaces. |
| NZ244928A NZ244928A (en) | 1991-10-29 | 1992-10-29 | Phosphate conversion coatings for metal surfaces, containing an organic polymer which has cationic nitrogens; article of manufacture |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03308227A JP3139795B2 (ja) | 1991-10-29 | 1991-10-29 | 複合皮膜形成用金属表面処理剤 |
| CN92112560A CN1086269A (zh) | 1991-10-29 | 1992-10-29 | 在金属表面形成耐蚀膜的处理方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1086269A true CN1086269A (zh) | 1994-05-04 |
Family
ID=36791816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92112560A Pending CN1086269A (zh) | 1991-10-29 | 1992-10-29 | 在金属表面形成耐蚀膜的处理方法 |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0610315A1 (zh) |
| JP (1) | JP3139795B2 (zh) |
| CN (1) | CN1086269A (zh) |
| AU (1) | AU2884192A (zh) |
| BR (1) | BR9206685A (zh) |
| CA (1) | CA2121486A1 (zh) |
| MX (1) | MX9206223A (zh) |
| NZ (1) | NZ244928A (zh) |
| WO (1) | WO1993009265A1 (zh) |
| ZA (1) | ZA928377B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532468C (zh) * | 2002-03-13 | 2009-08-26 | 罗狄亚化学公司 | 携带磷酸根和/或膦酸根官能团的嵌段共聚物作为粘合促进剂或作为防止金属表面腐蚀的保护剂的用途 |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306526A (en) * | 1992-04-02 | 1994-04-26 | Ppg Industries, Inc. | Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method |
| JP3193798B2 (ja) * | 1993-01-13 | 2001-07-30 | 日本パーカライジング株式会社 | 金属冷間加工用の複合皮膜形成用金属表面処理液及び複合皮膜形成方法 |
| DE4341602A1 (de) * | 1993-12-07 | 1995-06-08 | Bayer Ag | Verwendung einer Polyurethandispersion als Penetrationsgrund und ein Verfahren zur Herstellung von Mehrschichtlackierungen |
| JPH101782A (ja) * | 1996-06-13 | 1998-01-06 | Nippon Paint Co Ltd | 金属表面処理剤、処理方法及び表面処理された金属材料 |
| JPH1046101A (ja) * | 1996-08-01 | 1998-02-17 | Nippon Parkerizing Co Ltd | 金属材料の表面にフィルムラミネート用下地皮膜を形成させた被覆金属材料、およびその製造方法 |
| JPH10182916A (ja) * | 1996-10-21 | 1998-07-07 | Nippon Paint Co Ltd | Ｎ複素環を含むアクリル樹脂含有金属表面処理組成物、処理方法及び処理金属材料 |
| EP0933408B1 (en) | 1996-10-21 | 2003-02-12 | Nippon Paint Co., Ltd. | Metal surface treatment for food can using an acrylic resin containing composition and the so treated can |
| FR2769325B1 (fr) * | 1997-10-08 | 1999-12-03 | Cfpi Ind | Bain acide pour la phosphatation au zinc de substrats metalliques, concentre pour la preparation du bain et procede de phosphatation le mettant en oeuvre |
| US5972433A (en) * | 1997-12-05 | 1999-10-26 | Calgon Corporation | Method for treatment of metal substrates using Mannich-derived polyethers |
| JP2008057047A (ja) * | 2002-06-28 | 2008-03-13 | Jfe Steel Kk | 表面処理亜鉛系めっき鋼板の製造方法 |
| DE60324245D1 (de) | 2002-12-24 | 2008-12-04 | Chemetall Gmbh | Verfahren zur Vorbehandlung vor der Beschichtung |
| JP4989842B2 (ja) * | 2002-12-24 | 2012-08-01 | 日本ペイント株式会社 | 塗装前処理方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2159511B (en) * | 1984-04-25 | 1988-09-21 | Dearborn Chemicals Ltd | A method of inhibiting corrosion in aqueous systems |
| US4978399A (en) * | 1988-01-04 | 1990-12-18 | Kao Corporation | Metal surface treatment with an aqueous solution |
| DE3906898A1 (de) * | 1989-03-03 | 1990-09-06 | Henkel Kgaa | Zink-barium-phosphatierung von metalloberflaechen |
| JPH04193957A (ja) * | 1990-11-28 | 1992-07-14 | Nippon Parkerizing Co Ltd | クリヤー塗装下地用クロメート処理液 |
-
1991
- 1991-10-29 JP JP03308227A patent/JP3139795B2/ja not_active Expired - Lifetime
-
1992
- 1992-10-22 WO PCT/US1992/008811 patent/WO1993009265A1/en not_active Ceased
- 1992-10-22 BR BR9206685A patent/BR9206685A/pt active Search and Examination
- 1992-10-22 EP EP92922276A patent/EP0610315A1/en not_active Withdrawn
- 1992-10-22 AU AU28841/92A patent/AU2884192A/en not_active Abandoned
- 1992-10-22 CA CA002121486A patent/CA2121486A1/en not_active Abandoned
- 1992-10-28 MX MX9206223A patent/MX9206223A/es unknown
- 1992-10-29 NZ NZ244928A patent/NZ244928A/en unknown
- 1992-10-29 ZA ZA928377A patent/ZA928377B/xx unknown
- 1992-10-29 CN CN92112560A patent/CN1086269A/zh active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532468C (zh) * | 2002-03-13 | 2009-08-26 | 罗狄亚化学公司 | 携带磷酸根和/或膦酸根官能团的嵌段共聚物作为粘合促进剂或作为防止金属表面腐蚀的保护剂的用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9206223A (es) | 1993-11-30 |
| JPH05117869A (ja) | 1993-05-14 |
| ZA928377B (en) | 1993-05-14 |
| AU2884192A (en) | 1993-06-07 |
| EP0610315A1 (en) | 1994-08-17 |
| CA2121486A1 (en) | 1993-05-13 |
| WO1993009265A1 (en) | 1993-05-13 |
| JP3139795B2 (ja) | 2001-03-05 |
| BR9206685A (pt) | 1995-10-24 |
| NZ244928A (en) | 1994-10-26 |
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