CN1187133C - 聚合物涂覆的铝合金板材的制造方法和聚合物涂覆的铝合金板材 - Google Patents
聚合物涂覆的铝合金板材的制造方法和聚合物涂覆的铝合金板材 Download PDFInfo
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Abstract
提供一种制造适用于成型成食品或饮料容器本体或容器端盖板的聚合物涂覆的铝合金板材的方法，所述的方法包括：提供表面部分有氧化铝或氢氧化铝的铝合金板材；用乙烯基膦酸-丙烯酸共聚物的水溶液涂覆所述的表面部分，从而形成含有所述共聚物和所述氧化物或氢氧化物的反应产物的底漆层，其中所述水溶液不含其它共聚物；以及用含有选自聚氯乙烯、环氧树脂和聚酯的聚合物的涂料组合物涂覆所述的底漆层。此外，还提供聚合物涂覆的铝合金板材。
Description
技术领域
本发明涉及新型的食品容器本体或涉及新型食品或饮料容器端盖板(end panel)以及涉及由铝合金板材制造它们的方法。更具体地说，本发明涉及具有含有氧化物或氢氧化物层和乙烯基膦酸-丙烯酸共聚物的反应产物的底漆层的聚合物涂覆的铝合金板材。
背景技术
虽然铝通过形成天然氧化物涂层保护它免受腐蚀，但这种保护是不充分的。在水汽和电解质存在下，铝合金的腐蚀比纯铝更快。
因此，需要用底漆或其他化学品处理铝合金基材，它们提供更好的耐腐蚀性以及对聚合物强的粘合亲合性。
在现有的技术中，通过将金属表面“转变”成紧密附着的涂层而在铝合金上形成化学转化涂层，其一部分由铝的氧化形式组成。化学转化涂层提供了高耐腐蚀性以及对聚合物涂层高的粘合亲合性。通常通过铝与含有6价或3价铬离子、磷酸根离子和氟离子的水溶液接触来提供铬酸盐转化涂层。近年来，十分关心用这样的方法排放到排水道中的铬酸盐和磷酸盐的污染作用。由于6价铬离子的高度溶解性和强的氧化特性，必需使用昂贵的废物处理方法在废物处理中使6价铬离子还原成3价铬离子。
在现有技术中，试图制成用于铝的可接受的无铬酸盐的转化涂层。例如，一些无铬酸盐的转化涂层含有锆、钛、铪和/或硅，有时还与氟化物、表面活性剂和聚合物例如聚丙烯酸组合。尽管过去已作了广泛的努力，但仍然没有十分满意的无铬酸盐的转化涂层或底漆，来改进聚合物涂覆的铝合金基材的粘着性和耐腐蚀性。
Wefer等人(美国专利5103550)一般教导使用膦酸或亚膦酸和/或其衍生物，提供官能化层以改善将聚合物层施加到铝表面上。该专利没有教导或公开使用乙烯基膦酸-丙烯酸共聚物(VPA/AA)，也没有暗示其应用和优越的性质。
Herbst等人(美国专利3196039)教导了一种对磷化钢板的后处理的技术，该技术似乎并不适于铝合金，或甚至不适于裸露钢板本身。磷化处理通过在钢板上完全覆盖磷酸锌、磷酸铁或磷酸锰盐层而保护钢制品。这些金属盐保护钢防止腐蚀，并作为另外保护涂层例如油漆或油的底漆层。
发明内容
本发明的主要目的是提供具有含有乙烯基膦酸-丙烯酸共聚物和铝合金板材上的氧化铝或氢氧化铝层的反应产物的底漆层的聚合物涂覆的铝合金板材。
本发明的相关目的是提供一种铝合金板材用的不含铬化合物的底漆层。
在本发明的一个技术方案中，提供一种制造适用于成型成食品或饮料容器本体或容器端盖板的聚合物涂覆的铝合金板材的方法，所述的方法包括：
(a)提供表面部分有氧化铝或氢氧化铝的铝合金板材；
(b)用乙烯基膦酸-丙烯酸共聚物的水溶液涂覆所述的表面部分，从而形成含有所述共聚物和所述氧化物或氢氧化物的反应产物的底漆层，其中所述水溶液不含其它共聚物；以及
(c)用含有选自聚氯乙烯、环氧树脂和聚酯的聚合物的涂料组合物涂覆所述的底漆层。
在又一个技术方案中，提供一种聚合物涂覆的铝合金板材，它含有：
(a)包括AA5000系列铝-镁合金并且其表面部分含有氧化铝或氢氧化铝的铝合金板材；
(b)有所述的氧化物或氢氧化物与含有约20至40％摩尔的乙烯基膦酸单元的乙烯基膦酸-丙烯酸共聚物的反应产物的底漆层；以及
(c)粘着到所述底漆层的涂料组合物，所述的涂料组合物含有选自聚氯乙烯、环氧树脂和聚酯的聚合物。
在又一技术方案中，提供制造适用于成型成食品或饮料容器本体或容器端盖板的聚合物涂覆的铝合金板材的方法，它包括：
(a)提供包括AA5000系列铝-镁合金并具有含有氧化铝或氢氧化铝的表面部分的铝合金板材；
(b)用1-20克/升的乙烯基膦酸-丙烯酸共聚物的水溶液涂覆所述的表面部分，所述的共聚物含有5至50％摩尔的乙烯基膦酸，从而形成包括所述共聚物和所述氧化物或氢氧化物的反应产物的涂层；以及
(c)用含有选自聚氯乙烯、环氧树脂和聚酯的聚合物的涂料组合物涂覆所述的层。
对于熟悉本领域的技术人员来说，从以下详细的描述中，本发明的另外一些目的和优点是显而易见的。
附图说明
图1为本发明方法的流程图。
具体实施方式
根据本发明，提供了一种用于制造适用于成型成食品容器本体或食品或饮料容器底板的聚合物涂覆的铝合金板材的方法。
适用于制造聚合物涂覆的容器本体或容器端盖板(end panel)的一些铝合金包括AA5000系列的铝-镁合金，特别是AA5042和AA5182合金。
适用于容器端盖板的铝合金例如AA5182作为用本专业已知的铸造技术生产的锭料或坯料或板坯提供。在加工以前，锭料或坯料经升温均匀化。然后将合金料热轧，制得中间厚度板材。例如，该材料可以以在金属进口温度为约700至975°F下热轧，制得厚度约0.130至0.190英寸的中间产品。该材料经冷轧，制得厚度约0.008至0.015英寸的板材。我们推荐H19或H39硬度(temper)的AA5182铝合金板材。用于底材的铝合金5042板材优选H19硬度。
铝合金例如AA5042作为均匀化的锭料提供。随后热轧成约0.125英寸厚的中间厚度板材。通常，中间厚度板材经退火，随后热轧和冷轧，得到厚度约0.008至0.015英寸的最后厚度产品。用聚合物涂覆板材，然后拉拔和再拉拔成食品容器本体。我们推荐H2E72硬度(temper)的AA5042铝合金板材。
在铝合金板材表面上的天然氧化物涂层对于本发明的实施通常是足够的。所述的天然氧化物涂层的厚度通常约30至50埃。为了更好地耐腐蚀，所述的氧化物涂层可用各种处理来增长，例如阳极氧化或在水、水蒸汽或水溶液中水热处理。
本发明的铝合金板材通常用碱性表面清洁剂清洁，以便除去附着到表面的任何残留的润滑剂，然后用水清洗。如果残留的润滑剂含量可忽略，那么可不需清洁。
然后用含有约1-20克/升乙烯基膦酸-丙烯酸共聚物(VPA-AA共聚物)的水溶液的底漆组合物给清洁过的板材表面涂底漆。优选含有约4至10克/升所述共聚物的溶液。共聚物通常含有约5至50％(摩尔)乙烯基膦酸、优选约20至40％(摩尔)。特别优选的VPA-AA共聚物含有约30％(摩尔)VPA和约70％(摩尔)AA。溶液的温度约100至200°F、更优选约120至180°F。特别优选的溶液温度为约170°F。
可将板材表面浸到底漆组合物中，或将所述组合物辊涂或喷涂到板材表面上。优选的连续清洁和预处理生产线以约1000至1500英尺/分操作。当生产线以1000英尺/分操作时，板材表面和底漆组合物之间约6秒的接触时间是足够的。VPA-AA共聚物与氧化物涂层或氢氧化物涂层反应，在板材表面上形成底漆层。
任选的是，用水清洗涂底漆的板材，以便除去未与氧化物或氢氧化物涂层反应的VPA-AA共聚物的部分。清洗水的温度优选为约170至180°F。通过除去过量的水使清洗水浓缩，以便VPA-AA共聚物可循环使用。一些优选的浓缩技术包括反渗析和薄膜过滤。
用聚合物组合物涂覆涂底漆的板材，所述组合物优选包括有机聚合物和分散在有机溶剂中的颜料颗粒。三种优选的涂覆聚合物为环氧树脂、聚氯乙烯和聚酯。适合的环氧树脂包括苯酚改性的环氧树脂、聚酯改性的环氧树脂和环氧改性的聚氯乙烯。
另一方面，可用电涂法，缝涂法或挤出涂覆法涂覆涂底漆的板材。
颜料颗粒优选二氧化钛、氧化铝或氧化硅。我们推荐中值粒度范围为0.5-10微米的二氧化钛颗粒。
聚合物涂覆的板材经干燥、卷取，最后成型成容器本体或容器端盖板。
根据本发明，一些2英寸×4英寸AA5182铝合金板材样品经清洁，用乙烯基膦酸-丙烯酸共聚物涂底漆，然后用聚氯乙烯涂料组合物涂覆。VPA-AA共聚物含有30％(摩尔)VPA单元和70％(摩尔)AA单元。
用PVC涂覆的样品测试耐发白性(blushing resistance)和涂层粘着性。将一组样品放在装有啤酒的啤酒罐中，将啤酒罐密闭，然后将它在水浴中在180°F下加热30分钟。另一组样品在加热至180°F的去离子水浴中浸泡30分钟。
将测试样品从测试环境中取出，用去离子水清洗，然后干燥。如果用肉眼观测很明显，就记录发白性。用刮刀划开透过涂层至基础金属划成划格结构(大约1/8至3/16寸间隔水平线和竖直线)来测试涂层的粘附性。将高粘胶带(3M No.610)贴在划格区域上。接触5秒以后，迅速以对金属表面呈大约90°角的拉起除去胶带。用P(VPA-AA)底漆的胶带试验的结果和用聚乙烯基膦酸(PVPA)和聚丙烯酸(PAA)底漆的类似胶带试验的结果列入下表。
表1 胶带试验结果
试验环境
预处理
啤酒
水
PVPA-4.1克/升 不合格 不合格
180°F浴
PVPA-7.4克/升 不合格 不合格
180°F浴
PAA-1.0克/升 不合格 不合格
140°F浴
PAA-7.7克/升 不合格 不合格
140°F浴
P(VPA-AA)-4.4克/升 合格 合格
180°F浴
P(VPA-AA)-7.2克/升 合格 合格
180°F浴
虽然已描述了目前优选的实施方案，但应当理解，本发明可以其他方式体现在附后的权利要求书的范围内。
Claims (14)
1.一种制造适用于成型成食品或饮料容器本体或容器端盖板的聚合物涂覆的铝合金板材的方法，所述的方法包括：
(a)提供表面部分有氧化铝或氢氧化铝的铝合金板材；
(b)用乙烯基膦酸-丙烯酸共聚物的水溶液涂覆所述的表面部分，从而形成含有所述共聚物和所述氧化铝或氢氧化铝的反应产物的底漆层，其中所述水溶液不含其它共聚物；以及
(c)用含有选自聚氯乙烯、环氧树脂和聚酯的聚合物的涂料组合物涂覆所述的底漆层。
2.根据权利要求1的方法，还包括：
(d)将所述的板材成型成容器本体或容器端盖板。
3.根据权利要求1的方法，还包括：
(d′)在(b)以后和(c)以前，清洗所述的板材，以除去未与所述的氧化铝或氢氧化铝反应的所述共聚物部分。
4.根据权利要求1的方法，其中所述的共聚物含有5至50％摩尔的乙烯基膦酸。
5.根据权利要求1的方法，其中所述的共聚物含有20至40％摩尔的乙烯基膦酸。
6.根据权利要求1的方法，其中所述的水溶液含1至20克/升溶解在水中的所述共聚物。
7.根据权利要求1的方法，其中所述的水溶液在步骤(b)中的温度为49至93℃。
8.根据权利要求1的方法，其中所述的涂料组合物还含有有机溶剂。
9.根据权利要求1的方法，其中所述的涂料组合物还含有选自二氧化钛、氧化硅和氧化铝的颜料颗粒。
10.根据权利要求1的方法，其中所述的铝合金板材包括AA5000系列的铝-镁合金。
11.根据权利要求1的方法，其中所述的涂料组合物含聚氯乙烯。
12.根据权利要求1的方法，其中，步骤(a)中的铝合金包括AA5000系列铝镁合金；在步骤(b)中所述乙烯基膦酸-丙烯酸共聚物含有5至50％摩尔的乙烯基膦酸，所述水溶液中含1-20克/升的乙烯基膦酸-丙烯酸共聚物。
13.根据权利要求12的方法，其中所述的水溶液包括4至10克/升的共聚物。
14.聚合物涂覆的铝合金板材，它含有：
(a)包括AA5000系列铝-镁合金并且其表面部分含有氧化铝或氢氧化铝的铝合金板材；
(b)含有所述的氧化铝或氢氧化铝与含有20至40％摩尔的乙烯基膦酸单元的乙烯基膦酸-丙烯酸共聚物的反应产物的底漆层；以及
(c)粘着到所述底漆层的涂料组合物，所述的涂料组合物含有选自聚氯乙烯、环氧树脂和聚酯的聚合物。
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| PCT/US1999/030539 WO2001045866A1 (en) | 1999-12-21 | 1999-12-21 | Copolymer primer for aluminum alloy food and beverage containers |
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| US8133557B2 (en) | 2002-08-01 | 2012-03-13 | Valspar Sourcing, Inc. | Coating composition for metal substrates |
| JP4119218B2 (ja) * | 2002-10-16 | 2008-07-16 | 忠弘 大見 | 水分発生用反応炉の白金コーティング触媒層の形成方法 |
| JP4186080B2 (ja) * | 2002-12-20 | 2008-11-26 | 関西ペイント株式会社 | アルミニウム基材の塗膜形成方法 |
| US7416831B2 (en) * | 2004-08-20 | 2008-08-26 | Eastman Kodak Company | Substrate for lithographic printing plate precursor |
| JP2008127625A (ja) * | 2006-11-21 | 2008-06-05 | Furukawa Sky Kk | 成型加工後の樹脂密着性に優れたキャップ成型用アルミニウム板及びその製造方法 |
| US9365931B2 (en) | 2006-12-01 | 2016-06-14 | Kobe Steel, Ltd. | Aluminum alloy with high seawater corrosion resistance and plate-fin heat exchanger |
| DE102009003683B4 (de) * | 2009-03-26 | 2011-03-24 | Hydro Aluminium Deutschland Gmbh | Verfahren zur Herstellung eines beschichteten Aluminiumbandes, Aluminiumband und dessen Verwendung |
| RU2561968C2 (ru) | 2010-10-15 | 2015-09-10 | Вэлспар Сорсинг, Инк. | Состав покрытия на основе сложного полиэфира для нанесения на металлические подложки |
| CN102888604A (zh) * | 2012-09-21 | 2013-01-23 | 虞伟财 | 金属铝表面防腐蚀处理方法 |
| JP2014088508A (ja) * | 2012-10-30 | 2014-05-15 | Asahi Kasei Chemicals Corp | 樹脂被覆金属顔料及び塗料組成物 |
| CN103522654B (zh) * | 2013-10-10 | 2016-08-17 | 马良 | 一种金属镀层透明保护层结构及其工艺方法 |
| CN104403434A (zh) * | 2014-12-02 | 2015-03-11 | 苏州Ppg包装涂料有限公司 | 涂料组合物 |
| WO2020142264A1 (en) * | 2019-01-02 | 2020-07-09 | Novelis Inc. | Systems and methods for laminating can end stock |
| CN111330826A (zh) * | 2020-04-02 | 2020-06-26 | 广州丰旺科技应用有限公司 | 一种铝镁合金箱喷漆工艺 |
| CN112226041A (zh) * | 2020-10-12 | 2021-01-15 | 江苏华海诚科新材料股份有限公司 | 一种高导热型环氧树脂组合物及其制备方法 |
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| US5103550A (en) * | 1989-12-26 | 1992-04-14 | Aluminum Company Of America | Method of making a food or beverage container |
| US5368974A (en) * | 1993-05-25 | 1994-11-29 | Eastman Kodak Company | Lithographic printing plates having a hydrophilic barrier layer comprised of a copolymer of vinylphosphonic acid and acrylamide overlying an aluminum support |
| US6030710A (en) * | 1997-06-30 | 2000-02-29 | Alcoa Inc. | Copolymer primer for aluminum alloy food and beverage containers |
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| EP1239976A1 (en) | 2002-09-18 |
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| CA2380542A1 (en) | 2001-06-28 |
| PL353345A1 (en) | 2003-11-17 |
| TW518278B (en) | 2003-01-21 |
| RU2232649C2 (ru) | 2004-07-20 |
| HU225813B1 (hu) | 2007-10-29 |
| AU2205100A (en) | 2001-07-03 |
| NO20021039D0 (no) | 2002-03-01 |
| HUP0202408A2 (hu) | 2002-11-28 |
| CZ2002496A3 (cs) | 2003-02-12 |
| PT1239976E (pt) | 2003-12-31 |
| TR200200511T2 (tr) | 2002-06-21 |
| CN1367720A (zh) | 2002-09-04 |
| BR9917478B1 (pt) | 2010-05-18 |
| SK3182002A3 (en) | 2002-09-10 |
| MXPA02002200A (es) | 2003-04-10 |
| ATE246547T1 (de) | 2003-08-15 |
| KR20020069001A (ko) | 2002-08-28 |
| WO2001045866A1 (en) | 2001-06-28 |
| BR9917478A (pt) | 2002-05-14 |
| EP1239976B1 (en) | 2003-08-06 |
| NO20021039L (no) | 2002-04-30 |
| JP2003517929A (ja) | 2003-06-03 |
| ES2203241T3 (es) | 2004-04-01 |
| DK1239976T3 (da) | 2003-12-01 |
| DE69910265T2 (de) | 2004-06-09 |
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Address after: Pennsylvania Patentee after: Okkonen g Co. Ltd. Address before: Pennsylvania Patentee before: Alcoa Inc. |
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Granted publication date: 20050202 |