CN101056952A - 降低或抑制漆膜表面缺陷的水性油漆组合物和方法 - Google Patents
降低或抑制漆膜表面缺陷的水性油漆组合物和方法 Download PDFInfo
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Abstract
本发明涉及降低或抑制漆膜表面缺陷的形成的方法，包括：将丙烯酸丁酯的均聚物B和丙烯酸丁酯和可共聚合单体A的共聚物BA中的至少一种添加到水性油漆组合物中，其特征在于在该共聚物中源自共聚单体A的结构部分的质量分数不超过30％，和涉及包含丙烯酸丁酯的均聚物B和丙烯酸丁酯和可共聚合单体A的共聚物BA中的至少一种的水性油漆组合物。
Description
本发明涉及降低或抑制漆膜表面缺陷的方法。
在水性CED(阴极电沉积涂覆)浴中，尤其是在金属表面例如汽车车身的OEM涂覆中，需要添加剂以降低或抑制漆膜的表面缺陷，例如由金属板的污染以及浴液本身引起的针孔和弧坑，这归应于成形过程的拉拔润滑脂和油。进一步的要求是聚氯乙烯基密封材料在漆膜上的粘附性不应该受到添加剂的损害。
在基于本发明的实验中，已经令人惊讶地发现丙烯酸丁酯共聚物可以在CED浴中用作添加剂并且赋予所述CED浴所需的性能，其中在聚合物中源自共聚单体的结构部分的质量分数不超过30％。
因此，本发明的主题是降低或抑制漆膜表面缺陷的形成的方法，包括：将丙烯酸丁酯的均聚物B或丙烯酸丁酯和可共聚合单体A的共聚物BA添加到水性油漆组合物中，其特征在于在该共聚物BA中源自共聚单体A的结构部分的质量分数不超过30％。如果这种结构部分是通过用单键替代单体的碳-碳双键以形成双自由基结构(这种结构彼此连接以形成聚合物)而形成，那么认为结构部分源自共聚单体。优选的共聚单体A是丙烯酸丁酯之外的在烷基中含1-18，优选2-8个碳原子的(甲基)丙烯酸烷基酯A1(其中烷基可以是线性、支化、或环状的)和在羟烷基基团中含2-6，优选2-4个碳原子的(甲基)丙烯酸羟烷基酯A2。尤其优选的是施陶丁格指数Jg(在氯仿溶剂中，在23℃下测量)为3,5cm3/g到16.0cm3/g的均聚物和共聚物。优选地，根据本发明的聚合物应该具有4.5cm3/g到10.0cm3/g的施陶丁格指数。
之前还称为“特性粘度”、根据DIN 1342，2.4部分正确名称为“施陶丁格指数”Jg的物理量，是接近零的浓度和剪切梯度的施陶丁格函数Jv的极限值，其中Jv等于由于溶质的相对粘度的增量除以溶质B的质量浓度βB＝mB/V(在溶液的体积V中的溶质的质量mB)，即，
Jv＝(ηr-1)/βB·ηr-1
表示相对粘度的增量：
ηr-1＝(η-ηs)/ηs
其中相对粘度ηr是检测下的溶液的粘度η与纯溶剂的粘度ηs的比值。(施陶丁格指数的物理意义是溶剂化的聚合物卷材在无限稀释下且处于静止状态下的比流体动力学体积。)J的常用单位是“cm3/g”；之前还经常以单位“dl/g”表示。
本发明的另一个主题是水性油漆组合物，尤其是用于阴极电沉积(“CED”)的那些，其包含上文限定的均聚物B和共聚物BA中的至少一种。
本发明的又一主题是通过一种涂料组合物涂覆基材的方法，该基材优选是导电的，该涂料组合物包含上文限定的均聚物B和共聚物BA的至少一种。
在一个优选实施方案中，在共聚物BA中源自丙烯酸丁酯之外的共聚单体的结构部分的质量分数不超过25％，更优选不超过20％。在另一个优选实施方案中，源自包含羟基的共聚单体的结构部分的质量分数不超过5％，更优选不超过3％。
对根据本发明的方法必不可少的聚合物可以通过在溶剂中进行自由基聚合来制备，该溶剂在自由基聚合条件下是情性的。该溶剂可以在将所述聚合物作为添加剂混入CED浴中之前通过蒸馏除去。如果不除去溶剂，则使用水混溶性溶剂是有利的。如果溶剂在混合物中的质量分数至少为20％-80％的范围上，溶剂在室温下(20℃)与水形成单相混合物，在本发明范围内则认为溶剂是水混溶性的。
本发明中使用的均聚物B和共聚物BA本身在水中不是可溶的，也不是可乳化的或与水也不是可混溶的。换言之，它们不与水形成单相混合物，它们也不会形成至少24小时内不沉降的稳定分散体。因此，通常通过在用水将粘结剂本身稀释之前添加到该粘结剂而将它们引入水性油漆，优选CED浴中。基于水性油漆优选CED浴液中的固体质量，根据本发明的这些添加剂的质量分数优选为0.5％-5％，尤其优选0.9％-1.8％。“固体”是指水性油漆内的固体树脂部分，不包括其它的如催化剂残余物、颜料、流平添加剂和填料等组分。这一固体树脂部分在本发明范围内还称为“树脂部分”。
已经发现根据本发明的这些添加剂存在于水性油漆，特别是CED浴中，显著地降低在用这种油漆涂覆的(尤其是通过在这些浴中电沉积的)基材上形成表面缺陷的倾向。
将在导电性基材上阴极沉积的形成CED浴中主要成分的那些树脂优选是熟知的环氧树脂胺加合物。它们优选基于双酚A类型的环氧树脂，和脂族胺，该脂族胺具有连接到脂族碳原子上的氨基。在优选的方法中，用封端的异氰酸酯类固化剂将它们固化。当烘干或加热该已涂覆的基材时，如果烘烤温度在该封端的异氰酸酯的脱封端温度之上，封端剂分裂，异氰酸酯基重新产生。然后该重新产生的异氰酸酯基可以与环氧树脂胺加合物中的羟基或氨基反应，从而将涂膜交联。环氧树脂胺加合物可以按本领域已知的通过每个分子含至少两个环氧基团的多官能化环氧化物与伯或仲胺，或这些的混合物，或它们的盐反应来制备。
实施例
通过以下实施例进一步说明本发明。在这些实施例中，根据DIN ENISO 3682(DIN 53402)将酸值定义为氢氧化钾(需要它来中和所述的样品)的质量mKOH与样品的质量mB(或在溶液或分散体情形下样品中的固体质量)的比值；常用的单位是“mg/g”。将比环氧基团含量“SEC”定义为环氧基团的物质的量n(EP)与该物质的质量mB的比值(因此是所谓的“环氧化物值”或“环氧化物当量重量”的倒数)；SI的单位是“mol/kg”。
以“％”计的浓度或强度始终是溶质B在溶液中(或分散组份在分散体中)的质量分数wB，计算为wB＝mB/m，其中mB是溶质的质量，m是溶液的质量。
实施例1粘结剂A的合成
在装备有搅拌器、温度计、滴液漏斗和回流冷凝器的容器中，将1000克比环氧基团含量为2mol/kg的基于双酚A的环氧树脂溶于500g的70℃-90℃下的甲基异丁基酮中。添加0.2克氢醌和168克甲基丙烯酸。将温度升高到110℃，并继续该反应直到酸值跌至3mg/g以下。在冷却到60℃之后，添加650克由在甲基异丁基酮中的0.9摩尔N，N-二甲基乙醇胺/1摩尔亚苄基二异氰酸酯以70％浓度的溶液组成的一异氰酸酯溶液，并且让该混合物反应直到不再能检测到游离异氰酸酯基。
实施例2粘结剂B的合成
在装备有搅拌器、温度计、滴液漏斗和回流冷凝器的容器中，将400克比环氧基团含量为5mol/kg的基于双酚A的环氧树脂溶于172g的60℃-70℃下的甲基异丁基酮中。添加210克(2摩尔)的二乙醇胺。当停止放热时，在130℃(回流温度)下再继续该反应一小时。在冷却到75℃之后，添加830克由在甲基异丁基酮中的1摩尔亚苄基二异氰酸酯/1摩尔甲基丙烯酸羟乙酯以70％浓度的溶液组成的一异氰酸酯溶液，并且让该混合物反应直到不再能检测到游离异氰酸酯基。
实施例3根据本发明的添加剂的合成
由根据表1的单体的混合物制备丙烯酸丁酯的均聚物和共聚物。在回流温度(80℃-85℃)下在使用异丙醇作为溶剂的溶液中进行聚合，在6小时的时间内将该单体与自由基引发剂溶液(偶氮二异丁腈(AIBN)，在异丙醇中的浓度为5％)同时加入。引发剂的质量是单体质量的2％。在100hPa(100mbar)的减压下，同时温度升高直到120℃下通过溶剂的蒸发将所形成的聚合物从该溶液中分离出来。
表1丙烯酸丁酯(共)聚合物B1-B4和对比聚合物V1和V2的组成(质量分数，以％计)
| EA | BA | BMA | 2-EHA | 2-HEA | |
| B1 | 15 | 85 | - | - | - |
| B2 | - | 80 | 10 | 10 | - |
| B3 | - | 90 | - | 5 | 5 |
| B4 | - | 100 | - | - | - |
| V1 | - | - | - | 100 | - |
| V2 | 20 | 40 | - | 30 | 10 |
EA＝丙烯酸乙酯，BA＝丙烯酸丁酯，BMA＝甲基丙烯酸丁酯，
2-EHA＝丙烯酸2-乙基己酯，2-HEA＝丙烯酸2-羟乙酯
所用单体的质量分数的总和始终是100％。
实施例4分散体的制备
将得自实施例1和2的粘结剂A和B以80份A与20份B的这些粘结剂中的固体质量比混合。将聚合物B1-B4以及实施例3的V1和V2添加到这些混合物中，基于A和B的混合物的树脂固体，所添加的聚合物的质量分数为0.85％。添加30mmol的甲酸以中和该粘结剂。在80℃下，在减压下(100hPa＝100mbar)通过蒸馏将溶剂甲基异丁基酮除去，然后在强烈搅拌下添加去离子水以形成45％浓度的分散体。继续搅拌同时将该分散体冷却至环境温度(20℃)，再添加去离子水以形成35％浓度的分散体。通过将聚合物B1-B4和V1和V2添加到该混合物中，获得了粘合剂分散剂4.1-4.6。
实施例5 CED油漆的制备
根据EP 1 088 038B1的实施例1和2制备颜料糊剂。将1600g实施例4的粘合剂分散体4.1-4.6的每种与2870克去离子水和530克所述颜料糊剂混合。获得5000g油漆5.1-5.6的每种，固体的质量分数大约为17％，pH值为6.0。
实施例6钢板的涂覆
在30℃和300V下，使用实施例5的油漆5.1-5.6将已经通过磷化预处理过的钢板蘸涂2分钟，以形成干膜厚度大约为25μm的层。在80℃下冲刷10分钟后，在180℃下将钢板固化20分钟。
实施例7：表面的测试
表面质量
通过目测检查来评价：
好 没有任何弧坑、针孔或其它凹口的光滑无缺陷表面
少许 多达五处不太显著的弧坑，但是看不见金属表面
差 显著的缺陷如弧坑、针孔或其它凹口
滴油测试
通过以下测试评价添加剂的效果
将用油漆5.1-5.6涂覆的实施例6的涂覆钢板风干，将一滴滑模油(Anticorit RP 41078)沉积在该涂覆表面上，然后在180℃下烘烤该薄片15分钟。如果在漆膜上看不见任何印记，则试验结果是“好”；如果漆膜上存在单个的缺陷，看不见金属，和如果漆膜上存在多个凹痕或弧坑，则为“单个”，或如果可以看见金属，则结果是“失败”。
PVC粘附试验
将用油漆5.1-5.6涂覆的实施例6的另外四组涂覆钢板分别风干并在160℃和180℃下烘烤。将PVC基密封组合物(“PVC-N”，从Gurit-Essex AG，Switzerland获得)分别涂覆到经涂覆和烘烤的板材上以使用20mm×40mm的框架产生2mm的层厚度并在140℃和160℃下固化。冷却之后按以下方式测试粘附性：使用小刀从基材上切开PVC层的一个边缘的5mm测试条。用两个手指提起该松动部分，并试图扯离整个层。对PVC粘附性作出以下评价：
0没有粘附
1差的粘附
2弱的粘附
3充分的粘附
4良好的粘附
5非常好的粘附
结果编制在表2中。
表2添加剂的性能试验
| 表面质量 | PVC粘附性 | |||||
| 添加剂 | 单独 | 滴油测试 | CED固化160℃ | CED固化180℃ | ||
| PVC固化 | PVC固化 | |||||
| 140℃ | 160℃ | 140℃ | 160℃ | |||
| B1 | 好 | 好 | 3 | 4 | 3 | 5 |
| B2 | 好 | 好 | 3 | 4 | 2 | 4 |
| B3 | 好 | 单个 | 3 | 4 | 3 | 5 |
| B4 | 好 | 好 | 3 | 4 | 3 | 4 |
| V1 | 好 | 好 | 1 | 2 | 2 | 3 |
| V2 | 好 | 单个 | 2 | 3 | 3 | 3 |
| 空白 | 少许 | 失败 | 3 | 4 | 3 | 4 |
可以看出，即使将CKD涂层低温固化，在根据本发明的实施例中仍看出优异的PVC粘附性。如果CED在高温下固化，并且PVC在低温下固化，则看出更小的影响。因为降低涂层的固化温度在经济上是有利的，所以在160℃下固化CED涂层的结果是非常重要的。
Claims (10)
1.降低或抑制漆膜表面缺陷的形成的方法，包括：将丙烯酸丁酯的均聚物B和丙烯酸丁酯和可共聚合单体A的共聚物BA中的至少一种添加到水性油漆组合物中，其特征在于在该共聚物中源自共聚单体A的结构部分的质量分数不超过30％。
2.权利要求1的方法，其中在该共聚物中源自具有羟基的共聚单体A的结构部分的质量分数不超过5％。
3.权利要求1的方法，其中该水性油漆组合物包含环氧树脂胺加合物。
4.权利要求1的方法，其中基于树脂部分的质量，均聚物B或共聚物BA的质量分数为0.5％-5％。
5.权利要求1的方法，其中通过阴极电沉积将该水性油漆组合物涂覆到导电基材上。
6.包含丙烯酸丁酯的均聚物B和丙烯酸丁酯和可共聚合单体A的共聚物BA中的至少一种的水性油漆组合物，其特征在于在该共聚物中源自共聚单体A的结构部分的质量分数不超过30％。
7.权利要求6的水性油漆组合物，其中在该共聚物中源自具有羟基的共聚单体A的结构部分的质量分数不超过5％。
8.权利要求6的水性油漆组合物，其中基于该水性油漆的所述聚合物和树脂部分的质量总和，均聚物B或共聚物BA的质量分数为0.5％-5％。
9.权利要求6的水性油漆组合物，其中该油漆组合物包含环氧树脂胺加合物。
10.用权利要求6的水性油漆组合物涂覆的基材。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04026505.0 | 2004-11-09 | ||
| EP04026505A EP1655350A1 (en) | 2004-11-09 | 2004-11-09 | Aqueous paint composition and process to reduce or suppress surface defects in paint films |
| PCT/EP2005/011581 WO2006050828A2 (en) | 2004-11-09 | 2005-10-28 | Aqueous paint composition and process to reduce or suppress surface defects in paint films |
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| CN2012103103301A Pending CN102796411A (zh) | 2004-11-09 | 2005-10-28 | 降低或抑制漆膜表面缺陷的水性油漆组合物和方法 |
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| Country | Link |
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| US (1) | US20080017517A1 (zh) |
| EP (2) | EP1655350A1 (zh) |
| JP (1) | JP2008518766A (zh) |
| CN (2) | CN101056952B (zh) |
| AR (1) | AR051622A1 (zh) |
| AT (1) | ATE513020T1 (zh) |
| ES (1) | ES2368247T3 (zh) |
| MY (1) | MY143759A (zh) |
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| GB8712577D0 (en) * | 1987-05-28 | 1987-07-01 | Ici Plc | Coating compositions |
| AT392649B (de) * | 1989-10-12 | 1991-05-10 | Vianova Kunstharz Ag | Verwendung von acrylatcopolymerisaten als additive fuer waessrige kationische lacksysteme |
| DE4129766A1 (de) * | 1991-09-06 | 1993-03-11 | Basf Lacke & Farben | Verfahren zur herstellung von waessrigen dispersionen |
| JPH0625567A (ja) * | 1992-07-06 | 1994-02-01 | Nissan Motor Co Ltd | カチオン電着塗料組成物 |
| DE4308428A1 (de) * | 1993-03-17 | 1994-09-22 | Basf Lacke & Farben | Bindemittelsysteme für die Elektrotauchlackierung |
| AT409765B (de) * | 1998-05-08 | 2002-11-25 | Dupont Performance Coatings | Elektrotauchlackbäder mit zusätzen, die die bildung von kratern im eingebranntem zustand verhindern |
| JP4088371B2 (ja) * | 1998-06-25 | 2008-05-21 | 日本ペイント株式会社 | カチオン電着塗料組成物 |
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2004
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2005
- 2005-10-17 TW TW094136192A patent/TW200626689A/zh unknown
- 2005-10-28 ES ES05801770T patent/ES2368247T3/es active Active
- 2005-10-28 CN CN200580038012.2A patent/CN101056952B/zh active Active
- 2005-10-28 EP EP05801770A patent/EP1812521B1/en active Active
- 2005-10-28 WO PCT/EP2005/011581 patent/WO2006050828A2/en active Application Filing
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- 2005-10-28 CN CN2012103103301A patent/CN102796411A/zh active Pending
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| Publication number | Publication date |
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| AR051622A1 (es) | 2007-01-24 |
| CN101056952B (zh) | 2013-03-27 |
| ES2368247T3 (es) | 2011-11-15 |
| TW200626689A (en) | 2006-08-01 |
| ATE513020T1 (de) | 2011-07-15 |
| JP2008518766A (ja) | 2008-06-05 |
| MY143759A (en) | 2011-07-15 |
| WO2006050828A2 (en) | 2006-05-18 |
| CN102796411A (zh) | 2012-11-28 |
| EP1655350A1 (en) | 2006-05-10 |
| US20080017517A1 (en) | 2008-01-24 |
| EP1812521A2 (en) | 2007-08-01 |
| EP1812521B1 (en) | 2011-06-15 |
| WO2006050828A3 (en) | 2006-07-27 |
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