CN1480498A - 耐磨性得到改进的蜡-改性涂料组合物 - Google Patents
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Abstract
描述一种可固化涂料组合物，它基于羟基官能粘结剂和端基封堵的多异氰酸酯，包含精细分散、悬浮、涂蜡的聚酰胺，并表现出大大改进的耐磨数值。
Description
包含精细分散悬浮聚酰胺的基于羟基官能粘结剂和多异氰酸酯或聚酯-蜜胺树脂体系的可固化涂料组合物是已知的(EP B 0 047 508)。此类涂料组合物固化后生成具有良好可机械变形性、良好耐磨和良好耐化学侵蚀、耐天候老化和光稳定的涂层。
目前，主要基于聚酰胺11和聚酰胺12的聚酰胺细粉末被用在聚氨酯-和聚酯基涂料中作为凸纹剂和性能改进剂。还可想出其他粘结剂体系。
此种体系主要应用在卷材涂装工业，但也用于木材涂装行业并且，日益广泛地用于一般工业部门。例子包括地面覆盖物或厨房家具用耐磨木材涂料。
在当今的诸领域中，人们利用聚酰胺粉末非常好的耐磨，特别是作为凸纹剂，来延长涂层体系的寿命，例如用于防晒保护系统(卷帘门窗)。在卷材涂布过程中，该涂料体系施涂到铝片材和钢片材上，随后切割和成形为要求的零部件。
目前开发出的涂料组合物，例如是在烘炉内反应并固化的活性体系，其例子是，异氰酸酯在高于160℃温度的脱端基封堵，随后与聚酯的羟端基起反应。
以聚酰胺11粉末和/或聚酰胺12粉末为凸纹剂改进聚氨酯和/或聚酯涂料体系的基础是可证明地存在于聚酰胺中的游离活性端基基团，主要是端羧基基团和端氨基基团，与在烘炉内生成的活性组分之间的反应。伴随这，在烘炉内还发生聚酰胺化学地结合到形成的涂料膜中的过程。
影响涂层膜表面质量和耐磨的另一个合适的组分是蜡，特别是微粉化聚乙烯蜡。然而从性能的观点，高浓度蜡对涂层膜具有不利影响。这样的涂层常常表现出对指印的高度敏感。渗出现象也会在表面发生，这将降低涂层的光亮程度，或甚至导致涂层乳状浑浊。还观察到，高比例聚乙烯蜡在涂料中分散得不完全。不均匀分布的结果是最终涂层膜具有斑点组织。
因此，目的是提供一种涂料组合物，它不具有所描述的缺点，即便在高比例蜡的情况下也是如此。这一目的已按照本文的权利要求达到。
令人惊奇的是现已发现，采用包含聚酰胺粉末的上述涂料组合物，涂层膜耐磨性取得相当大的改进，尤其当按照本发明聚酰胺粉末预先涂以蜡时。
在这方面，现已惊奇地发现，若采用一种涂蜡的聚酰胺粉末，则涂层膜耐磨性最高，并且高于蜡和聚酰胺粉末按传统方式分别加入到涂料组合物时的耐磨性。
另外，采用本发明涂料体系还可能避免或大大减少上面提到的由高蜡浓度引起的缺陷，例如，指印敏感性、表面渗出和/或乳状浑浊。
认为聚酰胺粉末在涂层膜中的化学固着将由于涂蜡而大大受阻并从而令聚酰胺颗粒容易从涂层膜中被磨擦跑出这样的假设是错误的。相反，令人惊奇的是，据发现尽管有这一涂层，聚酰胺端基在烘炉内仍然能较好地化学固着在端基封堵的活性体系上。
适合本发明涂料组合物的蜡包括所有烯烃类和/或Fischer-Tropsch(费-托合成)蜡。这些蜡还可以改性形式使用。改性蜡的例子是含聚四氟乙烯的聚乙烯蜡。此种蜡有利地具有90℃～160℃的熔点。
下面的内容旨在举例说明本发明的产品及其制备。
本发明涂料组合物包含涂布的聚酰胺粉末。它们由聚酰胺粉末组成，优选包含聚酰胺11和/或聚酰胺12。可使用的聚酰胺粉末包括研磨粉末，即通过研磨聚酰胺粒料制备的，以及沉淀粉末。特别优选采用按DE 29 06 647 B1(Huls公司)的沉淀法制备的聚酰胺12粉末，因为此种粉末具有非常均一的颗粒形态和多孔表面。
在涂料行业使用的聚酰胺粉末的情况下，平均颗粒形态d50优选介于5～60μm，尽管某些领域，大到约150μm的d50的较大颗粒也可使用。
该聚酰胺粉末涂有蜡。在此种情况下，通常施涂0.5份～10份微粉化的蜡每100份聚酰胺粉末。
蜡施涂到聚酰胺上既可以在干掺混中的冷混合物形式，也可以借助粘结或其他已知热混合方法来实现，但须保证混合机中最高温度维持在低于聚酰胺粉末熔融温度的水平，以便使聚酰胺粉末不发生烧结或粘连在一起形成较大颗粒，同时使混合机不致被涂上熔融聚酰胺。
在本发明涂料组合物中，涂布的聚酰胺粉末的用量介于0.1～40wt％，优选介于0.5～5wt％，更优选1～3wt％。
此种涂料组合物还包含EP 0 047 508 A2中描述的组分。该涂料体系基于与多异氰酸酯的异氰酸酯基团起反应的羟基官能粘结剂。其例子是聚酯、多元醇、聚醚、聚氨酯、聚二醇、聚丙烯酸酯、蜜胺树脂、乙烯基树脂、环氧树脂、酚树脂、脲树脂，或者含羟基基团的，还有含其他含活性氢官能团如胺、多氨基酰胺等的可比聚合物。
本发明涂料组合物包含10～60wt％，优选20～40wt％封堵的多异氰酸酯和含羟基粘结剂之和，很可能，正如EP 0 047 508所述，这两种组分之间的比例可在0.5∶1～5∶1之间变化。
该涂料组合物还可进一步包含各种各样溶剂，还有染料、颜料和其他商业上惯用添加剂，例如，紫外稳定剂。对应化合物同样也描述在EP 0 047 508中。
本发明涂料组合物可按照任何惯用方法施涂到相应表面上：作为非限制性例子可举出喷涂方法、辊涂方法、卷材涂布方法、流涂和刮刀涂布方法。
备有该涂料组合物的表面随后加热到活性体系能够与粘结剂的和聚酰胺粉末的官能团起反应的温度。在此加热期间，涂料组合物流展开来形成涂层膜，并且固化。加热可在烘炉(强制通风烘炉)内进行或者用热源辐照或感应来实现。
下面的例子旨在举例说明本发明，但本发明不限于这些：
涂布的范例聚酰胺的制备
100份聚酰胺12沉淀粉末，按照DE 29 06 647 B1制备并具有d10＝7μm，d50＝21μm和d90＝38μm的平均粒度分布，与表1所载各种不同蜡在10 L Henschel高速混炼机中在600rpm条件下剧烈混合，每种情况3min。每种情况的混炼机功率消耗量为约3.4×104W。
表1：透明涂料用聚酰胺粉末
| 产品 | 蜡类型 | 蜡份数 |
| 聚酰胺A | VESTOWAX 1012 | 5份 |
| 聚酰胺B | Lanco-Wax TF1778 | 5份 |
| 聚酰胺C | Comomulus VP 45 | 5份 |
| 聚酰胺D | Lanco PE1500 SF | 5份 |
| 聚酰胺E | - | 0份 |
另外，还采用不涂蜡的聚酰胺12沉淀粉末作为对比例，标为聚酰胺E。诸聚酰胺粉末按照表2用于生产透明涂料：
表2：透明涂料组成
| 聚酯树脂，不含油 | 45％ |
| 多异氰酸酯，封端的 | 15％ |
| 聚丙烯酸酯 | 1％ |
| DBTL(催化剂) | 0.2％ |
| 聚酰胺12粉末(聚酰胺A～E) | 0～10％ |
| 溶剂混合物(芳烃) | 凑足100％ |
某些涂料另外还包含1％微粉化蜡(参见表3)。
这些涂料被用于在铝片材上制备干膜厚20μm的样品涂层。按照DIN ISO 53754采用泰伯尔耐磨试验机，2×50g CS 10辊筒，3000转，测定耐磨。耐磨数值载于表3a和3b。
表3a：
| 实例 | 聚酰胺粉末 | 微粉化蜡 | 耐磨[mg] |
| 1.(空白例) | - | - | 90 |
| 2.(对比例) | 10％聚酰胺E | - | 72 |
| 3. | 10％聚酰胺A | - | 58 |
| 4. | 10％聚酰胺B | - | 62 |
| 5. | 10％聚酰胺C | - | 62 |
| 6. | 10％聚酰胺D | - | 57 |
表3b：
| 实例 | 聚酰胺粉末 | 微粉化蜡 | 耐磨[mg] |
| 7.(空白例) | - | 1.5％VESTOWAX 1012 | 52 |
| 8.(对比例) | 10％聚酰胺E | 1.5％VESTOWAX 1012 | 53 |
| 9. | 10％聚酰胺A | 1 ％VESTOWAX 1012 | 30 |
Claims (14)
1.一种可固化涂料组合物，基于羟基官能粘结剂和多异氰酸酯，包含精细分散的悬浮聚酰胺，其中聚酰胺粉末涂有蜡。
2.权利要求1的可固化涂料组合物，其中烯烃类和/或Fischer-Tropsch蜡被用作蜡。
3.以上权利要求中任何一项的可固化涂料组合物，其中使用熔点介于90～160℃的蜡。
4.以上权利要求中任何一项的可固化涂料组合物，其中聚酰胺粉末包含聚酰胺11和/或聚酰胺12。
5.以上权利要求中任何一项的可固化涂料组合物，其中聚酰胺粉末包含聚酰胺12沉淀粉末。
6.以上权利要求中任何一项的可固化涂料组合物用于涂布铝卷材和铁卷材的应用。
7.以上权利要求中任何一项的可固化涂料组合物用于涂布木材表面的应用。
8.以上权利要求中任何一项的可固化涂料组合物用于涂布地板表面的应用。
9.一种制备包含精细分散悬浮聚酰胺的基于羟基官能粘结剂和端基封堵多异氰酸酯的可固化涂料组合物的方法，包括先用蜡涂布聚酰胺粉末，再将它加入到涂料组合物中。
10.一种用于权利要求1的可固化涂料组合物中的聚酰胺粉末，其中聚酰胺粉末涂有蜡。
11.权利要求10的聚酰胺粉末，其中烯烃类和/或Fischer-Tropsch蜡被用作蜡。
12.权利要求10或11的聚酰胺粉末，其中使用熔点介于90～160℃的蜡。
13.权利要求10～12中任何一项的聚酰胺粉末，其中聚酰胺粉末包含聚酰胺11和/或聚酰胺12。
14.权利要求10～13中任何一项的聚酰胺粉末，其中聚酰胺粉末包含聚酰胺12沉淀粉末。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10235933.4 | 2002-08-06 | ||
| DE10235933 | 2002-08-06 | ||
| DE10300118A DE10300118A1 (de) | 2002-08-06 | 2003-01-07 | Mit Wachs modifizierte Beschichtungsmittel mit verbesserten Abriebbeständigkeiten |
| DE10300118.2 | 2003-01-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1480498A true CN1480498A (zh) | 2004-03-10 |
| CN1290952C CN1290952C (zh) | 2006-12-20 |
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| CNB031275117A Expired - Lifetime CN1290952C (zh) | 2002-08-06 | 2003-08-05 | 耐磨性得到改进的蜡－改性涂料组合物 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US6933047B2 (zh) |
| EP (1) | EP1388580B1 (zh) |
| JP (1) | JP4528501B2 (zh) |
| KR (1) | KR20040030250A (zh) |
| CN (1) | CN1290952C (zh) |
| AT (1) | ATE376041T1 (zh) |
| CA (1) | CA2436458C (zh) |
| DE (1) | DE50308396D1 (zh) |
| ES (1) | ES2294222T3 (zh) |
| HU (1) | HUP0302460A3 (zh) |
| PL (1) | PL207188B1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106867010A (zh) * | 2015-12-14 | 2017-06-20 | 赢创德固赛有限公司 | 用于粉床熔融法的聚合物粉末 |
| CN107022100A (zh) * | 2015-12-14 | 2017-08-08 | 赢创德固赛有限公司 | 用于粉末床熔融法的聚合物粉末 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7387236B2 (en) * | 2001-10-09 | 2008-06-17 | Delaware Capital Formation, Inc. | Dispensing of currency |
| US20050098622A1 (en) * | 2001-10-09 | 2005-05-12 | Gregory Jantsch | Dispensing of currency |
| US7770691B2 (en) * | 2004-08-18 | 2010-08-10 | Schabel Polymer Technology, Llc | Lightweight pelletized materials |
| US20070001383A1 (en) * | 2005-06-20 | 2007-01-04 | Gregory Jantsch | Dispensing of currency |
| US9222254B2 (en) | 2012-03-13 | 2015-12-29 | Schabel Polymer Technology, Llc | Structural assembly insulation |
| DK3280763T4 (da) | 2015-04-06 | 2023-10-30 | Novelis Inc | Vandbaserede coatingsammensætninger og tilhørende produkter og fremgangsmåder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4253848A (en) * | 1980-01-21 | 1981-03-03 | The United States Of America As Represented By The Secretary Of The Army | Method for determining oxidative status of unsaturated lipids and method for evaluating antioxidant effectiveness in lipid-polypeptide layers |
| DE3033586A1 (de) * | 1980-09-06 | 1982-04-15 | Reichhold Chemie AG, 6050 Offenbach | Hitzehaertbares beschichtungsmittel und dessen verwendung |
| DE3510688A1 (de) * | 1985-03-23 | 1986-09-25 | Hüls AG, 4370 Marl | Beschichtungspulver fuer das schmelzueberzugsverfahren auf der basis von polyamiden und haftverbessernden zusaetzen |
| FR2707659B1 (fr) * | 1993-06-30 | 1995-09-22 | Atochem Elf Sa | Composition en poudre à base de polyamide pour le revêtement de substrats métalliques. |
| JP3342758B2 (ja) * | 1993-11-26 | 2002-11-11 | 鬼怒川ゴム工業株式会社 | ゴム成形品の滑面構造 |
| FR2731005B1 (fr) * | 1994-12-29 | 1997-04-04 | Atochem Elf Sa | Composition en poudre a base de polyamide pour le revetement de substrats metalliques |
| JPH10219188A (ja) * | 1997-02-05 | 1998-08-18 | Kansai Paint Co Ltd | 塗料組成物及びこれを用いた塗装金属板 |
| DE19823426A1 (de) * | 1998-05-26 | 1999-12-02 | Degussa | Elektrostatische Pulverlacke auf Basis von Polyamiden und Polyolefinen |
| FR2787995B1 (fr) * | 1998-12-30 | 2002-05-03 | Oreal | Compostion cosmetique hydrophobe anhydre sous forme de poudre compacte |
-
2003
- 2003-07-11 AT AT03015866T patent/ATE376041T1/de not_active IP Right Cessation
- 2003-07-11 EP EP20030015866 patent/EP1388580B1/de not_active Expired - Lifetime
- 2003-07-11 ES ES03015866T patent/ES2294222T3/es not_active Expired - Lifetime
- 2003-07-11 DE DE50308396T patent/DE50308396D1/de not_active Expired - Lifetime
- 2003-08-01 CA CA2436458A patent/CA2436458C/en not_active Expired - Lifetime
- 2003-08-04 JP JP2003205778A patent/JP4528501B2/ja not_active Expired - Fee Related
- 2003-08-05 KR KR1020030053978A patent/KR20040030250A/ko not_active Application Discontinuation
- 2003-08-05 CN CNB031275117A patent/CN1290952C/zh not_active Expired - Lifetime
- 2003-08-05 PL PL361552A patent/PL207188B1/pl unknown
- 2003-08-05 HU HU0302460A patent/HUP0302460A3/hu unknown
- 2003-08-06 US US10/634,831 patent/US6933047B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106867010A (zh) * | 2015-12-14 | 2017-06-20 | 赢创德固赛有限公司 | 用于粉床熔融法的聚合物粉末 |
| CN107022100A (zh) * | 2015-12-14 | 2017-08-08 | 赢创德固赛有限公司 | 用于粉末床熔融法的聚合物粉末 |
| CN107022100B (zh) * | 2015-12-14 | 2021-03-12 | 赢创运营有限公司 | 用于粉末床熔融法的聚合物粉末 |
| US10968314B2 (en) | 2015-12-14 | 2021-04-06 | Evonik Operations Gmbh | Polymer powder for powder bed fusion methods |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040096665A1 (en) | 2004-05-20 |
| JP2004068008A (ja) | 2004-03-04 |
| JP4528501B2 (ja) | 2010-08-18 |
| KR20040030250A (ko) | 2004-04-09 |
| EP1388580B1 (de) | 2007-10-17 |
| PL361552A1 (en) | 2004-02-09 |
| ES2294222T3 (es) | 2008-04-01 |
| CA2436458C (en) | 2011-04-26 |
| ATE376041T1 (de) | 2007-11-15 |
| PL207188B1 (pl) | 2010-11-30 |
| HUP0302460A3 (en) | 2005-11-28 |
| EP1388580A3 (de) | 2005-12-07 |
| US6933047B2 (en) | 2005-08-23 |
| DE50308396D1 (de) | 2007-11-29 |
| CA2436458A1 (en) | 2004-02-06 |
| HUP0302460A2 (hu) | 2003-11-28 |
| EP1388580A2 (de) | 2004-02-11 |
| CN1290952C (zh) | 2006-12-20 |
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