CN101636456B - 用于氟碳涂料组合物的超分散剂 - Google Patents
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Abstract
本发明公开了一种用于氟碳涂料组合物的超分散剂。该氟碳涂料组合物通常包含氟碳树脂、粘合剂树脂、交联剂和超分散剂。该超分散剂包含聚缩水甘油基低聚物与至少一种氨基化合物的反应产物。聚缩水甘油基低聚物包含具有内醚键和内酯键中至少一个的1~25个碳原子的碳链,并且包含多个环氧基。该至少一种氨基化合物具有环状、杂环、烷基或杂烷基结构,该结构被至少一个伯或仲胺基取代,所述伯或仲胺基用于与所述环氧基中的至少一个反应并且将其打开。
Description
相关申请的交叉引用
本申请是2006年2月3日提交的美国专利申请No.11/275,916的部分继续。
发明背景
1.发明领域
本发明大体上涉及一种超分散剂。更具体地,本发明的超分散剂可用于氟碳涂料组合物。
2.相关技术的描述
氟碳树脂,例如聚偏二氟乙烯(PVDF)可用于配制具有优良耐气候性的涂料。因为氟碳树脂具有差的流变特性和颜料润湿特性,通常将粘合剂树脂或超分散剂加入到氟碳涂料组合物中。为了获得最佳的耐气候和耐化学抗性,在涂料组合物中希望高的氟碳树脂含量。许多涂料应用要求具有70重量%或更多的氟碳树脂的涂料组合物,并且余下的部分是粘合剂树脂。含有氟碳树脂,特别是PVDF,和粘合剂树脂的涂料组合物趋向具有相对高的粘度。对于一些涂料应用,特别是卷材涂料应用,希望具有与粘合剂树脂组合的高的氟碳树脂含量,但与用目前相关技术领域的组合物可能具有的粘度相比,具有较低的粘度。
以前用于氟碳涂料组合物的典型粘合剂树脂具有羟基和胺官能团,这是因为由这些官能团产生的改进的耐机械应力性和耐化学性。然而,这类粘合剂树脂和超分散剂的来源在以前受到限制。原本的超分散剂是3-(2-甲基丙烯酰氧基乙基)-2,2-螺环己基噁唑烷(MESO),并且由于高的生产成本,MESO单体变得愈加难以和/或更加昂贵地获得。
由于MESO单体难以获得,一些相关技术领域的方法在形成期间使用粘合剂树脂。例如,粘合剂树脂由不具有另外的官能团的丙烯酸和丙烯酸酯、具有另外的官能团的丙烯酸和丙烯酸酯以及丙烯酰氧基烷基噁唑烷聚合而成。官能丙烯酸/酯提供了用于与交联剂交联的位点。丙烯酰氧基烷基噁唑烷减少了氟碳树脂和丙烯酸树脂分散体的粘度。降低丙烯酸树脂的粘度的其他尝试包括使丙烯酸树脂与聚酰亚胺、氨基、环氧基等聚合和/或反应。然而,这些改性的丙烯酸树脂的表现不如用MESO改性的丙烯酸树脂那样好。
本发明的受让人共同拥有的共同未决的专利申请描述了一种由可商购获得的组分配制粘合剂树脂的新方法,使得该粘合剂树脂的表现即使不比用MESO改性的丙烯酸树脂更好,也与用MESO改性的丙烯酸树脂一样好。在该共同未决的专利申请中,第一组分是具有环氧基的丙酸树脂,其可与具有伯或仲胺的氨基化合物反应,以打开环氧基。尽管该这样的粘合剂树脂的表现好,但发现在商业应用期间杂质将与环氧基反应(或者阻止与环氧基的反应),留下有限的可用于胺基反应的位点。因此,粘合剂树脂不能有效地分散氟碳树脂,因为粘合剂树脂具有有限的官能团。
因此,提供一种超分散剂是有利的,当该超分散剂被引入到涂料组合物中时,该超分散剂充分地降低粘度并且提供所希望的颜料润湿特性。另外,有利的是提供一种由可商购获得并且相对廉价的单体和起始组分形成超分散剂,以使得制备包括超分散剂的涂料组合物并未成本过高的方法。
发明概述和优点
本发明提供一种用于氟碳涂料组合物的超分散剂。该超分散剂包含聚缩水甘油基低聚物与至少一种氨基化合物的反应产物。该聚缩水甘油基低聚物包含具有至少一个内醚和酯键的1~25个碳原子的碳链,并且包含多个环氧基。该超分散剂具有至少一种氨基化合物,其具有环状、杂环、烷基或杂烷基结构,所述结构被至少一个伯或仲胺基取代,所述伯或仲胺基用于与所述环氧基中的至少一个反应并且将其打开。所得的超分散剂具有来自氨基化合物的胺官能团以有助于氟碳树脂的分散,并且具有由打开至少一个所述环氧基而得到的羟基官能团以增强与氟碳涂料组合物中的交联剂的交联。
根据本发明形成的氟碳涂料组合物包含氟碳树脂、粘合剂树脂、交联剂和超分散剂。该超分散剂具有来自氨基化合物的胺官能团以有助于氟碳树脂的分散,和由打开至少一个环氧基而得到的羟基官能团以增强与交联剂交联。换句话说,来自氨基化合物的胺官能团降低了涂料组合物的粘度,使得本发明可以代替使用丙烯酰氧基烷基噁唑烷的粘合剂树脂或超分散剂,并且特别是大量使用MESO的那些。
本发明克服了表现出相关技术领域的粘合剂树脂、超分散剂和氟碳涂料组合物表现出的不足。具体地,本发明提供了具有多个羟基的超分散剂,所述羟基由将多个环氧基打开而得到。当如共同拥有并且共同未决的美国专利申请No.11/275,916中披露的那样,超分散剂仅具有单个羟基时,在形成涂料组合物的同时存在的杂质可能与羟基反应,由此降低了超分散剂的有效性。因此,多个羟基能够弥补任何的杂质同时还有效地使氟碳树脂分散。本发明还由可商购获得并且相对廉价的单体制备超分散剂,使得可以通过将超分散剂引入到涂料组合物中来降低生产成本。另外,由于引入了根据本发明形成的超分散剂,因此充分降低了涂料组合物的粘度。
发明详述
公开了一种用于氟碳涂料组合物的超分散剂。该氟碳涂料组合物通常包含氟碳树脂、粘合剂树脂(或分散剂树脂)、交联剂、超分散剂、溶剂和添加剂。本领域那些普通技术人员理解的是其他粘合剂树脂,特别是非-氨基树脂可用于氟碳涂料组合物中。
粘合剂树脂优选是丙烯酸粘合剂树脂。丙烯酸粘合剂树脂包含多个丙烯酸酯或丙烯酸酯单体的反应产物。丙烯酸粘合剂树脂通常以约10~约60%的量存在,基于涂料组合物的总重量计。用于形成粘合剂树脂的丙烯酸酯的合适例子包括,但不限于,甲基丙烯酸甲酯、甲基丙烯酸乙酯和甲基丙烯酸羟乙酯。
用于本发明的合适的氟碳树脂包括聚偏二氟乙烯(PVDF),如在商标Kynar下出售的那些;聚氟乙烯、聚四氟乙烯;偏二氟乙烯和四氟乙烯的共聚物,如在商标Kynar SL下出售的那些;在商标Fluonate下出售的氟乙烯/乙烯基酯/乙烯基醚;在商标Kynar 500和Kynar SL下出售的专利的基于偏二氟乙烯的聚合物;和所述氟碳树脂的混合物。氟碳树脂具有高的分子量,典型地具有约100,000~约500,000的分子量(重均)。氟碳树脂优选以粉末形式使用。该粉末通常不溶于用于本发明的涂料组合物的溶剂,但被溶剂溶胀,这增加了涂料组合物的粘度。
氟碳树脂以约20~约50%,典型地约25~约45%,并且优选约25~约35%的量存在,基于涂料组合物的总重量计。为了获得最佳的耐化学性和耐机械压力性,希望的是粘合剂和氟碳树脂以总树脂含量的约70%的量存在。当粘合剂和氟碳树脂的量高于70%时,仅可以实现耐化学性和耐机械应力性的微小改进,但由于氟碳树脂的高成本,成本显著增加。
交联剂可以是氨基塑料树脂,例如三聚氰胺/甲醛树脂或三聚氰胺脲树脂。其他合适的交联剂包括异氰酸酯、封端的异氰酸酯、有机硅烷和乙二醇脲。交联剂通常被选择为在环境温度下基本不与超分散剂反应,但在升高的固化温度例如其上涂覆涂料组合物的基材的固化温度下与超分散剂交联。交联剂通常以约0.2~约10%的量使用,基于涂料组合物的总重量计。
超分散剂通常包含聚缩水甘油基低聚物与至少一种氨基化合物的反应产物。聚缩水甘油基低聚物包含具有内醚键和内酯键中至少一个的1~25个碳原子的碳链,并且包含多个环氧基。优选地,该碳链具有1~20并且更优选1~15个碳原子。本领域那些普通技术人员应理解的是如果存在酯键,则与两个氧原子相连的碳原子不包括在碳链中的碳原子数目内。碳链选自线性的、支化的和它们的组合。换句话说,碳链可以包括线性段、支化段,或两者。作为选择,碳链可以选自脂族、脂环族、芳族和它们的组合。换句话说,碳链可以具有脂族段、脂环族段或芳族段,和不同段的组合。
碳链还可以包括一个或多个醚键或酯键。例如,碳链可以具有单个醚键或单个酯键,或者碳链可以具有多个醚键或多个酯键。作为选择,碳链可以具有醚键和酯键的组合。不意在受理论的束缚,据信由于这些键存在于其中,醚和/或酯键有助于分散氟碳树脂。
聚缩水甘油基低聚物具有约150~约1000,优选约250~约750,并且更优选约350~约750的重均分子量。如一名本领域普通技术人员所理解的那样,聚缩水甘油基低聚物可由各种引发剂分子,如,但不限于,甘油、季戊四醇、三甲基丙烷(TMP)或它们的组合形成,然后可以将这些引发剂分子环氧化,以形成聚缩水甘油基低聚物。
其中R是碳链。聚缩水甘油基低聚物可以包含一个或多个上述通式并且以混合物的形式存在。聚缩水甘油基低聚物的一个示例性的实例可作为314从Nagase&Co.Ltd商购获得,并且具有如下所示的结构式:2,2’,2”-(丙烷-1,2,3-三基三(氧基))三(亚甲基)三环氧乙烷
聚缩水甘油基低聚物的另一个示例性实例可作为321从Nagase&Co.Ltd商购获得,并且具有下示的结构式:2,2’-(2-乙基-2-((环氧乙烷-2-基甲氧基)甲基)丙烷-1,3-二基)双(氧基)双(亚甲基)二环氧乙烷
314和321均具有三个环氧基和三个内醚键。具有四个环氧基和四个内醚键的聚缩水甘油基低聚物的另一个示例性实例可作为411从Nagase&Co.Ltd商购获得,并且具有如下所示的结构式:2,2’-(2,2-双((环氧乙烷-2-基甲氧基)甲基)丙烷-1,3-二基)双(氧基)双(亚甲基)二环氧乙烷
聚缩水甘油基低聚物的另一个示例性实例还可作为UVR-6107从Dow Chemical商购获得,并且具有如下所示的结构式:7-氧杂双环[4.1.0]庚烷-3-基甲基7-氧杂双环[4.1.0]庚烷-3-羧酸酯
聚缩水甘油基低聚物以约30~约90%,优选约50~约80%,并且更优选约50~约75%的量存在,各自基于超分散剂的总重量计。应理解的是除非特别说明,这些重量百分比不包括溶剂。当重量百分比包括溶剂时,聚缩水甘油基低聚物以约10~约60%的量存在,基于超分散剂的总重量计。
超分散剂还包括至少一种被伯或仲胺基取代的氨基化合物。该氨基化合物可以具有杂环、环状、烷基或杂烷基结构。该氨基化合物可与聚缩水甘油基低聚物反应,使得伯或仲胺基将至少一个环氧基打开,从而获得具有胺官能团和羟基官能团的超分散剂。
杂环化合物可以具有至少一个氮代替碳,并且可以进一步包括至少一个氧代替碳。当氨基化合物具有杂环结构时,氨基化合物具有通常的环结构。合适的杂环氨基化合物可以选自,但不限于,亚乙基脲、吡咯烷、2-吡咯烷酮、哌啶、所有的噁唑烷和吗啉中的至少一种。当氨基化合物具有环状结构时,氨基化合物具有带有至少一个伯或仲胺的环状烃。一种合适的环状氨基化合物包括二环己胺。当氨基化合物具有烷基结构时,烷基结构包括可以为支化的或为线性的具有至少一个伯或仲胺的烃链。合适的烷基氨基化合物包括叔丁胺、异丙胺、二异丙胺、2-氨基-2-甲基-1-丙醇和乙醇胺。杂烷基结构包括烃链并且可以具有至少一个伯或仲胺和/或氧作为烃链的一部分。合适的杂烷基氨基化合物包括N,N-二甲基-1,3-丙二胺、二甲胺和二乙醇胺。
氨基化合物以足以与多个环氧基反应的量使用。换句话说,氨基化合物以相对于聚缩水甘油基低聚物的多个环氧基化学计量等量地存在。一般而言,氨基化合物以约15~约50%,优选约20~约45%,并且更优选约25~约40%的量存在,各自基于超分散剂的总重量计。当包括溶剂时,氨基化合物以约5~约40%的量存在,基于超分散剂的总重量计。氨基化合物和聚缩水甘油基低聚物的反应产物降低了涂料组合物的粘度。另外,该反应产物有助于使得超分散剂与氟碳树脂更相容并且由此使涂料组合物的粘度稳定。
超分散剂以约1~约40%的量存在,基于氟碳涂料组合物的总重量计。优选地,超分散剂以约1~约20%,最优选约1~约5%的量存在,均基于氟碳涂料组合物的总重量计。那些本领域普通技术人员应理解的是超分散剂有助于使粘合剂树脂分散。然而,通过改变配方的其他方面,可以在没有粘合剂树脂的情况下使用超分散剂。一旦超分散剂形成,则超分散剂具有约200~约10,000,优选约350~约6,500,并且更优选约500~约1,000的化学式量,各自基于超分散剂的总重量计。
本发明的涂料组合物可基于有机溶剂或溶剂的混合物。合适的溶剂包括,但不限于,二醇、酯、醚酯、二醇酯、醚醇、脂族烃、芳族烃和邻苯二甲酸酯增塑剂,或者以组合的形式或者单独作为主溶剂。固含量通常为约30~约90%,基于涂料组合物的总重量计。最典型的是固含量为约45~约75%,基于涂料组合物的总重量计。合适的溶剂的实例包括aromatic 100、二甘醇丁醚乙酸酯、二元酯、甲基戊基酮和异佛尔酮。
当例如用作有色涂料上的透明涂料时,该涂料组合物可以是透明的。其也可以含有至多约30%的颜料和填料,基于涂料组合物总重量计。取决于颜色、物理需要、耐用性和耐化学性,可用于该涂料体系中的颜料类型包括用于涂料工业中的所有颜料。合适的颜料包括无机金属氧化物、有机化合物、金属薄片和云母颜料、填充剂或填料颜料,和腐蚀抑制性颜料如铬酸盐、二氧化硅、硅酸盐、磷酸盐和钼酸盐。底层的有色涂料和覆盖的透明涂料可以根据本发明配制。可以将涂料组合物施加到裸露的金属表面上,但优选施加到首先用底漆涂料涂覆或者通过其他已知的方法,包括电涂处理的金属上。合适的底漆包括丙烯酸酯类、聚酯类和用三聚氰胺交联的环氧化物类、封端的异氰酸酯和酚类。
可以通过各种工艺将根据本发明的涂料组合物施加到基材上。然而,特别地将涂料组合物配制用于卷涂工艺并且在卷涂工艺中是有用的。在逆辊卷涂中,通常在约400~500°F的最高金属温度(PMT)下施加涂料组合物。在PMT下的停留时间为约10秒~约5分钟。如果通过喷射涂覆涂料组合物,则固化温度类似,但由于更大的金属质量而因此需要显著更长的固化时间,例如约20分钟。
这里示出的说明了超分散剂和涂料组合物的形成并且说明了超分散剂和涂料组合物的某些性能的以下实施例意在解释,而非限制本发明。
实施例
根据下表中列出的组成形成超分散剂。除非另外说明,表1中的量以克计。
表1:超分散剂配方
实施例1 | |
聚缩水甘油基低聚物 | 200.0 |
氨基化合物 | 116.8 |
溶剂 | 273.4 |
总计 | 590.2 |
在实施例1中,聚缩水甘油基低聚物是314并且氨基化合物是哌啶。将Aromatic 100(200.0克)和聚缩水甘油基低聚物的混合物装入装有搅拌器、冷凝器、温度计、惰性气体入口和滴加漏斗的三升树脂反应烧瓶中。将反应器用氮气冲洗并且将进料加热至70℃。随后,制备Aromatic 100(58.4克)和氨基化合物的混合物,并且放入滴加漏斗中,并且在30分钟内加入反应器并且然后将温度保持在70℃60分钟。在完成加入之后,将反应器内容物用15.0克Aromatic 100冲洗并且将内容物的温度增至85℃,并且保持30分钟。然后将树脂冷却。
所得的树脂具有54~55%的固含量、以固体计19%的胺含量、25℃下A3-A2的粘度(Gardner-Holdt泡沫),和7.95LB/GAL的每加仑的重量。
然后将超分散剂引入到氟碳涂料组合物中。除非另外说明,组分以百分比列出,基于涂料组合物总量计。
表2:涂料组合物配方
实施例1 | |
氟碳树脂 | 20.4% |
分散剂/粘合剂树脂 | 8.3% |
交联剂 | 0.5 |
超分散剂 | 1% |
颜料 | 29% |
溶剂 | 40% |
酸催化剂 | 0.2% |
消泡剂 | 0.1% |
蜡溶液 | 0.5% |
在实施例1中,通过将15.8g氧化钛颜料分散在5g超分散剂、5g粘合剂树脂和20g溶剂(异佛尔酮)的混合物中形成颜料分散体。粘合剂树脂为90%的甲基丙烯酸甲酯、5%的甲基丙烯酸乙酯和5%的甲基丙烯酸羟乙酯。将粘合剂树脂用溶剂稀释,并且在搅拌下加入超分散剂和粉末状的二氧化钛颜料。使用高速桨叶将颜料完全分散。然后使树脂、溶剂和颜料混合物通过介质研磨机以实现完全分散。通过将22.1g氟碳树脂(聚偏二氟乙烯(PVDF))分散在4.2g粘合剂树脂、1g超分散剂和20g溶剂中制备氟碳基质。再次将粘合剂树脂和超分散剂用溶剂稀释,在搅拌下加入粉末状PVDF并且使用高速桨叶将PVDF完全分散。
通过将剩余的组分加入到氟碳基质中制备中间基质。例如将0.1g酸催化剂和0.5g三聚氰胺(交联剂)加入到氟碳基质中。同样,将0.3g消泡剂和0.2g蜡溶液加入到氟碳基质中。
通过将颜料分散体和氟碳基质共混并且用剩余的11.8g溶剂调节粘度来完成涂料组合物。在最终的配方上进行各种试验如粘度和密度以确保其的组成完整性。通过将薄膜施加到基材上并且在392~500°F(200~260℃)下烘焙20~60秒将该涂料组合物固化。
将实施例1的涂料组合物施加到钢板上并且在465°F下烘焙55秒,得到0.75~0.85密耳(.019~.022mm)薄膜。然后将薄膜的耐甲乙酮(MEK)性作为双重擦拭(double rubs)至薄膜失效的次数测量。实施例1对于200+擦拭而言表现良好,并且比较例1对于100+擦拭而言表现良好。这些结果表明如果不是更好的话,实施例1至少与依赖于MESO的涂料组合物表现得一样好,即使不是更好。如上所述,MESO变得愈加难以且昂贵地获得。因此,本发明的目的是提供一种同样起作用并且花费较少制备的替代性涂料组合物。
显然地,根据上述教导,本发明的许多改进和变化是可能的。本发明可以不同于在所附的权利要求范围内具体描述的那样实施。
Claims (15)
1.氟碳涂料组合物,其包含:
氟碳树脂;
粘合剂树脂;
交联剂;和
超分散剂,其包含1)聚缩水甘油基低聚物,其包含具有内醚键和内酯键中至少一个的1~25个碳原子的碳链,并且包含多个环氧基;和
2)至少一种氨基化合物,其具有环状、烷基或杂烷基结构,所述结构被伯或仲胺基取代,所述伯或仲胺基用于与所述环氧基中的一个反应并且将其打开;
其中,所述超分散剂具有来自所述氨基化合物的胺官能团,以有助于氟碳树脂在氟碳涂料组合物中分散,并且具有由打开至少一个所述环氧基而得到的羟基官能团,以增强与氟碳涂料组合物中的交联剂的交联。
2.如权利要求1所述的氟碳涂料组合物,其中,所述聚缩水甘油基低聚物以30~90%的量存在,基于所述超分散剂的总重量计。
3.如权利要求2所述的氟碳涂料组合物,其中,所述氨基化合物以15~50%的量存在,基于所述超分散剂的总重量计。
4.如权利要求1所述的氟碳涂料组合物,其中,所述聚缩水甘油基低聚物具有150~1000的重均分子量。
5.如权利要求1所述的氟碳涂料组合物,其中,所述碳链选自线性的、支化的和它们的组合。
6.如权利要求1所述的氟碳涂料组合物,其中,所述碳链选自脂族、芳族和它们的组合。
7.如权利要求6所述的氟碳涂料组合物,其中,所述碳链为脂环族碳链。
9.如权利要求1所述的氟碳涂料组合物,其中,所述氨基化合物选自亚乙基脲、吡咯烷、2-吡咯烷酮、哌啶、吗啉、叔丁胺、异丙胺、二异丙胺、2-氨基-2-甲基-1-丙醇、乙醇胺、二环己胺、N,N-二甲基-1,3-丙二胺、二甲胺、二乙醇胺,和它们的组合。
10.如权利要求1所述的氟碳涂料组合物,其进一步包含分散于所述氟碳树脂中的颜料。
11.如权利要求1所述的氟碳涂料组合物,其具有30~70%的固含量。
12.如权利要求1所述的氟碳涂料组合物,其中,所述氟碳树脂以30~99%的量存在,基于所述氟碳涂料组合物的总重量计。
13.如权利要求1所述的氟碳涂料组合物,其中,所述超分散剂以1~40%的量存在,基于所述氟碳涂料组合物的总重量计。
14.如权利要求1所述的氟碳涂料组合物,其中,所述交联剂以0.2~10%的量存在,基于所述氟碳涂料组合物的总重量计。
15.如权利要求1所述的氟碳涂料组合物,其中,所述氟碳树脂是氟碳粉末。
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US20090012235A1 (en) * | 2006-02-03 | 2009-01-08 | Basf Corporation | Dispersant for use in a fluorocarbon coating composition |
US7956144B2 (en) | 2006-02-03 | 2011-06-07 | Ppg Industries Ohio, Inc. | Acrylic resin for use in fluorocarbon coating compositions and method of forming the same |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86106083A (zh) * | 1985-09-19 | 1987-03-18 | 标准石油公司 | 环氧碳氟涂料组合物及其制法 |
US5310770A (en) * | 1992-12-30 | 1994-05-10 | Hi-Tek Polymers, Inc. | Water reducible epoxy-amine adducts based on the diglycidyl ether of cyclohexane dimethanol |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2909448A (en) * | 1955-03-07 | 1959-10-20 | Shell Dev | Salts of polyamine polyepoxide adducts and their use as curing agents for polyepoxides |
NL266645A (zh) | 1960-07-05 | |||
US3668193A (en) | 1971-01-27 | 1972-06-06 | Pennwalt Corp | Vinylidene fluoride coating compositions containing polyimides |
US3944689A (en) | 1971-10-22 | 1976-03-16 | Ppg Industries, Inc. | Glossy coating compositions from copolymers of vinylidene fluoride |
US4157996A (en) | 1977-03-18 | 1979-06-12 | General Electric Company | Coating solution of polyetherimide-forming monomers |
US4433104A (en) | 1982-03-18 | 1984-02-21 | General Electric Company | Polyetherimide-fluorinated polyolefin blends |
AU566792B2 (en) | 1983-06-30 | 1987-10-29 | E.I. Du Pont De Nemours And Company | Curing agent for fluorocarbon polymer |
JPH083041B2 (ja) | 1986-06-30 | 1996-01-17 | 三井東圧化学株式会社 | ポリイミド樹脂組成物 |
GB2194539B (en) | 1986-09-01 | 1990-08-01 | Labofina Sa | Pvdf-based powder coatings |
JPH01201373A (ja) * | 1988-02-05 | 1989-08-14 | Nippon Paint Co Ltd | 水性塗料用組成物 |
US5030394A (en) | 1988-11-08 | 1991-07-09 | Labofina, S.A. | PVdF-based powder coatings |
US5312866A (en) | 1989-11-30 | 1994-05-17 | Mitsui Toatsu Chemicals, Incorporated | Polyimide based resin composition |
US5284893A (en) | 1989-10-13 | 1994-02-08 | Daikin Industries, Ltd. | Coating composition |
JPH04211445A (ja) * | 1990-03-13 | 1992-08-03 | Daikin Ind Ltd | 湿気硬化型樹脂組成物 |
US5185403A (en) | 1991-07-31 | 1993-02-09 | Morton Coatings, Inc. | Thermosetting acrylic polymers and coating compositions containing said acrylic polymers and fluorocarbon resins |
US6037412A (en) | 1994-07-21 | 2000-03-14 | Fina Research, S.A. | Preparing powder primer of thermoset binder and PVdF-compatible thermoplastic |
US5700578A (en) | 1995-06-26 | 1997-12-23 | Crane Plastics Company Limited Partnership | Fluoropolymer/terpolymer composite |
JPH0912967A (ja) * | 1995-06-28 | 1997-01-14 | Sumitomo Metal Ind Ltd | フッ素系塗料組成物及びそれを用いた塗装ステンレス鋼板 |
JP3941128B2 (ja) * | 1995-12-18 | 2007-07-04 | ダイキン工業株式会社 | 粉体塗料用組成物 |
US6017639A (en) | 1996-10-23 | 2000-01-25 | Valspar Corporation | Vinylidene difluoride-based coating compositions |
US5959022A (en) | 1998-04-01 | 1999-09-28 | Ausimont Usa, Inc. | Compatible polyvinylidene fluoride blends with polymers containing imide moieties |
DE69921718T2 (de) | 1998-04-01 | 2005-12-22 | Solvay Solexis, Inc., Wilmington | Verträgliche Mischungen aus Polyvinylidenfluorid und aromatischem Polyimid |
JP2000313838A (ja) * | 1999-04-28 | 2000-11-14 | Toagosei Co Ltd | 塗料用組成物 |
US6255398B1 (en) | 1999-06-29 | 2001-07-03 | Basf Corporation | High volume solids fluorocarbon coatings |
US6699933B2 (en) | 2001-08-07 | 2004-03-02 | Ppg Industries Ohio, Inc. | Method of coating coils using a high solids fluorocarbon coating composition |
US6679943B1 (en) | 2002-05-01 | 2004-01-20 | Basf Corporation | Coating containing adhesion promoting additive |
JP4440590B2 (ja) | 2003-09-29 | 2010-03-24 | 関西ペイント株式会社 | カチオン性塗料組成物及び塗膜形成方法 |
US7956144B2 (en) | 2006-02-03 | 2011-06-07 | Ppg Industries Ohio, Inc. | Acrylic resin for use in fluorocarbon coating compositions and method of forming the same |
-
2007
- 2007-03-12 US US11/684,823 patent/US7838582B2/en active Active
- 2007-11-05 CN CN2007800521365A patent/CN101636456B/zh not_active Expired - Fee Related
- 2007-11-05 CA CA2637767A patent/CA2637767C/en not_active Expired - Fee Related
- 2007-11-05 JP JP2009553568A patent/JP5455656B2/ja not_active Expired - Fee Related
- 2007-11-05 WO PCT/US2007/083587 patent/WO2008112026A1/en active Application Filing
- 2007-11-05 AT AT07863874T patent/ATE550397T1/de active
- 2007-11-05 RU RU2009137616/05A patent/RU2460749C2/ru not_active IP Right Cessation
- 2007-11-05 MX MX2008010784A patent/MX2008010784A/es active IP Right Grant
- 2007-11-05 EP EP07863874A patent/EP2121854B1/en not_active Not-in-force
-
2009
- 2009-09-04 ZA ZA200906151A patent/ZA200906151B/xx unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86106083A (zh) * | 1985-09-19 | 1987-03-18 | 标准石油公司 | 环氧碳氟涂料组合物及其制法 |
US5310770A (en) * | 1992-12-30 | 1994-05-10 | Hi-Tek Polymers, Inc. | Water reducible epoxy-amine adducts based on the diglycidyl ether of cyclohexane dimethanol |
Also Published As
Publication number | Publication date |
---|---|
MX2008010784A (es) | 2009-03-02 |
ZA200906151B (en) | 2010-05-26 |
CA2637767C (en) | 2012-04-10 |
US20070185249A1 (en) | 2007-08-09 |
EP2121854B1 (en) | 2012-03-21 |
ATE550397T1 (de) | 2012-04-15 |
JP2010521551A (ja) | 2010-06-24 |
US7838582B2 (en) | 2010-11-23 |
CA2637767A1 (en) | 2008-09-12 |
RU2009137616A (ru) | 2011-04-20 |
JP5455656B2 (ja) | 2014-03-26 |
WO2008112026A1 (en) | 2008-09-18 |
EP2121854A1 (en) | 2009-11-25 |
CN101636456A (zh) | 2010-01-27 |
RU2460749C2 (ru) | 2012-09-10 |
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