CN108633281B - 粉体涂料用潜伏性固化剂及包括它的环氧粉体涂料组合物 - Google Patents
粉体涂料用潜伏性固化剂及包括它的环氧粉体涂料组合物 Download PDFInfo
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Abstract
本发明涉及一种粉体涂料用潜伏性固化剂及包括它的环氧粉体涂料组合物,更详细地涉及一种由咪唑、氨基醇以及环氧树脂的加成反应产物与酚类固化剂树脂进行热共混制备而成,并且通过抑制酚类固化剂的反应性来确保潜伏性(latency),作为固化剂适用于粉体涂料时能提供提高的涂膜外观以及耐弯曲性,且还能改善涂料制备作业性的粉体涂料用潜伏性固化剂及包括它的环氧粉体涂料组合物。
Description
技术领域
本发明涉及一种粉体涂料用潜伏性固化剂及包括它的环氧粉体涂料组合物,更详细地涉及一种如下的粉体涂料用潜伏性固化剂及包括它的环氧粉体涂料组合物,其由咪唑、氨基醇(amino alcohol)以及环氧树脂的加成反应产物与酚类固化剂树脂进行热共混制备而成,且通过抑制酚类固化剂的反应性来确保潜伏性(latency),并且作为固化剂适用于粉体涂料时能提供提高的涂膜外观以及耐弯曲性,并且还能改善涂料制备作业性。
背景技术
美国专利第4250293号公开了对双酚-A(bisphenol A,BPA)和二甲氨基丙胺(Dimethylaminopropylamine,DMAPA)类的胺进行盐化(salt)的潜伏性固化剂及适用它的环氧粉体涂料组合物。
并且,美国专利第6184273号公开了脂环族酸酐(phthalic anhydride)和聚胺的反应所产生的潜伏性固化剂及适用了上述固化剂和碳化(carbonated)环氧树脂的涂料组合物。
而且,美国专利第6592994号公开了使用双氰胺(dicyandiamide,DICY)潜伏性固化剂的透明漆(clear coat)用环氧粉体组合物。
但是,对于上述现有技术文献里记载的潜伏性固化剂而言,由于缺乏潜伏性,涂料制备作业性的改善可能会不够明显,且对于双氰胺而言,由于熔点高,使得相应的潜伏性会看似优异,但适用于钢筋(rebar)用粉体涂料时,会产生弯曲性明显降低的问题。
发明内容
本发明要解决的技术问题
本发明的技术问题在于,提供通过抑制酚类固化剂的反应性来确保潜伏性(latency),且作为固化剂适用于粉体涂料时,能够提供提高的涂膜外观及耐柔韧性,并且还能改善涂料制备作业性的粉体涂料用潜伏性固化剂及包括它的环氧粉体涂料组合物。
技术方案
为了解决上述技术问题,本发明提供由咪唑、氨基醇以及环氧树脂的加成反应产物(adduct)与酚类固化剂树脂进行热共混(hot blending)制备而成的潜伏性固化剂。
根据本发明的其他方面,能够提供包括作为主剂的环氧树脂、及上述潜伏性固化剂的粉体涂料组合物。
根据本发明的另一方面,能够提供包括由上述粉体涂料组合物形成的涂膜的、被涂装的物品(优选为管或者钢筋(rebar))。
有益效果
根据本发明的潜伏性固化剂及包括它的粉体涂料组合物,能够提供提高的涂膜外观及耐弯曲性,从而尤其适合用于管或钢筋(rebar)等材料的快速固化型涂装。
附图说明
图1为分别由实施例(左侧)以及比较例(右侧)的粉体涂料涂装的钢筋外观的照片。
图2为用于对比实施例(左侧)以及比较例(右侧)的粉体涂料固化行为的示差扫描热量计(DSC)分析结果。
具体实施方式
以下,详细说明本发明。
本发明的潜伏性固化剂由咪唑、氨基醇以及环氧树脂的加成反应产物(adduct)与酚类固化剂树脂进行热共混(hot blending)制备而成。
上述咪唑可以是具有1个以上活性氢的咪唑,例如能使用1种以上的由如下化学式1表示的咪唑。
[化学式1]
在上述化学式1中,R1及R2可相同或者不同,且表示氢、烷基(例如,C1-C6烷基)或者芳基(例如,C6-C18芳基)基团。
具体地,上述咪唑可以为选自2-甲基咪唑(2-methylimidazole)、2-苯基咪唑(2-phenylimidazole)、2-乙基-4-甲基咪唑(2-ethyl-4-methylimidazole)及它们的混合物。更优选地,使用2-甲基咪唑。
上述氨基醇可以为具有1个以上(例如,1至3个)的羟烷基(hydroxyalkyl)的胺化合物,且具体为选自单烷醇胺(monoalkanolamine)(更具体地,单(C1-C6)烷醇胺,例如,N-甲基乙醇胺)、二烷醇胺(dialkanolamine)(更具体地,为二(C1-C6)烷醇胺,例如,二乙醇胺(diethanolamine))、三烷醇烷烃胺(trialkanolalkanamine)(更具体地,为三(C1-C6)烷醇(C1-C6)烷烃胺,例如,三羟甲基氨基甲烷(trimethylol aminomethane))及它们的混合物。更具体地,二乙醇胺。
上述环氧树脂可以为双酚A型(bisphenol A type)环氧树脂或者双酚F型(bisphenol F type)环氧树脂,其当量具体可以为100~1500。更具体地,可以使用当量为100~300的液体状环氧树脂、当量为400~1500的固体状环氧树脂或者它们的混合物,相比更具体地可以使用当量为150~250的液体状环氧树脂。
在制备咪唑、氨基醇及环氧树脂的加成反应产物时,其成分的使用量上没有特别的限制,但例如,以咪唑、氨基醇及环氧树脂的总和100重量份为基准,咪唑可以为10~30重量份(更具体地,为15~25重量份),氨基醇可以为5~20重量份(更具体地,为10~15重量份),并且环氧树脂可以为50~80重量份(更具体地,为60~75重量份)。
另外,所使用的咪唑和氨基醇的当量比可以为咪唑当量与氨基醇当量相同或者大于氨基醇当量,例如,咪唑当量:氨基醇当量可以为3:1~1:3,但不会限定于此。当咪唑当量比上述范围高时,会出现固化速度变快而潜伏性降低的问题,并且当液体状的氨基醇的量相对较少而与环氧树脂进行加成反应时,为了溶解固体状的咪唑需使用更多的不必要的溶剂。相反,当咪唑当量比上述范围低时,会出现固化速度降低的问题。
咪唑、氨基醇及环氧树脂的加成反应为放热反应,因此能在适当的溶剂内进行。可使用的溶剂可以选自乙醇之类的极性溶剂、甲苯和二甲苯之类的非极性溶剂以及它们的混合物。并且,咪唑、氨基醇及环氧树脂的加成反应可以在升温(例如,90~120℃的温度范围内的升温)下进行。
上述酚类固化剂树脂可以由酚类化合物和环氧树脂的反应制备而成,其分子量例如为200~1000,更具体地可以为400~800。
在制备上述酚类固化剂树脂时,酚类化合物可以选自双酚A(BPA)、双酚F(BPF)及它们的混合物,环氧树脂可以为如上所述的成分。
在制备酚类固化剂树脂时,酚类化合物和环氧树脂的使用量是没有特别的限定,例如可以是以酚类化合物和环氧树脂的总和为100重量份为基准,酚类化合物为40~80重量份(更具体地,为50~70重量份),且环氧树脂为20~60重量份(更具体地,为30~50重量份)。
酚类化合物和环氧树脂的反应可在适当的催化剂条件下进行。可使用的催化剂可以选自磷类催化剂(例如,乙基三苯基溴化膦(ethyltriphenylphosphonium bromide)、乙基三苯基碘化膦(ethyltriphenylphosphonium iodide)等)、胺类催化剂(例如,2-乙基-4-甲基咪唑等)及它们的混合物。并且,酚类化合物和环氧树脂的反应可在升温下(例如,120~200℃)进行。
将上述咪唑、氨基醇及环氧树脂的加成反应产物和上述酚类固化剂树脂进行热共混(hot blending)而制备本发明的潜伏性固化剂。对于咪唑、氨基醇及环氧树脂的加成反应产物100重量份,热共混的酚类固化剂树脂的量例如为100~150重量份,更具体地,可以为110~140重量份,但不会限定于此。
咪唑、氨基醇及环氧树脂的加成反应产物和上述酚类固化剂的热共混可以在例如80~200℃下进行。当进行热共混时,或者在之后,除去残留在混合物内的溶剂,从而能获得固体组分为99%以上的粉末状的潜伏性固化剂。
根据本发明的另一方面,能提供包括作为主剂的环氧树脂以及上述本发明的潜伏性固化剂的粉体涂料组合物。
本发明粉体涂料组合物所包括的主剂环氧树脂,例如,可以使用环氧当量为800~1200(更具体地,为900~1000)的环氧树脂,具体地,可选自双酚A型环氧树脂、双酚F型环氧树脂及它们的混合物。
对于本发明粉体涂料组合物所包括的主剂环氧树脂的量,以涂料组合物总共为100重量份为基准,例如可以为40~80重量份,更具体地可以为50~70重量份。并且,对于本发明粉体涂料组合物所包括的潜伏性固化剂的量,以涂料组合物总共为100重量份为基准,例如可以为5~20重量份,更具体地可以为8~15重量份。
本发明的粉体涂料组合物的特征在于,包括作为固化剂的上述潜伏性固化剂,但不意味着其排除其他固化剂的使用。即,本发明粉体涂料组合物除上述固化剂之外,在可达成本发明的目的范围内根据需要,可另外包括现有的粉体涂料用固化剂(例如,酚类固化剂)。
并且本发明的粉体涂料组合物除上述成分外,以常规使用的标准量还包括常规使用于粉体涂料的1种以上的添加剂(例如,颜料、流动性改进剂、填料等)。
在制备本发明的粉体涂料组合物的方法上没有特别的限制,可通过使用常规的粉体涂料制备方法及设备本身,或者适当地变更来制备。
以下,通过实施例进一步详细地说明本发明。只是,下述实施例仅用于例示本发明,本发明并不会限制于此。
[实施例]
潜伏性固化剂制备例
1)制备咪唑、氨基醇及液体状环氧树脂的加成反应产物
向带有温度计、搅拌装置的合成用4口烧瓶中依次投入110g的2-甲基咪唑、80g的二乙醇胺、30g的丁醇,吹入氮气且逐渐升温至100℃。其中,控制370g的当量为190的液体状双酚A环氧树脂的放热且将其慢慢投入后,在相同的温度维持2h以上。然后,对反应混合物进行冷却且用二甲苯溶剂进行稀释而获得咪唑、氨基醇及液体状环氧树脂的加成反应产物,即中间体树脂(固体组分65%)。
2)制备酚类固化剂
向带有温度计、搅拌装置的合成用4口烧瓶中依次投入400g的双酚A、250g的液体状双酚A环氧树脂,吹入氮气且逐渐升温至140℃。在双酚A完全溶解的时刻,投入0.1g的乙基三苯基碘化膦后,升温至180℃并维持2h以上。维持后,冷却至常温来制备粉末状的酚类固化剂树脂。
3)制备潜伏性固化剂
在上述2)工艺制备的酚类固化剂树脂中投入上述1)工艺制备的中间体树脂500g,进行热共混且除去溶剂而制备固体组分99%以上的粉末状潜伏性固化剂树脂。
粉体涂料组合物制备例
使用如下表1所示的含量的成分,分别制备实施例及比较例的粉体涂料组合物。作为固化剂,在实施例中使用上述制备例中制备的潜伏性固化剂,在比较例中使用现有的酚类固化剂。
通过步骤1的过程,均匀混合主剂、固化剂、催化剂、颜料及添加剂等原料后,通过使用亨舍尔混合机(henschel mixer)以2000~5000rpm干式预混合约100~600s,从而在熔融混合时以维持均匀的物理性质的方式进行干式混合的预先混合过程。
通过步骤2的过程,利用分散机(PLK46,Buss Co.)在90~120℃的温度下对经上述步骤1的过程被预先分散的原料进行熔融混合分散。使熔融混合的原料通过冷却辊和冷却带来制备成大小为50~100mm、厚度为1~5mm的碎片。
通过步骤3的过程,利用粉碎机(锤磨机(hammer mill))机械性地研磨(平均粒子大小:40~60μm)经上述步骤2的过程被熔融混合分散的碎片。
[表1]
(含量单位:重量份)
成分 | 实施例 | 比较例 |
主剂 | 60 | 60 |
固化剂1 | - | 11.3 |
固化剂2 | 12.3 | - |
催化剂 | - | 1 |
颜料1 | 3 | 3 |
颜料2 | 5 | 5 |
添加剂 | 0.3 | 0.3 |
填料 | 19.4 | 19.4 |
合计 | 100 | 100 |
主剂:双酚A型环氧树脂(当量:900~1000)
固化剂1:制备例2)的酚类固化剂
固化剂2:制备例3)的潜伏性固化剂
催化剂:2-甲基咪唑(四国(Shikoku))
颜料1:有色颜料/拜耳乐(Bayferrox)130M(拜耳)
颜料2:有色颜料/CR-80(石原)
添加剂:流动性改进剂(PLP-100,KS Chemical)
填料:欧米亚碳酸钙5(Omyacarb 5)(韩国欧米亚)
试验例
将预先喷砂(blasting)处理过的19mm直径的钢筋素材预热至180~250℃,并且将实施例及比较例的粉体涂料组合物通过静电喷涂机分别涂装至200~500μm的厚度。然后,将涂装的钢筋素材在常温下放置约1min,然后直接沉积在冷水里并最终形成涂膜。对涂装的试片及粉体涂料进行了以下项目的测定及评价,其结果示于表2。
弯曲性
根据ASTM A776,将喷砂处理过的钢筋素材在弯曲性试验设备中使用114mm芯棒(mandrel)弯曲试片时,测定涂膜是否开裂。
固化性
(1)△Tg:在温度为232℃的热板上,以300~400μm的厚度适当地涂敷粉体涂料。在涂敷的粉体涂料形成涂膜的30s后,将涂膜取出并沉积在冷水中。对取出的涂膜使用示差扫描量热量计求出△Tg。△Tg越少越优异。
(2)凝胶时间(gel-time)在温度为200℃的热板上涂敷1g左右的粉体涂料后,测定粘度瞬间上升的时刻。表2示出了通过多次重复后获得的范围。
阴极剥离性
在涂装的钢筋素材上钻3mm直径的孔来制作试验素材。在3.5英尺直径的汽缸中填满3%的NaCl溶液,再浸渍铂金线和试验素材。然后,向铂金线和试验素材施加1.5V的电压且施加7天。7天后取出素材,用刀以放射状的方式刮初期钻的3mm的孔周边(共8处)直至露出素材,再以涂膜剥离部位为中心,将刀推入涂膜和素材之间并以杠杆原理测定粘附性后,求出其长度的平均。平均长度越短越优异。表2示出了通过多次重复后获得的范围。
外观(肉眼观察)
肉眼观察涂装的钢筋的外观后评价。并且,图1为分别示出了由实施例(左侧)以及比较例(右侧)的粉体涂料涂装的钢筋外观的照片。
比较固化行为
为了比较固化行为,对实施例及比较例的粉体涂料分别进行DSC分析,其结果如图2所示。
参照图2,可确定实施例的固化开始温度为130.15℃,比较例为110.72℃。即,使用潜伏性固化剂的粉体涂料的固化开始温度会移至更高的温度,这能够使得在预热(180~250℃)的被涂物上涂装粉体涂料时,延迟可瞬间发生的固化。因此,能够提高对于被涂物的涂料的渗透性(wetting)(即,有充分的时间获得渗透性),从而使涂料具有优异的粘附性、弯曲性及外观。
并且,参照表2及图2,与比较例进行比较时,实施例的发热量更高且△Tg接近0。这意味着△Tg越接近0,固化越完全,△Tg值越大,固化不完全。即,在实施例的情况下,完全固化,所以能够确认相比比较例提高了物理性质。
[表2]
项目 | 实施例 | 比较例 |
弯曲性 | 无涂膜开裂 | 发生涂膜开裂 |
△Tg(℃) | 0.40 | 1.89 |
凝胶时间(秒) | 11.5~12.0 | 9.5~10.0 |
阴极剥离性(mm) | 3.1~4.0 | 3.8~5.0 |
外观 | 非常优异 | 良好 |
作业性 | 便于批量生产 | 不易涂装 |
固化开始温度(℃) | 130.15 | 110.72 |
发热峰曲线 | 陡峭 | 平缓 |
发热量(J/g) | 35.7 | 29.0 |
Claims (6)
1.一种潜伏性固化剂,其由咪唑、氨基醇以及环氧树脂的加成反应产物与酚类固化剂树脂进行热共混制备而成,
其中,咪唑当量:氨基醇当量为3:1~1:0.57。
3.根据权利要求2所述的潜伏性固化剂,其中,所述咪唑选自2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑及它们的混合物。
4.根据权利要求1所述的潜伏性固化剂,其中,氨基醇选自单烷醇胺、二烷醇胺、三烷醇烷烃胺及它们的混合物。
5.根据权利要求1所述的潜伏性固化剂,其中,在80~200℃下进行所述热共混。
6.一种粉体涂料组合物,其包括作为主剂的环氧树脂、及根据权利要求1至5之一所述的潜伏性固化剂。
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KR101803123B1 (ko) | 2010-08-12 | 2017-11-29 | 가부시키가이샤 아데카 | 잠재성 경화제 조성물 및 일액 경화성 에폭시 수지 조성물 |
JP6098864B2 (ja) * | 2012-08-30 | 2017-03-22 | 荒川化学工業株式会社 | 反応生成物および当該反応生成物を含有する防錆性組成物 |
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2015
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2016
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- 2016-05-04 CN CN201680022384.4A patent/CN108633281B/zh not_active Expired - Fee Related
- 2016-05-04 WO PCT/KR2016/004690 patent/WO2016182259A1/ko active Application Filing
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CN101998970A (zh) * | 2008-04-14 | 2011-03-30 | 陶氏环球技术公司 | 用于粉末涂料应用的环氧-咪唑催化剂 |
CN103952057A (zh) * | 2014-04-09 | 2014-07-30 | 国润恒科(天津)防腐工程技术有限公司 | 一种超韧可急速弯曲钢筋防腐粉末涂料组合物及其制备方法和应用 |
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WO2016182259A1 (ko) | 2016-11-17 |
RU2676286C1 (ru) | 2018-12-27 |
US10683386B2 (en) | 2020-06-16 |
SA517390224B1 (ar) | 2021-02-07 |
CN108633281A (zh) | 2018-10-09 |
KR101741652B1 (ko) | 2017-06-01 |
KR20160132278A (ko) | 2016-11-17 |
US20180201720A1 (en) | 2018-07-19 |
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