CN105593259B - 涂料组合物 - Google Patents
涂料组合物 Download PDFInfo
- Publication number
- CN105593259B CN105593259B CN201480054540.6A CN201480054540A CN105593259B CN 105593259 B CN105593259 B CN 105593259B CN 201480054540 A CN201480054540 A CN 201480054540A CN 105593259 B CN105593259 B CN 105593259B
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- Prior art keywords
- coating composition
- coating
- secondary amine
- polymer
- amino resins
- Prior art date
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- 239000008199 coating composition Substances 0.000 title claims abstract description 85
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 39
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 229920003180 amino resin Polymers 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract 8
- 238000000576 coating method Methods 0.000 claims description 70
- 239000011248 coating agent Substances 0.000 claims description 67
- 239000000463 material Substances 0.000 claims description 53
- -1 ester amine Chemical class 0.000 claims description 29
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 23
- 108010064470 polyaspartate Proteins 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 19
- 239000012948 isocyanate Substances 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000004806 packaging method and process Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
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- 229920006037 cross link polymer Polymers 0.000 claims description 2
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- 239000000203 mixture Substances 0.000 description 18
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical class NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
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- 239000002184 metal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
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- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
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- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
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Abstract
一种涂料组合物,其包含:a)包含仲胺基团的成膜树脂,b)多异氰酸酯固化剂,及c)基于氨基树脂的聚合物的固体粒子。
Description
本发明涉及VOC低(低于250g/l)、干燥快速且抗蚀性优异的保护涂料组合物。这些涂料组合物尤其适用于涂覆风机叶片。
风力使用风力涡轮机将风能转化成诸如电的适用形式。风力产生于与电网连接的大规模风力农场以及独立涡轮机中用于将电提供至分离的位置。风力涡轮机通常具有2至4个经设计以持续约20年至25年的大叶片。风力涡轮机叶片或“风机叶片”连续暴露于自然环境,且其经理想设计以经受极限温度、风切、沉淀及/或其他环境危害而故障最少。在叶片前沿上常常观测到因侵蚀所致的涂料失效。叶片的“前沿”应理解为指叶片首先切入风中的部分,而后边缘则为相对边缘。前沿通常经历诸如盐、砂、尘土及其他造成干磨蚀的粒子的环境因素,以及诸如风、雨、雪等的湿润环境因素。因此,在前沿上可观测到加速的涂料失效及/或侵蚀。
因此,用于风机叶片上的保护涂料必须符合极严格的标准以便其持续其约20-25年的寿命。在与诸如风机叶片的基材冲撞期间,水滴显著改变其形状。大部分时间,雨滴在涂膜表面上产生类似冲击波的涟波,而仅在涟波的震央造成很小损害。对欲长期经受住雨滴多次冲撞的风机叶片上的涂料而言,涂膜应具有针对基材的优良粘着性及优良的回弹性。
目前用于涂覆风机叶片的主要市售产品为基于聚酯的聚氨酯。尽管这些涂料产品具有合理的粘着性及抗性特性,但其高挥发性有机物含量 (Volatile Organic Content,VOC)均高于250g/l,且在环境温度下常常干燥缓慢。为了提高这些涂料的干燥速率,可将其在空气烘箱中加热。另外,风机叶片上常常需要聚氨酯涂料的多层涂料以获得所需的雨蚀保护。将多层涂料涂覆于风机叶片耗时且昂贵。相比而言,本发明的涂料组合物能够在基材表面初步处理程度最低的情况下很容易地以一个涂层涂覆至基材,且此涂层提供优良的雨蚀保护。
包含聚脲型树脂的涂料组合物,例如由聚天冬氨酸酯胺及异氰酸酯固化剂形成的组合物在保护涂料产业中为已知的。然而,已知该类涂料的抗蚀性不及市售主要的基于聚酯的聚氨酯体系优良。意外地,本发明人已发现当将基于氨基树脂的聚合物添加至聚脲涂料体系中时,该涂料的抗蚀性大大提高至以下程度,即本发明的涂料所提供的抗蚀性至少与主要的基于聚酯的聚氨酯涂料体系的抗蚀性一样优良。然而,本发明的聚脲涂料不仅确实提供优良抗蚀性,而且有利的是,与主要的基于聚酯的聚氨酯涂料体系相比,其VOC也较低。另外,本发明的涂料组合物能够以较少涂层(例如仅一个涂层)提供相同保护,且能够使用标准技术涂覆。本发明的涂料能够在风力涡轮机叶片所经历的尤其恶劣的雨蚀条件下提供保护。
本发明提供的涂料组合物VOC低(优选为低于250g/l),在环境条件(优选为不到3小时,在50%RH及25℃下)中干燥时间短,贮存期良好(例如在25℃下90min或更长),且可使用标准技术容易地涂覆。另外,与已知基于聚脲的涂料体系相比,该涂料所提供的优越侵蚀保护(尤其雨蚀保护) 可仅以一个涂层实现。
发明概述
本申请涉及一种涂料组合物,其包含:
a)包含仲胺基团的成膜树脂,
b)多异氰酸酯固化剂,及
c)基于氨基树脂的聚合物的固体粒子。
优选地,(a)及(b)以如下量存在于涂料组合物中:异氰酸酯基团:仲胺基团的化学计量比率为1.0:1.0至2.5:1.0。
包含仲胺基团的成膜树脂可为聚天冬氨酸酯胺。
基于氨基树脂的聚合物可为基于甲基脲的聚合物。基于氨基树脂的聚合物可为交联的聚合物。以整个涂料组合物的重量计,基于氨基树脂的聚合物的固体粒子一般以1重量%至25重量%的量存在。
多异氰酸酯固化剂的异氰酸酯当量可在280g/eq与840g/eq之间,例如在280g/eq与500g/eq之间。
包含仲胺基团的成膜树脂的胺当量可在150g/eq与450g/eq之间。
优选地,(a)及(b)以如下量存在于涂料组合物中:异氰酸酯基团:仲胺基团的化学计量比率为大于1.2:1.0、大于1.3:1.0且优选大于1.5:1.0,最高比率为2.5:1.0。
本发明利用已知聚天冬氨酸酯胺。在一个实施方案中,聚天冬氨酸酯胺具有以下通式结构:
其中X表示在最高达100℃的温度下对异氰酸酯基团具有惰性的脂环烃;
R1及R2各自独立地选自在最高达100℃的温度下对异氰酸酯基团具有惰性的有机基团;
R3及R4各自独立地选自氢及在最高达100℃的温度下对异氰酸酯基团具有惰性的有机基团;及
n为至少2的整数。
涂料组合物通常以两个包装提供,第一包装包含聚天冬氨酸酯胺且第二包装包含多异氰酸酯固化剂。
本发明也涉及一种保护基材不受侵蚀(例如雨蚀或固体粒子侵蚀)的方法,其通过以下步骤实现:
-提供如本文所述的涂料组合物(例如,包括包含仲胺基团的成膜树脂、多异氰酸酯固化剂及基于氨基树脂的聚合物的固体粒子的涂料组合物),
-将涂料组合物涂覆至基材以在基材上形成一个或多个涂层,及
-使所述涂层于环境温度下在基材上硬化/固化。
本发明的涂料组合物可例如仅以一个涂层在约100μm至约300μm的厚度下涂覆。
基材可为风机叶片或其一部分。侵蚀可为固体粒子侵蚀或雨蚀。能够在环境温度下硬化/固化的涂料组合物为不需要人工加热以实现固化/硬化的涂料组合物。因此,一旦在无额外加热的情况下涂覆本发明的涂料组合物,其即能够在基材上固化以形成涂膜。本领域中通常也已知的环境温度为0℃至30℃的范围内的温度。
本发明也涉及经涂覆的基材,例如风机叶片或其一部分,其中该基材涂覆有本文所述的涂料组合物。
本发明也涉及基于氨基树脂的聚合物的固体粒子在涂料组合物中的用途,其用于改进由该涂料组合物形成的涂料的抗雨蚀性或抗固体粒子侵蚀性。
可根据ASTM G73-10量测抗雨蚀性的改进。可根据用于粒子侵蚀测试的ASTM G76量测抗固体粒子侵蚀性的改进。
发明详述
包含仲胺基团的成膜树脂(a)
包含仲胺基团的成膜树脂的适合实例包括例如脂族聚酯胺、脂族聚醚胺及聚天冬氨酸酯胺。
包含仲胺基团的成膜树脂的数均分子量优选在500g/mol与1200 g/mol之间,例如550g/mol与900g/mol之间的范围内。可根据ISO 13885-1:2008通过GPC量测分子量。
包含仲胺基团的成膜树脂的胺当量可在150g/eq与450g/eq之间,例如200-350g/eq。
胺当量按照下式自胺值计算:
胺当量=56.1×1000/[胺值],其中胺值可根据ASTM D 2074测定。
优选的包含仲胺基团的成膜树脂为聚天冬氨酸酯胺如描述于美国专利第5,126,170号中且对应于以下通式(I)的那些:
其中X表示在最高达100℃的温度下对异氰酸酯基团具有惰性的脂环烃;
R1及R2各自独立地选自在最高达100℃的温度下对异氰酸酯基团具有惰性的有机基团;
R3及R4各自独立地选自氢及在最高达100℃的温度下对异氰酸酯基团具有惰性的有机基团;及
n为至少2的整数。
举例而言,X可为包含6至20个碳原子的脂环烃。优选地,X表示通过自以下移除氨基所获得的二价烃基:1,4-二氨基丁烷、1,6-二氨基己烷、 2,2,4-及2,4,4-三甲基-1,6-二氨基己烷、1-氨基-3,3,5-三甲基-5-氨基甲基-环己烷、4,4'-二氨基-二环己基甲烷或3,3-二甲基-4,4'-二氨基-二环己基甲烷。
优选地,n为2。
优选地,R1及R2表示C1-C6烷基,例如甲基或乙基。优选地,R3及 R4表示氢。
如美国专利第5,126,170号中所描述,可通过使包含伯胺基团的一或多种环状多胺与不饱和二烷基酯反应来制备聚天冬氨酸酯胺。
用于制造聚天冬氨酸酯的包含一个以上伯胺基团的环状多胺组分通常包含6至25个碳原子,且含有至少一个脂环族环。适合的脂环族二胺组分的实例包括1,3-二氨基环己烷,1,4-二氨基环己烷,1,6-二氨基环己烷,2,2,4- 及2,4,4-三甲基-1,6-二氨基己烷,1-氨基-3,3,5-三甲基-5-氨基甲基己烷且优选为包括1,3-双(氨基甲基)环己烷、1,4-双(氨基甲基)环己烷的双(氨基甲基) 环己烷,异佛尔酮二胺,双(4-氨基环己基)甲烷,双(4-氨基环己基)丙烷, 4,4-二氨基-3,3-二甲基二环己基甲烷,4,4-二氨基-3,3-二甲基二环己基丙烷, 4,4-二氨基-3,3-二甲基-5,5-二甲基二环己基甲烷,4,4-二氨基-3,3-二甲基 -5,5-二甲基二环己基丙烷。
用于制造聚天冬氨酸酯的不饱和二烷基酯优选为丁烯二酸二乙酯,例如马来酸或富马酸的酯,例如马来酸及富马酸的二甲酯、二乙酯、二丙酯及二正丁酯。
或者,聚天冬氨酸酯可对应于通式(I),然而其中X为包含5至10个碳原子的脂族二价烃基而R1、R2、R3、R4及n与上述定义相同。
举例而言,X可表示通过自2-甲基戊烷二胺或己二胺移除氨基所获得的二价烃基。可通过使包含伯胺基团的一或多种脂族多胺与不饱和二烷基酯(如上所述)反应来制备聚天冬氨酸酯。
可用于本发明的聚天冬氨酸酯的一实例为NH1420(购自 BayerMaterial Science AG)。
如先前所提及,包含仲胺基团的成膜树脂的其他适合实例包括例如脂族聚酯胺及脂族聚醚胺。脂族聚醚胺的市售实例包括SD- 仲聚醚胺,诸如SD-231胺、SD-401胺、SD-2001胺,其均来自Huntsman Corporation。
(b)多异氰酸酯固化剂
多异氰酸酯固化剂可为一或多种多异氰酸酯固化剂。
一或多种多异氰酸酯固化剂的异氰酸酯当量的范围可在280g/eq与 1500g/eq之间,例如280g/eq至1200g/eq或280g/eq至840g/eq。
异氰酸酯当量(“NCO eq.wt”)意谓1当量异氰酸酯(“NCO”)反应性基团所需产品的克数。
异氰酸酯当量(g/eq)=4,200/[多异氰酸酯的NCO重量%]。举例而言,对于NCO重量%为10的已知多异氰酸酯固化剂,所计算出的异氰酸酯当量为4,200/10=420g/eq。可根据ASTM D2572-87通过使用二正丁胺的滴定法来量测多异氰酸酯组分的异氰酸酯基团含量。
在所有实施方案中,异氰酸酯当量可为大于300g/eq,或大于320g/eq,或大于340g/eq。
在所有实施方案中,多异氰酸酯固化剂的异氰酸酯当量可为小于1500 g/eq,或小于1200g/eq、840g/eq、800g/eq、750g/eq、700g/eq、650g/eq、 600g/eq、550g/eg或500g/eq。
举例而言,多异氰酸酯固化剂的异氰酸酯当量为280g/eq至1500g/eq, 280g/eq至1200g/eq,280g/eq至840g/eq,300g/eq至1500g/eq,300g/eq 至1200g/eq,300g/eq至800g/eq,300g/eq至700g/eq,300g/eq至600g/eq, 300g/eq至500g/eq,350g/eq至1500g/eq,350g/eq至1200g/eq,350g/eq 至840g/eq,或350g/eq至450g/eq。
另外,多异氰酸酯固化剂的数均分子量的范围可在550g/mol与2000 g/mol之间,例如1000g/mol至2000g/mol或1200g/mol至1800g/mol。可根据ISO-13885-1:2008通过GPC量测分子量。
一或多种多异氰酸酯固化剂可选自一或多种芳族或脂族多异氰酸酯。该类多异氰酸酯包括如二异氰酸酯及三异氰酸酯,包括缩二脲及异氰脲酸酯。优选多异氰酸酯固化剂包含至少一种脂族多异氰酸酯固化剂。优选地,脂族多异氰酸酯基于六亚甲基二异氰酸酯。
二异氰酸酯包括甲苯二异氰酸酯,4,4'-亚甲基-双(环己基异氰酸酯),异佛尔酮二异氰酸酯,2,2,4-及2,4,4-三甲基六亚甲基二异氰酸酯的异构混合物,1,6-六亚甲基二异氰酸酯,四甲代苯二甲撑二异氰酸酯及/或4,4'-二苯基亚甲基二异氰酸酯。
二异氰酸酯的缩二脲包括1,4-四亚甲基二异氰酸酯及1,6-六亚甲基二异氰酸酯,以及环脂族二异氰酸酯,诸如异佛尔酮二异氰酸酯及4,4'-亚甲基-双(环己基异氰酸酯)的缩二脲。可自其制备缩二脲的芳烷基二异氰酸酯的实例为间苯二甲撑二异氰酸酯及α.,.α.,.α.',.α.'-四甲基间苯二甲撑二异氰酸酯。
三官能异氰酸酯包括异佛尔酮二异氰酸酯、三异氰酸酯基壬烷、三苯基甲烷三异氰酸酯、1,3,5-苯三异氰酸酯、2,4,6-甲苯三异氰酸酯及六亚甲基二异氰酸酯的异氰脲酸酯的三聚体。尤其使用的多异氰酸酯为脂环族异氰酸酯,特别地,为二异氰酸酯如六亚甲基二异氰酸酯及异佛尔酮二异氰酸酯的异氰脲酸酯。
多异氰酸酯固化剂可为一或多种多异氰酸酯预聚物。多异氰酸酯预聚物为本领域中已知的。其为通过使多元醇与过量二异氰酸酯单体反应而产生的离散分子。用于本发明的适合多异氰酸酯预聚物的实例为六亚甲基二异氰酸酯的多异氰酸酯预聚物。该类适合的多异氰酸酯预聚物可自例如 Bayer Corporation的N3800及E3370商购获得。N3800为脂族多异氰酸酯(HDI异氰脲酸酯三聚体),其NCO含量为11±0.5%(异氰酸酯当量=4,200/11=382g/eq)。E3370为也基于六亚甲基二异氰酸酯的脂族多异氰酸酯预聚物,其NCO含量为 10.0±0.5%(异氰酸酯当量=4,200/11=400g/eq)。这些多异氰酸酯预聚物可单独或彼此组合使用。
异氰酸酯基团与仲胺基团的化学计量比率
异氰酸酯基团与仲胺基团的“1:1的化学计量比率”应以其通常方式理解为:存在相等数量的异氰酸酯基团与仲胺基团。
包含仲胺基团的成膜树脂(例如聚天冬氨酸酯胺)及多异氰酸酯固化剂优选以如下量存在于涂料组合物中:异氰酸酯基团(NCO):仲胺基团(NR2H) 的化学计量比率为1.0:1.0至2.5:1.0。(即1.0至2.5异氰酸酯基团对每1.0 仲胺基团)。
组分(a)及(b)可以如下量存在于涂料组合物中:异氰酸酯基团:仲胺基团的化学计量比率为大于1.3:1.0,大于1.4:1.0,大于1.5:1.0及适当地大于 1.6:1.0,达至最高的化学计量比率2.5:1.0。
异氰酸酯基团:仲胺基团的化学计量比率可为最高2.4:1.0、2.3:1.0、 2.2:1.0、2.1:1.0或1.9:1.0。
(c)基于氨基树脂的聚合物的固体粒子
涂料组合物包含基于氨基树脂的聚合物的固体粒子。
基于涂料组合物的总重量计算,基于氨基树脂的聚合物的固体粒子可以如下量存在于涂料组合物中:至少1重量%,或至少2重量%,或至少 4重量%。基于组合物的总重量计算,粒子量的上限适当地为25重量%,或20重量%,或14重量%。平均粒度一般在1μm至150μm的范围内。所使用的粒子一般具有粒度分布。举例而言,全部粒子的90%可小于14 μm,且全部粒子的50%可小于6.5μm。粒度可用激光衍射法量测,例如通过使用Horiba激光衍射粒度分析器。
粒子的横向尺寸及纵向尺寸可为类似数量级。粒子基本上可例如为球形。然而,粒子也可具有其他形状,例如片状或针状。
基于氨基树脂的聚合物可适当地通过氨基树脂或氨基树脂前体与甲醛的缩合反应或通过胺的其他缩合及/或加成反应制备。适合的基于氨基树脂的聚合物的实例为基于胍的聚合物,基于三聚氰胺的聚合物,基于氨基甲酸酯的聚合物,基于酰胺的聚合物,及基于脲的聚合物,特别地基于甲基脲的聚合物。基于氨基树脂的聚合物适当地为交联的,即该聚合物为硬塑料(duroplast)。交联可在氨基树脂与甲醛的缩合反应中进行。然而,交联也可由额外的交联剂引起。适合的基于氨基树脂的聚合物的固体粒子为例如以商标名MK购自Deuteron GmbH,德国。MK 粒子基于甲基脲聚合物。
(iv)溶剂
涂料组合物通常包含溶剂。可使用的溶剂的实例包括例如二甲苯,脂族石油溶剂(white spirit),矿油精,诸如以下C3-C8酮溶剂的酮溶剂:甲基异戊基酮、甲基正丁基酮、甲基异丁基酮、甲基乙基酮、二乙基酮及丙酮,及诸如以下乙酸酯的酯溶剂:乙酸乙酯、乙酸丙酯、乙酸丁酯及乙酸1-甲氧基-2-丙酯。涂料组合物中可使用一或多种溶剂。
(v)涂料组合物中的其他组分
涂料组合物也可包括各种其他填料及添加剂,例如颜料、体质颜料、着色剂、颜料分散剂、腐蚀抑制剂、强化剂、流变控制剂、均染剂、赋脂剂、湿润剂、抗缩孔剂、消泡剂、杀生物剂、促进剂、表面活性剂、(有机) 溶剂、塑化剂、轻型稳定剂、UV光吸收剂(例如292)、湿气清除剂、抗氧化剂及恶臭掩蔽剂。
填料为溶剂不可溶的固体物质,其通常用以在不损害涂料混合物(例如颜料及体质颜料)的反应化学性质的情况下增加总体积或用以扩展颜料的能力。填料可以涂料组合物总重量的2重量%至30重量%的浓度采用。
也可包括填料以抑制腐蚀或提供强度。填料的实例包括细微粉碎的矿物,诸如硫酸钡、包括热解法二氧化硅及/或胶态二氧化硅的二氧化硅、氧化铝、高岭土、胶态氧化铝、二氧化钛、氧化锆、胶态氧化锆、粘土、云母、白云石、滑石、碳酸镁、碳酸钙、硫酸钙、硅酸钙及/或偏硅酸钙。其他填料包括陶瓷微球与空心聚合微球,诸如以商品名购自Akzo Nobel的那些,及空心玻璃微球(诸如以商标名“K37”TM购自3M Company, St.Paul,Minn的那些)。
涂料组合物可包括着色剂。如本文中所使用,术语“着色剂”意谓对组合物赋予颜色及/或其他不透明度及/或其他视觉效果的任何物质。着色剂可以诸如离散粒子、分散体、溶液及/或薄片的任何适合形式添加至涂料中。单种着色剂或者两种或两种以上着色剂的混合物可用于本发明的涂料中。
着色剂的实例包括颜料、染料及色彩(tint),诸如油漆工业中所使用及 /或干颜料制造商协会(the Dry Color Manufacturers Association,DCMA) 中所列的那些以及特殊效果组合物。着色剂可包括例如不可溶但可在使用条件下湿润的细微粉碎的固体粉末。着色剂可为有机的或无机的,且可为聚结的或非聚结的。着色剂可通过研磨或简单混合并入涂料中。着色剂可通过使用研磨媒剂(grind vehicle)(诸如丙烯酸研磨媒剂)进行研磨而并入涂料中,研磨媒剂的使用应为本领域熟练技术人员所熟悉。着色剂可通过使用色料/颜色浓缩物并入。
(vi)典型涂料组合物
本发明的典型涂料组合物包含:
·5重量%至30重量%包含仲胺基团的成膜树脂,例如聚天冬氨酸酯胺;
·20重量%至50重量%多异氰酸酯固化剂,及
·5重量%至20重量%基于氨基树脂的聚合物的固体粒子。
涂料组合物也可包含5重量%至20重量%铝硅酸盐。
铝硅酸盐为由铝、硅及氧加相反离子构成的矿物。其为高岭土及其他粘土矿物的主要组分。红柱石、蓝晶石及硅线石为天然存在的具有Al2SiO5组成的铝硅酸盐矿物。水合铝硅酸盐矿物称为沸石且为具有多孔结构的天然存在的材料。
本发明的典型涂料组合物包含:
●5重量%至30重量%包含仲胺基团的成膜树脂,例如聚天冬氨酸酯胺;
●20重量%至50重量%多异氰酸酯固化剂,及
●5重量%至20重量%基于氨基树脂的聚合物的固体粒子,
●15重量%至30重量%一或多种颜料及/或体质颜料,
●10重量%至30重量%一或多种有机溶剂。
典型涂料组合物也可包含1重量%至10重量%一或多种未列于上文的其他添加剂,例如用于辅助湿润、分散、均染、流动、吸收UV(例如 292)、减少变形的添加剂及触变剂(例如膨润土触变剂)。
除非另外陈述,否则涂料组合物中各组分的重量%以包括溶剂的涂料组合物中组分的总重量计。
(vii)制造涂料组合物的方法
涂料组合物可通过通常在生产油漆的技术领域内使用的任何适合技术制备。因此,可使用高速分散器、球磨机、珠磨机、三辊研磨机、砂磨机、篮式研磨机等将各种组分混合在一起。可使用袋滤器、保护过滤器(patron filter)、线隙过滤器(wire gap filter)、楔形网过滤器(wedge wire filter)、金属边缘过滤器(metal edge filter)、EGLMturnoclean过滤器(购自Cuno)、 DELTA应力过滤器(购自Cuno)及Jenag Strainer过滤器(购自Jenag)或通过振动过滤来过滤本发明的油漆。
本发明的涂料组合物通常以两包装组合物的形式提供,一个包装中为包含仲胺基团的成膜树脂且另一个包装中为多异氰酸酯固化剂。基于氨基树脂的聚合物的固体粒子也通常在含有聚天冬氨酸酯的包装中。在涂覆涂料组合物之前,将两个包装混合在一起。
(viii)涂料组合物的应用
涂料组合物可通过包括以下的多个方法中的一或多个涂覆至基材:喷涂、辊压、帘式涂覆、浸渍/浸没、刷涂或流动涂覆,但涂料组合物最常通过喷涂及辊压涂覆。常见喷涂技术及设备为空气喷涂及静电喷涂,且可为手动或自动方法。举例而言,可使用机械喷涂方法。
涂料组合物通常在环境温度下固化。能够在环境温度下固化的涂料组合物为不需要人工加热以实现固化的涂料组合物。因此,一旦在无额外加热的情况下涂覆本发明的涂料组合物,其即能够在基材上固化以形成涂膜。本领域中通常也为已知的环境温度为0℃至30℃的范围内的温度。
涂料组合物又可在低烘烤条件下固化以加速固化(例如,高于30℃至约 35℃)。本发明的涂料组合物的优点为其(i)具有能够使用常规技术(例如,标准无空气/空气辅助设备)将其涂覆的贮存期,且(ii)其可在环境温度下快速固化。若利用环境温度固化,则对组合物而言在50%相对湿度(50%RH) 及25℃下不到3小时固化为可能的。组合物常常在50%相对湿度(50%RH) 及25℃下不到2小时固化。
风机叶片通常由复合材料制成。“复合物”一般应理解为指由两种或两种以上不同材料制造的工程材料。通常,该两种或两种以上材料具有不同(有时显著不同)的物理及/或化学特性。复合物通常具有基质材料及强化材料;基质材料包围且支撑强化材料。本发明的复合物通常包含聚合材料作为基质材料及纤维作为强化材料。纤维可包含例如玻璃纤维(即纤维玻璃)、碳纤维、芳族聚酰胺纤维、克维拉(Kevlar)纤维、由天然材料制造的纤维及由纳米粒子制造的纤维。适合聚合材料可为热塑性或热固性的且包括例如聚酯及环氧树脂。通常,纤维中的至少一种应至少部分涂覆有聚合材料或嵌入聚合材料中。特定实例包括纤维强化型复合材料,诸如强化型玻璃纤维复合物,其尤其适用于风机叶片结构。诸如塑料的纤维强化型聚合物也在如本文所使用的术语“复合物”的范畴内。本发明的复合物基材可具有一个连续表面,诸如两个相对表面的两个或两个以上表面,或任何其他构造。在一特定实施方案中,基材为呈风机叶片形式的复合物。
涂料体系可涂覆至复合物的至少一部分,例如涂覆至风机叶片的前沿。
在复合物表面上沉积任何涂料组合物之前,通常需要通过彻底清洁且必要时对该表面除油来自该表面移除外来物质。该类清洁通常在使基材成形(例如,通过模制)为最终使用形状之后进行。基材表面可通过物理或化学手段或两者来清洁,诸如机械摩擦该表面(例如喷砂清洁)或用本领域熟练技术人员所熟知的市售的碱性或酸性清洁剂,诸如偏硅酸钠及氢氧化钠来清洁/除油。
清洁步骤之后,可用去离子水或漂洗剂的水溶液漂洗基材以移除任何残留物。可例如通过使用气刀,通过使基材短暂暴露于高温以闪蒸掉水,或通过使基材在压辊之间穿过来风干基材。为了使表面准备(光滑度)达至最佳,可涂覆油灰/填料以填充表面缺陷。已知适用于航空及汽车基材初步处理或修复的领域的油灰组合物及涂料为适于使用的。油灰通常用刀片手工涂覆且经砂磨以获得可接受的光滑表面。气刀也可用于由砂磨移除残留物。
本发明的涂料组合物的一个优点为其适于用作底漆涂层及顶涂层。这意谓仅需要一层涂料组合物来涂覆风机叶片。有利的是,涂料组合物能够仅以一个涂层以约100μm至约300μm的干膜厚度涂覆。涂层数量减少使得进行风机叶片维护所需时间较少,且无本发明的风机叶片涂层与任何其他涂层的兼容性问题。
准备涂覆的涂料组合物的粘度应适合于使用标准涂覆技术进行涂覆。举例而言,根据ASTM D4287所量测,准备涂覆的涂料组合物的粘度优选为25℃下在0.1泊与10泊之间。
本发明的涂料组合物也可用于修复风机叶片的方法中。用于修复风机叶片的方法应包含将本申请的涂料组合物涂覆至风机叶片的至少一部分的步骤。涂料可实质上涂覆至风机叶片的所有部分,或仅涂覆至风机叶片的一部分,诸如风机叶片的前沿。在某些实施方案中,涂层中的一或多个可涂覆至风机叶片的至少一部分。以此方式修复的风机叶片可具有预先存在的涂料或涂层,其一些或全部可在涂覆顶涂层之前移除。或者,新增的顶涂层可在存在的涂层上方涂敷且将为“第二”顶涂层。在该实施方案中,可将连接涂层或其他促进粘着的层涂覆至存在的涂层。
(ix)其他应用
本文所公开的涂料组合物尤其适于在风机叶片上使用以保护风机叶片不受雨蚀,然而其也可用于保护风机叶片及其他基材不受固体粒子侵蚀。其他应用的实例包括采矿及建筑产业中的使用,及用作土工设备上OEM (原始设备制造商(original equipmentmanufacturer))面漆。
因此,本发明涉及本文所公开的涂料组合物的用途,其用于涂覆基材,尤其当需要保护基材不受例如水/雨蚀及固体粒子侵蚀的侵蚀时。
基材包括诸如金属、混凝土及塑料的材料,或这些已涂覆有或部分涂覆有油漆或填料的材料。油漆可为例如本发明的涂料或包含基于聚脲(例如芳族或脂族聚天冬氨酸树脂)、聚氨酯或环氧的树脂的不同涂料。有利的是,涂料组合物可直接涂覆至上述材料。
本发明也涉及涂覆有本发明的涂料组合物的这些基材。
实施例
以下实施例意欲说明本发明的各种实施方案,且不应解释为以任何方式限制本发明。
实施例1及实施例2涂料组合物通过使用高速分散器及砂磨机将表1 中的组分1至组分9混合在一起来制备。组分1至组分7首先混合在一起,随后添加预混的组分8及组分9。异氰酸酯基团:仲胺基团的化学计量比率为1.8:1。
表1-表1中的值对应于各组分的重量%的量:
NH1420(购自Bayer Material Science AG)-聚天冬氨酸酯胺;
MK,购自Deuteron-基于氨基树脂的聚合物粒子;
996,购自BYK-Chemie GmBH-微米化聚乙烯蜡/PTFE的混合物;
BYK-077,购自BYK-Chemie GmBH-甲基烷基聚硅氧烷;
BYK-066N,购自BYK-Chemie GmBH-异丁基酮聚硅氧烷;
Airex 900,购自Evonik Industries AG-经有机改性的聚硅氧烷;
BYK-307,购自BYK-Chemie GmBH-经聚酯改性的硅氧烷;
Tinuvin 292,购自BASF Resins-液体位阻胺光稳定剂;
N3800-基于HDI三聚体且NCO含量为11.0的不含溶剂的脂族多异氰酸酯。
除实施例1中基于氨基树脂的聚合物粒子在实施例2中用常规的填充材料滑石(水合硅酸镁)替换以外,用于配制实施例1及比较实施例2的全部组分为相同的。
与实施例1相同,实施例2及实施例3中异氰酸酯基团:仲胺基团的化学计量比率为1.8:1。
涂料测试
通过喷涂技术将各实施例的涂料组合物以200μm的干膜厚度涂覆至由玻璃强化型环氧复合物基材制造的翼形模具且使其在27℃下固化。随后,使测试涂料持续21天成熟作用以发展完整的薄膜特性。
根据ASTM G73-10测定各涂料的抗雨蚀性。此测试涉及将测试样本附接至旋转臂,使得测试样本在其环形路径中反复通过水喷雾且受到水喷雾冲击。其为加速测试方法,其中测试极高速度下样本对多次水滴冲击的抗性。在此加速测试中展示良好效能的涂料预期在技术领域中具有良好耐久性。
测试参数:
抗雨蚀性的评估基于因雨滴的重复多次冲击所致的对涂料的可见损害的量。每30分钟以肉眼评估涂料,持续3小时。就全部涂料而言,最初损害均在速度最大的叶片端部。在测试期间,也发现对涂料的损害逐渐向上延伸至叶片的根部。与抗雨蚀性较低的涂料相比,抗雨蚀性较高的涂料受损面积的长度较短。
雨蚀测试的结果展示于表2中。
时间(hr) | 实施例1 | 比较实施例2 |
0.5 | 5 | 16 |
1.0 | 13 | 22* |
1.5 | 16 | 22* |
2.0 | 20 | 22* |
2.5 | 22* | 22* |
3.0 | 22* | 22* |
表2-表2中的值对应于叶片上受损面积的长度/cm
*最大可能的损害长度为22cm。
比较实施例2的涂料在仅1小时之后沿叶片的整个长度受损。然而,实施例1的涂料具有优异的抗雨蚀性。实施例1的涂料花费2.5小时(2.5 倍长)才沿叶片的整个长度受损。与实施例2的比较涂料相比,实施例1的涂料具有优越的抗雨蚀性。
通过BK干燥轨道记录器(ASTM D 5895)量测DFT为200微米的涂料硬干的时间,其中改变为温度/湿度为27℃,RH-78%。涂料的硬干时间为 130分钟。作为比较,使用相同测试量测用于涂覆风机叶片的主要市售的基于聚酯的聚氨酯产物的硬干时间。发现主要市售的基于聚酯的聚氨酯产品的干燥时间为180分钟。
根据EPA联邦参考法(EPA Federal Reference Method)24测定涂料组合物1及比较涂料组合物2的挥发性有机物含量(VOC)。两种涂料组合物的VOC低于250g/L。这显著低于用于涂覆风机叶片的主要市售的基于聚酯的聚氨酯产品,其VOC测定为420g/L。
Claims (14)
1.一种涂料组合物,其包含:
a)包含仲胺基团的成膜树脂,
b)多异氰酸酯固化剂,及
c)基于氨基树脂的聚合物的固体粒子,
其中包含仲胺基团的成膜树脂为聚天冬氨酸酯胺,基于氨基树脂的聚合物为交联的聚合物,并且所述涂料组合物可在0℃至30℃下固化。
2.根据权利要求1的涂料组合物,其中(a)及(b)以使得异氰酸酯基团:仲胺基团的化学计量比率为1.0:1.0至2.5:1.0的量存在于涂料组合物中。
3.根据权利要求1或2的涂料组合物,其特征在于基于氨基树脂的聚合物为基于甲基脲的聚合物。
4.根据权利要求1或2的涂料组合物,其特征在于以整个涂料组合物的重量计,基于氨基树脂的聚合物的固体粒子以1重量%至25重量%的量存在。
5.根据权利要求1或2的涂料组合物,其中多异氰酸酯固化剂的异氰酸酯当量在280g/eq与840g/eq之间。
6.根据权利要求中5的涂料组合物,其中多异氰酸酯固化剂的异氰酸酯当量在280g/eq与500g/eq之间。
7.根据权利要求1或2的涂料组合物,其中包含仲胺基团的成膜树脂的胺当量在150g/eq与450g/eq之间。
8.根据权利要求1或2的涂料组合物,其中(a)及(b)以使得异氰酸酯基团:仲胺基团的化学计量比率为大于1.5:1.0至最高比率为2.5:1.0的量存在于涂料组合物中。
9.根据权利要求1或2的涂料组合物,其中聚天冬氨酸酯胺具有以下结构:
其中X表示在最高达100℃的温度下对异氰酸酯基团为惰性的脂环烃;
R1及R2各自独立地选自在最高达100℃的温度下对异氰酸酯基团为惰性的有机基团;
R3及R4各自独立地选自氢及在最高达100℃的温度下对异氰酸酯基团为惰性的有机基团;及
n为至少2的整数。
10.根据权利要求1或2的涂料组合物,其中涂料组合物以两个包装提供,第一包装包含聚天冬氨酸酯胺且第二包装包含多异氰酸酯固化剂。
11.一种保护基材不受雨蚀或固体粒子侵蚀的方法,其通过以下进行:
-提供根据权利要求1至10中任一项的涂料组合物,其包括包含仲胺基团的成膜树脂、多异氰酸酯固化剂及基于氨基树脂的聚合物的固体粒子,
-将涂料组合物涂覆至基材以在基材上形成一个或多个涂层,及
-使涂层于0℃至30℃的环境温度下在基材上硬化,
其中包含仲胺基团的成膜树脂为聚天冬氨酸酯胺,基于氨基树脂的聚合物为交联的聚合物。
12.根据权利要求11的方法,其中基材为风机叶片或其一部分。
13.一种经涂覆的风机叶片或其一部分,其中风机叶片或其一部分涂覆有根据权利要求1至10中任一项的涂料组合物。
14.基于氨基树脂的聚合物的固体粒子于根据权利要求1至10中任一项的涂料组合物中的用途,其用于改进由涂料组合物形成的涂料的抗雨蚀性或抗固体粒子侵蚀性,其中基于氨基树脂的聚合物为交联的聚合物。
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- 2014-10-01 JP JP2016518748A patent/JP2016539196A/ja active Pending
- 2014-10-01 CA CA2925499A patent/CA2925499A1/en not_active Abandoned
- 2014-10-01 CN CN201480054540.6A patent/CN105593259B/zh not_active Expired - Fee Related
- 2014-10-01 BR BR112016006626A patent/BR112016006626A2/pt active Search and Examination
- 2014-10-01 AU AU2014331180A patent/AU2014331180B2/en not_active Expired - Fee Related
- 2014-10-01 MX MX2016004029A patent/MX2016004029A/es unknown
- 2014-10-01 WO PCT/EP2014/070998 patent/WO2015049260A1/en active Application Filing
- 2014-10-01 KR KR1020167009896A patent/KR20160065874A/ko not_active Application Discontinuation
- 2014-10-01 SG SG11201602613VA patent/SG11201602613VA/en unknown
- 2014-10-01 EP EP14781137.6A patent/EP3074442A1/en not_active Withdrawn
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CA2925499A1 (en) | 2015-04-09 |
RU2016116267A (ru) | 2017-11-10 |
US20160244635A1 (en) | 2016-08-25 |
WO2015049260A1 (en) | 2015-04-09 |
KR20160065874A (ko) | 2016-06-09 |
AU2014331180B2 (en) | 2017-09-14 |
BR112016006626A2 (pt) | 2017-08-01 |
US10030166B2 (en) | 2018-07-24 |
RU2016116267A3 (zh) | 2018-05-29 |
SG11201602613VA (en) | 2016-04-28 |
EP3074442A1 (en) | 2016-10-05 |
AU2014331180A1 (en) | 2016-04-07 |
CN105593259A (zh) | 2016-05-18 |
TW201522538A (zh) | 2015-06-16 |
JP2016539196A (ja) | 2016-12-15 |
MX2016004029A (es) | 2016-06-02 |
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