CN111527160A - 含有镁的镀锌钢板的涂覆组合物及涂覆该组合物的钢板 - Google Patents
含有镁的镀锌钢板的涂覆组合物及涂覆该组合物的钢板 Download PDFInfo
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- CN111527160A CN111527160A CN201880084157.3A CN201880084157A CN111527160A CN 111527160 A CN111527160 A CN 111527160A CN 201880084157 A CN201880084157 A CN 201880084157A CN 111527160 A CN111527160 A CN 111527160A
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- steel sheet
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 76
- 239000010959 steel Substances 0.000 title claims abstract description 76
- 239000008199 coating composition Substances 0.000 title claims abstract description 56
- 239000011777 magnesium Substances 0.000 title claims abstract description 51
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001335 Galvanized steel Inorganic materials 0.000 title abstract description 12
- 239000008397 galvanized steel Substances 0.000 title abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 239000000178 monomer Substances 0.000 claims description 39
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 239000000839 emulsion Substances 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 238000007334 copolymerization reaction Methods 0.000 claims description 13
- 239000004908 Emulsion polymer Substances 0.000 claims description 11
- -1 carboxyethyl Chemical group 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- HMENQNSSJFLQOP-UHFFFAOYSA-N 2-bromoprop-2-enoic acid Chemical compound OC(=O)C(Br)=C HMENQNSSJFLQOP-UHFFFAOYSA-N 0.000 claims description 3
- HEBDGRTWECSNNT-UHFFFAOYSA-N 2-methylidenepentanoic acid Chemical compound CCCC(=C)C(O)=O HEBDGRTWECSNNT-UHFFFAOYSA-N 0.000 claims description 3
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 claims description 3
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 3
- PLPDHGOODMBBGN-VOTSOKGWSA-N (e)-4-oxo-4-phenylbut-2-enoic acid Chemical compound OC(=O)\C=C\C(=O)C1=CC=CC=C1 PLPDHGOODMBBGN-VOTSOKGWSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 2
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 claims description 2
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 claims description 2
- CWMPPVPFLSZGCY-VOTSOKGWSA-N (2E)-oct-2-enoic acid Chemical compound CCCCC\C=C\C(O)=O CWMPPVPFLSZGCY-VOTSOKGWSA-N 0.000 claims 1
- CWMPPVPFLSZGCY-UHFFFAOYSA-N 2-Octenoic Acid Natural products CCCCCC=CC(O)=O CWMPPVPFLSZGCY-UHFFFAOYSA-N 0.000 claims 1
- VWXZFDWVWMQRQR-UHFFFAOYSA-N 3-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=C)=C1 VWXZFDWVWMQRQR-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- RLYNGYDVXRKEOO-XQHVRGAUSA-N (e)-but-2-enoic acid Chemical compound C\C=C\C(O)=O.C\C=C\C(O)=O RLYNGYDVXRKEOO-XQHVRGAUSA-N 0.000 description 2
- ORFRDAORPHYSRD-UHFFFAOYSA-N 3-ethenylbenzoic acid Chemical compound C(=C)C=1C=C(C(=O)O)C=CC1.C(=C)C=1C=C(C(=O)O)C=CC1 ORFRDAORPHYSRD-UHFFFAOYSA-N 0.000 description 2
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VSXZUMHGZGTXOL-UHFFFAOYSA-N oct-2-enoic acid Chemical compound C(C=CCCCCC)(=O)O.C(C=CCCCCC)(=O)O VSXZUMHGZGTXOL-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 239000011347 resin Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
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- ZZCYWXPAATXVCD-UHDJGPCESA-N C(C1=CC=CC=C1)(=O)/C=C/C(=O)O.C(=O)(O)CCOC(C=C)=O Chemical compound C(C1=CC=CC=C1)(=O)/C=C/C(=O)O.C(=O)(O)CCOC(C=C)=O ZZCYWXPAATXVCD-UHDJGPCESA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical compound [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
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- 230000008520 organization Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- VKWHEBRSOGACFC-UHFFFAOYSA-N pent-2-enoic acid Chemical compound CCC=CC(O)=O.CCC=CC(O)=O VKWHEBRSOGACFC-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种涂覆组合物及涂覆该涂覆组合物的包含Mg的镀锌钢板,其能够防止包含Mg的镀锌钢板在暴露于高温高湿的环境中时发生黑变和黑斑。根据本发明,提供一种钢板涂覆组合物和具有由该涂覆组合物形成的涂覆薄膜层并且镀层中含有镁的镀覆钢板,所述钢板涂覆组合物包含:10至20重量%的羧化亚乙烯基共聚物、相对于羧化亚乙烯基共聚物的重量的1至5重量%的水分散***联剂以及余量的水。根据本发明的涂覆组合物形成涂膜的镀覆钢板可以防止发生黑变和/或黑斑。尤其,在暴露于高温高湿的环境的情况下,也表现出防止发生黑变和/或黑斑的优异的物理性质。
Description
技术领域
本发明涉及一种含有镁的镀锌钢板的涂覆组合物及利用该涂覆组合物涂覆的含有镁的镀锌钢板。更具体地,本发明涉及一种防止包含Mg的镀锌钢板在暴露于高温高湿的环境时发生黑变和黑斑的涂覆组合物及涂覆该涂覆组合物的包含Mg的镀锌钢板。
背景技术
作为用于提高镀层中含有Mg的合金镀敷钢板的耐蚀性和耐黑变性的技术,有包含烯烃树脂、有机硅烷、防黑变剂、无机金属防锈剂等的水溶性涂覆组合物的专利(韩国专利第10-1586840B1,韩国专利第10-1262497B1等),但是,在镀层组成物中占据大部分的烯烃树脂的水分和/或氧渗透性高,因此从根本上抑制黑变和黑斑的产生。另外,在所述专利中并没有提及镀层的氧和/或水分的渗透性。
另外,作为防止由Mg金属板材的湿气引起的黑变的技术,有利用大气等离子体涂覆包含硅氧烷前体的组合物以形成无机涂层,并且在所述无机涂层上部涂覆包含聚亚乙烯基类高分子的组合物以形成有机涂层的技术(韩国专利第10-1758474)。但是,所述涂层仅由未交联的聚亚乙烯基类高分子构成,因此相比由交联的聚亚乙烯基类高分子构成的涂层,其水分和氧的渗透性高,从而会发生黑变和黑斑,并且为了将聚亚乙烯基类高分子制造成具有流动性的涂覆溶液,不得不使用有机溶剂。
提及包含羧基的聚亚乙烯树脂的的专利有美国专利US6037124A(Carboxylatedpolyvinylidene fluoride solid supports for the immobilization of biomoleculesand methods of use thereof)、美国专利公开US2013-0231428A1(FAST FILM FORMATIONWATER BASED BARRIER COATING,快速成膜水性障碍涂料)等,但是并没有关于包含Mg的镀覆钢板的防黑变的应用和交联的专利。
另外,在现有技术中,在有机溶剂中溶解聚亚乙烯基类高分子并涂覆在包含Mg的钢板,以防止水分和氧的渗透,但是由于使用有机溶剂而产生环境污染问题,并且由于聚亚乙烯基类高分子之间没有交联而耐化学性不足且在降低水分和氧的渗透率的方面存在局限性。另外,为了通过乳液(共)聚合合成聚亚乙烯基高分子(共聚物)而使用乳化剂,但是当将如上所述合成的聚亚乙烯基高分子(共聚物)分散材料涂覆在镀覆钢板上并形成薄膜时,由于包含低分子量的盐的乳化剂,容易受潮,并且在长时间暴露于高温高湿环境中时,会引起黄变现象(ref.Emulsion Polymerization and Emulsion Polymers,by PeterA.Lovell(Editor),Mohamed S.El-Aasser(Editor),March 1997)。
现有技术文献
专利文献
(专利文献1)韩国专利第10-1586840
(专利文献2)韩国专利第10-1262497
(专利文献3)韩国专利第10-1758474
(专利文献4)美国专利第6037124A
(专利文献5)美国专利公开第2013-0231428A1
非专利文献
(非专利文献1)Emulsion Polymerization and Emulsion Polymers,by PeterA.Lovell(Editor),Mohamed S.El-Aasser(Editor),March 1997
发明内容
(一)要解决的技术问题
本发明为了解决如上所述的问题而提供一种含有镁的镀覆钢板的涂覆组合物及涂覆该涂覆组合物的含有镁的镀覆钢板。另外,本发明提供一种用于抑制镀层中包含Mg的镀覆钢板发生黑变和黑斑的含有镁的镀锌钢板的涂覆组合物及涂覆该涂覆组合物的含有镁的镀锌钢板。
(二)技术方案
根据本发明的一个方面,提供一种钢板涂覆组合物,其包含:10至20重量%的羧化亚乙烯基共聚物、相对于羧化亚乙烯基共聚物的重量的1至5重量%的水分散***联剂以及余量的水。
所述羧化亚乙烯基共聚物可以以亚乙烯基类单体和包含羧基的单体为主要成分并且通过无皂乳液共聚合制造。
所述亚乙烯基类单体可以是选自由偏二氟乙烯(vinylidene fluoride)、偏二氯乙烯(vinylidene chloride)、偏二氟乙烯-六氟丙烯共聚物(vinylidene fluoride-co-hexafluoropropylene)、偏二氯乙烯-丙烯腈共聚物(vinylidene chloride-co-acrylonitrile)、偏二氯乙烯-丙烯腈-甲基丙烯酸甲酯共聚物(vinylidene chloride-co-acrylonitrile-co-methyl methacrylate)、偏二氯乙烯-氯乙烯共聚物(vinylidenechloride-co-vinyl chloride)以及偏二氯乙烯-丙烯酸甲酯共聚物(vinylidenechloride-co-methyl acrylate)组成的组中的至少一种。
所述包含羟基的单体可以是选自由丙烯酸(acrylic acid)、甲基丙烯酸(methacrylic acid)、巴豆酸(Crotonic acid)、2-乙基丙烯酸、2-戊烯酸(2-Pentenicacid)、4-戊烯酸、2-丙基丙烯酸、2-辛烯酸(2-Octenoic acid)、3-乙烯基苯甲酸(3-Vinylbenzoic acid)、4-乙烯基苯甲酸、2-丙烯酸羧乙酯反式-3-苯甲酰丙烯酸、2-溴丙烯酸以及2-溴甲基丙烯酸组成的组中的至少一种。
以所述亚乙烯基类单体和所述包含羟基的单体为主要成分进行的无皂乳液共聚合中,对乳化聚合物进行无皂乳液共聚合,以乳化聚合物的整体重量为基准,所述乳化聚合物可以包含:10~15重量%的所述亚乙烯基类单体、相对于所述亚乙烯基类单体的0.5~1.5重量%的所述包含羟基的单体以及余量的水。
所述水分散***联剂可以是选自由氮丙啶(aziridine)、异氰酸酯(isocyanate)化合物以及碳二亚胺(carbodiimide)化合物组成的组中的至少一种。
另外,根据本发明的另一方面,提供一种镀覆钢板,其具有由本发明的钢板涂覆组合物形成的涂覆薄膜层并且镀层中含有镁。
所述钢板涂覆组合物可以被应用于含有镁的镀覆钢板上并且使干燥薄膜附着量成为500~800mg/m2,从而形成涂覆薄膜层。
(三)有益效果
根据本发明的涂覆组合物在涂覆于镀覆钢板的表面后进行干燥的过程中进行交联并形成三维的致密的分子结构。因此,相比由没有交联的聚亚乙烯基类高分子形成的涂覆剂,可以进一步降低水分和/或氧的渗透性,从而在长时间暴露于高温高湿的环境中时能够防止发生黑变和/或黑斑。另外,在涂覆组合物中没有使用有机溶剂,因此环保。因此,由根据所述本发明的涂覆组合物形成涂膜的镀覆钢板可以防止发生黑变/或黑斑。尤其,即使在暴露于高温高湿的环境中时也显示出防止发生黑变和/或黑斑的优异的物理性质。
附图说明
图1是涂覆本发明的涂覆组合物和现有材料后在50℃、95%的相对湿度下放置120小时之后评价钢板的黑变的照片。(a)表示比较列,(b)表示发明例。
最佳实施方式
下面,对本发明的优选实施方式进行说明。但是,本发明的实施方式可以变更为其他各种方式,本发明的范围不会限定于以下说明的实施方式。
根据本发明的一个方面,提供一种钢板涂覆组合物,其包含:10至20重量%的羧化亚乙烯基共聚物、相对于羧化亚乙烯基共聚物的重量的1至5重量%的水分散***联剂以及余量的水。
本发明的所述钢板涂覆组合物包含水分和/或氧渗透性低的水分散类聚亚乙烯基类高分子(分子结构内包含羟基),即羧化亚乙烯基共聚物和可与羟基反应的水分散***联剂(固化剂),并且不包含乳化剂、分散剂等。
因此,形成在钢板上的涂膜没有洞(hole)等缺陷,并且通过充分的交联使水分和/或氧的渗透性最小化。因此,当含有Mg的镀覆钢板暴露于高温高湿环境中时,使黑变和黑斑的发生最小化。
用于本发明的所述钢板涂覆组合物的羧化亚乙烯基共聚物具有水分散性。这是为了在本发明的钢板涂覆组合物中不使用有机溶剂,以使钢板涂覆组合物环保。另外,所述羧化亚乙烯基共聚物可以是以亚乙烯基类单体和包含羧基的单体为主要成分并通过无皂乳液共聚合(surfactant-free emulsion copolymerization)反应制造的。其目的在于,在使用本发明的涂覆组合物在钢板上形成涂膜的情况下,防止发生由残余的乳化剂等引起的缺陷。
所述亚乙烯基类单体并不限定于此,例如,可以是选自由偏二氟乙烯(vinylidenefluoride)、偏二氯乙烯(vinylidene chloride)、偏二氟乙烯-六氟丙烯共聚物(vinylidene fluoride-co-hexafluoropropylene)、偏二氯乙烯-丙烯腈共聚物(vinylidene chloride-co-acrylonitrile)、偏二氯乙烯-丙烯腈-甲基丙烯酸甲酯共聚物(vinylidene chloride-co-acrylonitrile-co-methyl methacrylate)、偏二氯乙烯-氯乙烯共聚物(vinylidene chloride-co-vinyl chloride)以及偏二氯乙烯-丙烯酸甲酯共聚物(vinylidene chloride-co-methyl acrylate)组成的组中的一种以上。并且根据需要可以单独使用或将两种以上一起使用。由所述亚乙烯基类单体合成的高分子薄膜具有氧和水分的渗透性低的性质。
在所述亚乙烯基类单体和包含羟基的单体的无皂乳液共聚合时,优选包含乳化聚合物整体重量的10~15重量%的所述亚乙烯基类单体。当所述亚乙烯基类单体的含量小于10重量%时,由于涂覆组合物中包含的高分子物质的含量低,需要涂覆包含大量的水的材料以获得所需要的薄膜厚度,因此,在干燥涂膜时由于沸腾现象会在涂膜中形成洞(hole),从而无法防止位于薄膜下部的镀层的黑变现象。另外,根据高分子薄膜的氧和/或水分阻断性可能不充分,和/或,由于包含羟基的单体的含量相对增加,在形成共聚物的过程中水上形成大量的高分子电解质,由此水分散稳定性可能会变差。当亚乙烯基类单体的含量超过15重量%时,由于不包含用于乳化聚合的乳化剂,羧化亚乙烯基共聚物的水分散稳定性降低,由此容易凝胶(gel)化。
所述包含羟基的单体并不限定于此,可以是选自由丙烯酸(acrylic acid)、甲基丙烯酸(methacrylic acid)、巴豆酸(Crotonic acid)、2-乙基丙烯酸、2-戊烯酸(2-Pentenic acid)、4-戊烯酸、2-丙基丙烯酸、2-辛烯酸(2-Octenoic acid)、3-乙烯基苯甲酸(3-Vinylbenzoic acid)、4-乙烯基苯甲酸、2-丙烯酸羧乙酯反式-3-苯甲酰丙烯酸、2-溴丙烯酸以及2-溴甲基丙烯酸组成的组中的至少一种。并且根据需要可以单独使用或将两种以上一起使用。
包含羟基的单体和亚乙烯基类单体通过乳化共聚合起到提高羟化亚乙烯基共聚物的水分散稳定性以及在干燥和固化过程中与交联剂反应而形成网状结构的致密的薄膜的效果。
在所述亚乙烯基类单体和所述包含羟基的单体的无皂乳液共聚合时,优选包含相对于亚乙烯基类单体的0.5~1.5重量%的包含羟基的单体。当包含羟基的单体的含量小于0.5重量%时,羟化亚乙烯基共聚物的水分散稳定性降低,并且由于可与交联剂反应的部位(site)少,难以形成致密的网状结构的涂膜。当包含羟基的单体的含量超过1.5重量%时,在形成羟化亚乙烯基共聚物的过程中在水上形成大量的高分子电解质,从而水分散稳定性变差。
在所述乳化聚合物中,除所述亚乙烯基类单体和所述包含羟基的单体以外其余为水。水可以是在制造共聚物时通常使用的水,但并不限定于此,可以使用蒸馏水、自来水、脱离子水、超纯净水等。另外,乳化聚合物可以根据需要包含在无皂乳液共聚合反应中通常使用的诸如聚合引发剂等其他添加剂。这些其他添加剂是在本技术领域中通常使用的,因此在本说明书中不作详细说明。
通过无皂乳液共聚合反应的羟化亚乙烯基共聚物的制造方法在本技术领域中是众所周知的,可以通过公知的任何无皂乳液共聚合方法来进行。因此,在本说明书中不会对无皂乳液共聚合法的条件,例如,包含温度和时间条件的条件和用于其的其他添加剂等进行另外的说明,另外,本发明并不限定于此。本发明的涂覆组合物可以使用通过现有的任何方法制造的羟化亚乙烯基共聚物。
在本发明的钢板涂覆组合物中包含有10至20重量%的所述羟化亚乙烯基共聚物。当包含在钢板涂覆组合物中的羟化亚乙烯基共聚物的含量小于10重量%时,由于涂覆组合物中包含的高分子物质的含量低,所期望的薄膜的厚度变薄,并且需要涂覆包含大量的水的材料,因此,在干燥涂膜时因沸腾现象在涂膜形成洞,从而无法防止位于薄膜下部的镀层的黑变现象。当羟化亚乙烯基共聚物的含量超过20重量%时,水分散稳定性降低,从而容易凝胶(gel)化。
本发明的钢板涂覆组合物还包含水分散***联剂(固化剂)。可用于本发明的钢板涂覆组合物中的水分散***联剂并不限定于此,例如,可以使用选自由氮丙啶(aziridine)、异氰酸酯(isocyanate)化合物以及碳二亚胺(carbodiimide)化合物组成的组中的至少一种。但并不限定于此,作为氮丙啶可以具体使用CROSSLINKER CX100(DSMChemical公司),作为异氰酸酯化合物可以具体使用拜海都(Bayhydur)(covestrochemical公司),作为碳二亚胺化合物可以使用STAHL EVO permutex(Stahl公司)。
包含相对于羟化亚乙烯基共聚物(以羟化亚乙烯基共聚物的重量为基准)的1重量%至5重量%的所述水分散***联剂,优选为1重量%至3重量%的所述水分散***联剂。在包含Mg的镀覆钢板上涂覆涂覆材料并进行干燥和固化的过程中,所述水分散***联剂与位于羟化亚乙烯基共聚物表面的羟基反应并形成致密的三维结构的薄膜,从而起到阻断水分和氧的作用。当所述水分散***联剂的含量小于1重量%时,无法满足固化反应中所需的交联剂的量,由此交联不充分,当所述水分散***联剂的含量超过5重量%时,除交联所需的量以外的未参与交联的成分在薄膜中以杂质形式存在,由此产生缺陷,阻断水分的效果降低。
在本发明的钢板涂覆组合物中,除所述羟化亚乙烯基共聚物和水分散***联剂以外的部分为水。所述水并不限定于此,例如,可以是自来水、纯净水、超纯净水、蒸馏水、脱离子水等。
本发明的钢板涂覆组合物必须包含所述羟化亚乙烯基共聚物、水分散***联剂以及水,或者可以由其构成。本发明的钢板涂覆组合物可以根据需要包含在本技术领域中通常配入钢板表面处理组合物中的诸如附着强化剂、防锈剂、润滑剂等添加剂。
本发明的钢板涂覆组合物通过混合所述羟化亚乙烯基共聚物、水分散***联剂以及水而制造,对制造方法不作特别限制。
将本发明的所述钢板涂覆组合物涂覆在具有含有Mg的镀层的镀覆钢板,然后进行干燥以在镀覆钢板表面形成镀层,从而钢板的水分和/或氧的渗透性降低,并且防止发生黑变和/或黑斑。
为了提高钢板的耐蚀性,一般在镀层中含有Mg。通常,使用包含0.5重量%至5重量%的Mg的镀层,以提高钢板的耐蚀性。但是,在含有Mg的镀层中,Mg以氧化物的形式集中在镀层最上层(与空气直接接触的面),容易与大气中的氧和/或水分接触,则因不完全的氧化腐蚀反应而发生黑变和/或黑斑。因此,当利用水分和/或氧的渗透性小的涂层阻断(blocking)镀层以使氧和/或水分无法通过涂层时,防止位于镀层最上层的Mg氧化物的腐蚀,从而可以抑制发生黑变/黑斑现象。因此,如上所述,在本发明中,在含有Mg的镀层中应用本发明的所述钢板涂覆组合物来形成涂层,以防止含有Mg的镀层发生黑变和/黑斑。
如上所述,本发明防止因镀层中含有的Mg而发生黑变和/或黑斑,可以应用于镀层中含有所述Mg的任何镀覆钢板中。如上所述,为了提高钢板的耐蚀性,通常镀层中含有0.5重量至5重量%的Mg,优选为1.5重量%至3重量%左右的Mg。当镀层中的Mg的含量超过5重量%时,因镀浴表面的氧化而无法制造镀浴,当Mg的含量小于0.5重量%时,耐蚀性的改善效果小。
因此,本发明可以应用于具有包含0.5重量%至5重量%的Mg,优选为1.5重量%至3重量%的Mg的镀层的镀覆钢板。其中,镀层的其余部分可以是现有的本技术领域中公知的任何组成,例如,镀层的其余部分可以是Zn、Al,但并不限定于此。
具体地,镀层中含有所述Mg的镀覆钢板可以是镀锌钢板,更具体地,可以是由Mg/Al/Zn构成镀层的三维镀锌钢板。更具体地,所述镀层可以包含0.5重量%至5重量%的Mg,优选地,可以包含1.5重量%至3重量%的Mg、1.5重量%至11重量%的Al以及余量的Zn。
可以通过本技术领域中公知的任何涂覆方法将本发明的所述钢板涂覆组合物应用于在镀层中含有Mg的镀覆钢板,并不限定涂覆方法。例如,可以应用浸涂、棒涂、辊涂、喷涂等任何涂覆方法。
将薄膜的附着量设定为干燥薄膜附着量为500~800mg/m2。当干燥薄膜附着量小于500mg/m2时,由于水分和氧的阻断效果不充分,容易发生黑变,因此不优选,当干燥薄膜附着量超过800mg/m2时,在造管等加工时树脂脱落或焊接性降低,因此不优选。
本发明的钢板涂覆组合物可以应用于在镀层中含有Mg的镀覆钢板的一面或两面。
将本发明的所述钢板涂覆组合物涂覆于在镀层中含有Mg的镀覆钢板后进行干燥。并且可以通过在本技术领域中公知的任何干燥方法和/或条件来进行干燥,不作特别限制。例如,可以在100℃至200℃的温度下干燥5秒至30秒左右,以在镀覆钢板上形成涂层。通过在所述温度和时间范围内进行干燥,使钢板涂覆组合物进行交联和干燥,从而形成三维的致密的分子结构。
在所述涂覆和干燥过程中,在根据本发明的分子结构内包含羟基的水分散类的羟化聚亚乙烯基类共聚物和可与羟基反应的水分散***联剂(固化剂)交联而形成三维的致密的分子结构。因此,水分和/或氧的渗透性降低,并且在长时间暴露于高温高湿环境中时也防止发生黑变和/或黑斑。不仅如此,由于在涂覆材料中没有使用有机溶剂,因此是环保的。
具体实施方式
下面,通过实施例对本发明进行更详细的说明。但是,以下的实施例仅仅用于更详细地说明本发明,而并不限定本发明的权利范围。这是因为本发明的权利范围由权利要求书中记载的内容和由此合理推出的内容而确定。
(实施例)
1.制造羟化聚亚乙烯基类乳液共聚物
在100g的蒸馏水中投入12g的亚乙烯基(vinlylidiene)和0.1g的丙烯酸并升温至约30℃,然后在用搅拌机以200rpm的速度搅拌的同时,投入0.02g的过氧硫酸氢钾(potassium peroxysulfate)、0.01g的亚硫酸氢钠(sodium bisulfite)并进行约5小时的乳化聚合反应,以制造转换率为99.5%以上的羟化聚亚乙烯基类乳液共聚物分散液。其中,制造的高分子粒子的大小为0.1~0.5μm。
2.制造用于防止含有Mg的镀覆钢板黑变的涂覆材料
在常温下,在分散液中混合0.1g的氮丙啶交联剂(商品名为CX-100,DSM公司)以制造涂覆材料,所述分散液是通过在85g的蒸馏水中分散10g的所述第1项中制造的羟化聚亚乙烯基类乳液共聚物而获得。
3.防黑变交联薄膜形成步骤
通过棒涂将在所述第2项中制造的涂覆材料涂覆于在镀层中包含Al-Mg-Zn的三维镀覆钢板(镀层组成:3.0重量%的Mg、1.5重量%的Al、余量的Zn)上,然后通过热风干燥。热风条件为在200℃的温度中进行10秒。将干燥薄膜的附着量调节为500~800mg/m2。
在干燥过程中,如以下反应式1所示,将涂覆组合物中的羟化聚亚乙烯基类共聚物和交联剂进行交联,以形成三维的致密的分子结构的涂层。
(R:烷基)
4.评价防黑变性能
对镀覆钢板的防黑变性能进行评价。
针对评价,将形成所述第3项的涂层的镀覆钢板(发明例)和未进行涂覆处理的包含Al-Mg-Zn的三维类镀覆钢板(所述第3项的钢板,比较列)分别装入气氛温度为50℃、95%的恒温恒湿器中并经过120小时后(放置在高温高湿条件中),通过肉眼和色差仪评价是否发生黑变。另外,将放置于高温高湿条件后的比较列(a)和发明例(b)的表面照片示出在图1中。色差仪以δ(delta)E为基准在发明例中显示1.5单位,在比较列中显示10单位。
如图1所示,由根据本发明的涂覆组合物形成涂层的发明例(b)的镀覆钢板没有产生红锈,并且表面没有颜色的变化,从而在外观上也表现出良好的结果。
Claims (8)
1.一种钢板涂覆组合物,包含:10至20重量%的羧化亚乙烯基共聚物、相对于羧化亚乙烯基共聚物的重量的1至5重量%的水分散***联剂以及余量的水。
2.根据权利要求1所述的钢板涂覆组合物,其中,
所述羧化亚乙烯基共聚物以亚乙烯基类单体和包含羧基的单体为主要成分,并且通过无皂乳液共聚合制造。
3.根据权利要求2所述的钢板涂覆组合物,其中,
所述亚乙烯基类单体为选自由偏二氟乙烯、偏二氯乙烯、偏二氟乙烯-六氟丙烯共聚物、偏二氯乙烯-丙烯腈共聚物、偏二氯乙烯-丙烯腈-甲基丙烯酸甲酯共聚物、偏二氯乙烯-氯乙烯共聚物以及偏二氯乙烯-丙烯酸甲酯共聚物组成的组中的至少一种。
4.根据权利要求2所述的钢板涂覆组合物,其中,
所述包含羟基的单体为选自由丙烯酸、甲基丙烯酸、巴豆酸、2-乙基丙烯酸、2-戊烯酸、4-戊烯酸、2-丙基丙烯酸、2-辛烯酸、3-乙烯基苯甲酸、4-乙烯基苯甲酸、2-丙烯酸羧乙酯反式-3-苯甲酰丙烯酸、2-溴丙烯酸以及2-溴甲基丙烯酸组成的组中的至少一种。
5.根据权利要求2所述的钢板涂覆组合物,其中,
在以所述亚乙烯基类单体和所述包含羟基的单体为主要成分进行的无皂乳液共聚合中,对乳化聚合物进行无皂乳液共聚合,以乳化聚合物的整体重量为基准,所述乳化聚合物包含:10~15重量%的所述亚乙烯基类单体、相对于所述亚乙烯基类单体的0.5~1.5重量%的所述包含羟基的单体以及余量的水。
6.根据权利要求1所述的钢板涂覆组合物,其中,
所述水分散***联剂为选自由氮丙啶、异氰酸酯化合物以及碳二亚胺化合物组成的组中的至少一种。
7.一种镀覆钢板,其具有由权利要求1至6中任一项所述的钢板涂覆组合物形成的涂覆薄膜层,并且所述镀覆钢板的镀层中含有镁。
8.根据权利要求7所述的镀覆钢板,其含有镁,
所述钢板涂覆组合物被应用于含有镁的镀覆钢板上并且使干燥薄膜附着量成为500~800mg/m2,从而形成涂覆薄膜层。
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