CN116472362A - 有机树脂被覆用表面处理钢板及其制造方法和有机树脂被覆钢板及其制造方法 - Google Patents
有机树脂被覆用表面处理钢板及其制造方法和有机树脂被覆钢板及其制造方法 Download PDFInfo
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- CN116472362A CN116472362A CN202180067736.9A CN202180067736A CN116472362A CN 116472362 A CN116472362 A CN 116472362A CN 202180067736 A CN202180067736 A CN 202180067736A CN 116472362 A CN116472362 A CN 116472362A
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
本发明提供一种有机树脂被覆用表面处理钢板的制造方法,其特征在于,将以特定的比例含有具有特定的双酚骨架的树脂化合物、阳离子性聚氨酯树脂乳液、具有特定的反应性官能团的硅烷偶联剂、有机钛螯合化合物、4价的钒化合物、钼酸化合物、氟化合物以及水且pH为4~5的表面处理液涂布于锌系镀覆钢板的表面,使其干燥,形成每单面的附着量为0.005~0.18g/m2的表面处理被膜。
Description
技术领域
本发明涉及一种有机树脂被覆用表面处理钢板及其制造方法和有机树脂被覆钢板及其制造方法。
背景技术
锌系镀覆钢板在汽车、家电、建材等领域中广泛利用。以往,出于提高耐腐蚀性的目的,广泛使用对锌系镀覆钢板的表面利用以铬酸、重铬酸或者其盐类为主要成分的处理液实施了铬酸盐处理的表面处理钢板。然而,从最近的地球环境问题考虑,向采用实施了无铬酸盐的表面处理的锌系镀覆钢板(以下,也称为“无铬酸盐的处理钢板”)的要求变高,各种无铬酸盐的处理钢板正在开发和实用化。
考虑无铬酸盐处理钢板在汽车、家电、建材等各种用途中使用,则除了耐腐蚀性之外,还要求耐黑变性、表面处理液的储存稳定性优异。
专利文献1中记载了一种表面处理钢板的制造方法,其特征在于,将以特定的比例含有具有特定的双酚骨架的树脂化合物、阳离子性聚氨酯树脂乳液、具有特定的反应性官能团的硅烷偶联剂、有机钛螯合化合物、4价的钒化合物、钼酸化合物、氟化合物和水、且pH为4~5的表面处理液涂布在锌系镀覆钢板的表面并干燥,形成每单面的附着量为0.2~1.8g/m2的表面处理被膜。
现有技术文献
专利文献
专利文献1:日本特开2012-67369号公报
发明内容
专利文献1记载的表面处理钢板的制造方法能够制造出耐腐蚀性和耐黑变性优异的表面处理钢板,从表面处理液的储存稳定性也优异的方面是优选的。然而,专利文献1中,对于(i)在表面处理钢板上形成厚度60μm以上的有机树脂被膜或者伸长率小的有机树脂被膜时的耐腐蚀性,(ii)在表面处理钢板上形成上述有机树脂被膜,然后实施严格的加工时的有机树脂被膜与表面处理被膜的密合性和表面处理被膜与镀层的密合性没有研究。在表面处理钢板上形成有机树脂被膜的主要目的是赋予外观设计性和耐久性对确保膜厚很有效。适当的膜厚也取决于有机树脂被膜的种类、所使用的环境,但大多为60μm以上。本发明人等进行了研究,发现在专利文献1记载的表面处理钢板的制造方法中,关于上述(i)和(ii)还有改善的余地。
因此,本发明鉴于上述课题,目的在于提供一种有机树脂被覆用表面处理钢板的制造方法,能够制造表面处理被膜不包含铬化合物,不仅耐黑变性优异,而且(i)在表面处理钢板上形成厚度60μm以上的有机树脂被膜或者伸长率小的有机树脂被膜时的耐腐蚀性,(ii)在表面处理钢板上形成上述有机树脂被膜,然后实施严格的加工时的有机树脂被膜与表面处理被膜的密合性和表面处理被膜与镀层的密合性也优异的表面处理钢板,并且表面处理液的储存稳定性也优异。
本发明人等反复进行了深入的研究,其结果发现通过以下的(A)和(B)的组合能够改善上述(i)和(ii)的特性,能够解决上述课题,(A)使用以特定的比例具有特定的双酚骨架的树脂化合物、阳离子性聚氨酯树脂乳液、具有特定的反应性官能团的硅烷偶联剂、有机钛螯合化合物、4价的钒化合物、钼酸化合物、氟化合物以及水、且pH为4~5的表面处理液,此时在上述特定的比例中,特别是有意地将氟化合物的含量设定得较高;以及(B)将该表面处理液涂布于锌系镀覆钢板的表面并使其干燥,形成表面处理被膜,此时将每单面的附着量设定为0.005~0.18g/m2的少量。
本发明是基于这样的情况而完成的,其主旨构成如下。
[1]一种有机树脂被覆用表面处理钢板的制造方法,其特征在于,将以满足下述(1)~(6)的条件的范围含有以下(A)~(H)且pH为4~5的表面处理液涂布于锌系镀覆钢板的表面,进行干燥,形成每单面的附着量为0.005~0.18g/m2的表面处理被膜,
具有由下述的通式(I)表示的双酚骨架的树脂化合物(A);
具有选白伯氨基~叔氨基和季铵盐基团中的至少一种阳离子性官能团的阳离子性聚氨酯树脂乳液(B);
具有选白含活性氢的氨基、环氧基、巯基和甲基丙烯酰氧基中的至少一种反应性官能团的硅烷偶联剂(C);
有机钛螯合化合物(D);
4价的钒化合物(E);
钼酸化合物(F);
氟化合物(G);以及
水(H);
(1)上述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)相对于上述树脂化合物(A)的固体成分质量(AS)、上述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及上述硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(BS)/{(AS)+(BS)+(CS)}]为0.10~0.30
(2)上述硅烷偶联剂(C)的固体成分质量(CS)相对于上述树脂化合物(A)的固体成分质量(AS)、上述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及上述硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(CS)/{(AS)+(BS)+(CS)}]为0.60~0.85
(3)上述硅烷偶联剂(C)的固体成分质量(CS)相对于上述有机钛螯合化合物(D)的钛换算质量(DTi)的比{(CS)/(DTi)}为50~70
(4)上述4价的钒化合物(E)的钒换算质量(EV)相对于上述有机钛螯合化合物(D)的钛换算质量(DTi)的比{(EV)/(DTi)}为0.30~0.50
(5)上述钼酸化合物(F)的钼换算质量(FMo)相对于上述树脂化合物(A)的固体成分质量(AS)、上述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及上述硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(FMo)/{(AS)+(BS)+(CS)}]为0.003~0.030
(6)上述氟化合物(G)的氟换算质量(GF)相对于上述树脂化合物(A)的固体成分质量(AS)、上述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及上述硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(GF)/{(AS)+(BS)+(CS)}]为0.101~0.200
式(I)中,与苯环键合的Y1和Y2分别相互独立地为氢原子或者由以下的通式(II)或者(III)表示的Z基团,每1个苯环的Z基团的取代数的平均值为0.2~1.0,n表示2~50的整数,
式(II)和(III)中,R1、R2、R3、R4和R5分别相互独立地表示氢原子、碳原子数1~10的烷基、或者碳原子数1~10的羟基烷基,A-表示氢氧根离子或者酸根离子。
[2]根据上述[1]所述的有机树脂被覆用表面处理钢板的制造方法,其中,在最高到达板温为50~180℃的条件下进行上述表面处理液的干燥。
[3]一种有机树脂被覆用表面处理钢板,是由上述[1]或[2]所述的有机树脂被覆用表面处理钢板的制造方法制造的。
[4]一种有机树脂被覆钢板的制造方法,具有:
上述[1]或[2]所述的有机树脂被覆用表面处理钢板的制造方法;以及
在上述有机树脂被覆用表面处理钢板的上述表面处理被膜上形成机树脂被膜的工序。
[5]根据上述[4]所述的有机树脂被覆钢板的制造方法,其中,上述有机树脂被膜通过在上述表面处理被膜上层压有机树脂膜而形成。
[6]根据上述[5]所述的有机树脂被覆钢板的制造方法,其中,上述有机树脂膜具有60μm以上的厚度。
[7]根据上述[5]或[6]所述的有机树脂被覆钢板的制造方法,其中,上述有机树脂膜是选白聚氯乙烯膜、聚烯烃系膜、聚酯系膜以及氟树脂系膜中的1种以上的膜。
[8]一种有机树脂被覆钢板,是由上述[4]~[7]中任一项所述的有机树脂被覆钢板的制造方法制造的。
本发明的有机树脂被覆用表面处理钢板的制造方法能够制造在表面处理被膜不包含铬化合物,不仅耐黑变性优异,而且(i)在表面处理钢板上形成厚度60μm以上的有机树脂被膜或者伸长率小的有机树脂被膜时的耐腐蚀性、(ii)在表面处理钢板上形成上述有机树脂被膜,然后实施严格加工时的有机树脂被膜与表面处理被膜的密合性和表面处理被膜与镀层的密合性也优异的表面处理钢板,并且表面处理液的储存稳定性也优异。
具体实施方式
[锌系镀覆钢板]
本发明中使用的锌系镀覆钢板可以使用以冷轧钢板作为基础的电镀Zn钢板、热浸镀Zn钢板、镀Zn-Al钢板、镀Zn-Al-Mg钢板、镀Zn-Mg钢板、镀Zn-Fe钢板、镀Zn-Ni钢板等。镀覆方法可以为电镀、热浸镀中的任一种。另外,上述的锌系镀覆钢板出于提高锌系镀覆钢板的耐黑变性的目的,镀覆可以使用微量添加Ni、Co或者包含Ni、Co、Fe的酸性或碱性的水溶液,使这些金属在锌系镀覆钢板表面析出。从耐腐蚀性确保的观点考虑,上述的锌系镀覆钢板的镀覆附着量优选为每单面5g/m2以上。
[表面处理液]
本发明中使用的表面处理液含有具有特定的双酚骨架的树脂化合物(A)、阳离子性聚氨酯树脂乳液(B)、具有特定的反应性官能团的硅烷偶联剂(C)、有机钛螯合化合物(D)、4价的钒化合物(E)、钼酸化合物(F)、氟化合物(G)以及水。
<树脂化合物(A)>
表面处理液中包含的树脂化合物(A)具有由下述的通式(I)表示的双酚骨架。
式(I)中,与苯环键合的Y1和Y2分别相互独立地为氢原子或者由以下的通式(II)或者(III)表示的Z基团,每1个苯环的Z基团的取代数的平均值为0.2~1.0,n表示2~50的整数。
这里,Z基团的取代数的平均值是指全部Z基团导入数除以全部苯环数(即2n)而得的数值。在本发明中,作为Y1和Y2中的至少一方选择Z基团的情况下,树脂化合物(A)具有选自仲氨基、叔氨基和季铵盐基团中的至少一种阳离子性官能团,因此能够相对于表面处理液更稳定地溶解。Z基团的取代数的平均值小于0.2时,表面处理液的稳定性降低,超过1.0时,上述(i)所示的耐腐蚀性和上述(ii)所示的密合性(特别是沸水试验后的密合性)劣化。另外,本发明中,将平均聚合度n设为2~50。n小于2时,上述(i)所示的耐腐蚀性变得不充分。另一方面,如果n超过50,则由于水溶性的降低、增粘等使表面处理液中的树脂化合物(A)的稳定性降低,储存稳定性变得不充分。优选地n为2~10。
式(II)和(III)中,R1、R2、R3、R4以及R5分别相互独立地为氢原子、碳原子数1~10的烷基或者碳原子数1~10的羟基烷基。如果烷基或者羟基烷基的碳原子数超过10,则无法使树脂化合物(A)充分地水溶化,在表面处理液中变得不稳定。作为R1、R2、R3、R4和R5的具体例,可以举出甲基、乙基、丙基、丁基、羟基乙基、2-羟基丙基、羟基异丁基等。A-表示氢氧根离子或者酸根离子。作为酸根离子的具体例,可举出乙酸根离子、磷酸根离子、甲酸根离子等。
由通式(I)表示的树脂化合物(A)是双酚-福尔马林缩合物,该合成方法没有限定,例如可以通过在碱催化剂存在下使福尔马林和胺与双酚A作用而得到。
<阳离子性聚氨酯树脂乳液(B)>
表面处理液中包含的阳离子性聚氨酯树脂乳液(B)只要具有选自伯氨基、仲氨基、叔氨基以及季铵盐基团中的至少一种阳离子性官能团,作为构成的单体成分的多元醇、异氰酸酯成分以及聚合方法就不特别限定。作为阳离子性官能团,例如可举出氨基、甲基氨基、乙基氨基、二甲基氨基、二乙基氨基、三甲基氨基、三乙基氨基等,只要为伯氨基、仲氨基、叔氨基或者季铵盐基团,就没有特别限定。
<硅烷偶联剂(C)>
表面处理液中包含的硅烷偶联剂(C)只要具有选自含活性氢的氨基、环氧基、巯基以及甲基丙烯酰氧基中的至少一种反应性官能团就没有特别限定。特别优选为具有三个烷氧基的三烷氧基硅烷。如果举出具体例,则可以使用N-(2-氨基乙基)3-氨基丙基三甲氧基硅烷、3一氨基丙基三甲氧基硅烷、3-缩水甘油氧基丙基三甲氧基硅烷、3-缩水甘油氧基丙基甲基二甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、2-(3,4环氧基环己基)乙基三乙氧基硅烷、3-巯基丙基三甲氧基硅烷等。
<有机钛螯合化合物(D)>
表面处理液中包含的有机钛螯合化合物(D)没有特别限定,可举出乙酰丙酮钛、辛二醇酸钛(titanium octylene glycolate)、四乙酰丙酮钛(titaniumtetraacetylacetonate)、乙基乙酰乙酸钛(titanium ethylacetoacetate)等。在硝酸钛、硫酸钛、乙酸钛、磷酸钛、碳酸钛等无机盐类中,由于不发挥提高上述(i)所示的耐腐蚀性的效果,因此不优选。应予说明,将有机钛螯合化合物(D)溶解于水中而使用时,钛作为螯合物配体溶解,因此优选不添加影响该配体的极性高的水溶性溶剂、过氧化物。
<4价的钒化合物(E)>
表面处理液中包含的4价的钒化合物(E)没有特别限定,可举出硫酸氧钒、二氯化氧钒、磷酸氧钒、草酸氧钒、乙酰丙酮氧钒等。从进一步得到更高的耐腐蚀性的效果的观点考虑,作为4价的钒化合物(E),优选为产生VO2+(氧钒)离子的钒化合物。5价的钒化合物(例如偏钒酸铵)由于水溶性过高,因此从被膜的溶出性高,上述(ii)所示的密合性(特别是沸水试验后的密合性)变得不充分,因此本发明中不使用。
<钼酸化合物(F)>
表面处理液中包含的钼酸化合物(F)没有特别限定,可以举出钼酸、钼酸铵、钼酸钠、钼酸钾、钼酸镁、钼酸锌等,另外,也可以举出磷钼酸、磷钼酸铵、磷钼酸钠等。本发明中,优选使用从这些化合物中选择的一种以上。
<氟化合物(G)>
表面处理液中包含的氟化合物(G)没有特别限定,可举出氢氟酸、氟硅酸、氟硼酸、氟钛酸、酸性氟化铵、氟化钠、氟锆酸等酸以及它们的盐。本发明中,优选使用选白这些中的一种以上。
[(BS)/{(AS)+(BS)+(CS))]:0.10~0.30
表面处理液中,阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)相对于树脂化合物(A)的固体成分质量(AS),阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(BS)/{(AS)+(BS)+(CS))]必须为0.10~0.30。如果上述质量比小于0.10,则聚氨酯树脂的比例变得过少,有表面处理被膜变硬的趋势。其结果是如果在表面处理钢板的上层形成有机树脂被膜后进行加工,则表面处理被膜被破坏,以该部分作为起点,引起表面处理被膜与形成在其上的有机树脂被膜的剥离。即上述(ii)所示的密合性(特别是沸水试验后的密合性)劣化。因此,上述质量比为0.10以上,优选为0.12以上。另一方面,如果上述质量比超过0.30,则上述(ii)所示的密合性(特别是沸水试验后的密合性)劣化。因此,上述质量比为0.30以下,优选为0.28以下。
[(CS)/{(AS)+(BS)+(CS)}]:0.60~0.85
表面处理液中,硅烷偶联剂(C)的固体成分质量(CS)相对于树脂化合物(A)的固体成分质量(AS)、阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(CS)/{(AS)+(BS)+(CS)}]必须为0.60~0.85。如果上述质量比小于0.60,则上述(ii)所示的密合性(特别是沸水试验后的密合性)劣化。因此,上述质量比为0.60以上,优选为0.65以上。另一方面,如果上述质量比超过0.85,则表面处理液的储存稳定性降低。因此,上述质量比为0.85以下,优选为0.80以下。
{(CS)/(DTi)}:50~70
表面处理液中,硅烷偶联剂(C)的固体成分质量(CS)相对于有机钛螯合化合物(D)的钛换算质量(DTi)的比{(CS)/(DTi)}必须为50~70。如果上述质量比小于50,则上述(i)所示的耐腐蚀性和上述(ii)所示的密合性(特别是沸水试验后的密合性)劣化。因此,上述质量比为50以上,优选为55以上。另一方面,如果上述质量比超过70,则表面处理被膜的溶出性提高,上述(ii)所示的密合性(特别是沸水试验后的密合性)差。因此,上述质量比为70以下,优选为65以下。
应予说明,本发明中,在计算各种质量比时,硅烷偶联剂(C)的固体成分质量(CS)是指烷氧基硅烷(R-Si(-OR1)3)水解而成为硅烷醇(R-Si(-OH)3)的状态的质量。这是由于将硅烷偶联剂溶解于水时,大部分发生了水解,由水解产生的醇爱将表面处理液涂布干燥而形成表面处理被膜时挥发,不作为有效成分发挥作用。
{(EV)/(DTi)}:0.30~0.50
表面处理液中,4价的钒化合物(E)的钒换算质量(EV)相对于有机钛螯合化合物(D)的钛换算质量(DTi)的比{(EV)/(DTi)}必须为0.30~0.50。如果上述质量比小于0.30,则上述(i)所示的耐腐蚀性劣化。因此,上述质量比为0.30以上,优选为0.35以上。另一方面,如果上述质量比超过0.50,则上述(ii)所示的密合性(特别是沸水试验后的密合性)差。因此,上述质量比为0.50以下,优选为0.48以下。
[(FMo)/{(AS)+(BS)+(CS)}]:0.003~0.030
表面处理液中,钼酸化合物(F)的钼换算质量(FMo)相对于树脂化合物(A)的固体成分质量(AS)、阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)、以及硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(FMo)/{(AS)+(BS)+(CS)}]必须为0.003~0.030。上述质量比小于0.003时,耐黑变性劣化。因此,上述质量比为0.003以上,优选为0.006以上。另一方面,如果上述质量比超过0.030,则表面处理液的储存稳定性降低。因此,上述质量比为0.030以下。
[(GF)/{(AS)+(BS)+(CS)}]:0.101~0.200
表面处理液中,氟化合物(G)的氟换算质量(GF)相对于树脂化合物(A)的固体成分质量(AS)、阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(GF)/{(AS)+(BS)+(CS)}]必须为0.101~0.200。如果上述质量比小于0.101,则上述(ii)所示的密合性(特别是沸水试验后的密合性)差。因此,上述质量比为0.101以上,优选为0.105以上。另一方面,如果上述质量比超过0.200,则表面处理被膜的可溶成分增加,因此上述(i)所示的耐腐蚀性和上述(ii)所示的密合性(特别是沸水试验后的密合性)劣化。因此,上述质量比为0.200以下。
pH:4~5
表面处理液的pH为4~5。如果pH小于4,则锌从锌系镀覆钢板的镀层的溶出变多,上述(i)所示的耐腐蚀性劣化。另一方面,如果pH超过5,则得不到表面处理液的储存稳定性。
在此,作为将pH调整为4~5时所使用的酸性剂,优选为磷酸(正磷酸)、乙酸、甲酸、氟酸、氟化物等。乙酸、甲酸由于为弱酸,适宜进行pH调整。并且,它们挥发性高,表面处理液的干燥时挥发,表面处理被膜中的残留少,因此即使过量添加,性能降低也少,因此优选。另一方面,在pH变得过低的情况等,作为将pH调整为4~5时使用的碱性剂,优选氨水、沸点为100℃以下的胺类。
<水>
表面处理液中包含的水优选对树脂化合物(A)、阳离子性聚氨酯树脂乳液(B)、硅烷偶联剂(C)以及有机钛螯合化合物(D)的各成分、以及pH调整所使用的酸成分或者碱成分的影响少。在水中作为杂质包含的Na、Cl等在被膜中残留的情况下有时降低耐腐蚀性,或者降低涂装性。因此,使用的水优选杂质少,例如优选其电导率小于100μS/cm。更优选为50μS/cm以下,进一步优选为10μS/cm以下。
<固体成分浓度>
表面处理液的固体成分浓度以在110℃下干燥2小时时的固体成分浓度计优选为0.05~5质量%。这是因为如果将固体成分浓度设为0.05~5质量%的范围,则容易确保后述的表面处理被膜的附着量,除此以外,能够确保表面处理液的稳定性。
<其它成分>
表面处理液中可以根据需要添加消泡剂、润湿性提高剂。消泡剂的种类没有特别限定,例如可以使用有机硅系、脂肪酸系的乳液型等。润湿性提高剂降低表面处理液的表面张力,提高对锌系镀覆钢板的润湿性,提高外观均匀性。作为润湿性提高剂,可举出水溶性溶剂、例如乙醇、叔丁醇、丁基溶纤剂等,并不限定于这些。并且,含有乙炔的润湿性提高剂等也具有消泡效果,因此很适合。出于进一步提高耐黑变性的目的,表面处理液中可以加入硝酸镍、硝酸铵等硝酸盐。在表面处理液中,包含这些消泡剂、润湿性提高剂以及硝酸盐的其它成分以固体成分量计为7质量%以下。
[有机树脂被覆用表面处理钢板的制造方法]
本发明的有机树脂被覆用表面处理钢板的制造方法包括将上述的表面处理液涂布在锌系镀覆钢板的表面并进行干燥,形成每单面的附着量为0.005~0.18g/m2的表面处理被膜的工序,由此能够制造表面处理被膜不包含铬化合物,耐黑变性以及上述(i)所示的耐腐蚀性和上述(ii)所示的密合性优异的有机树脂被覆用表面处理钢板。
作为将表面处理液涂布在锌系镀覆钢板的表面的方法,可以为涂布法、浸渍法、喷涂法中的任一者。作为涂布法,可以是辊涂机(3辊方式、2辊方式等)、挤压涂布机、模涂机、棒涂机等中任一方法。另外,在涂布表面处理液后,通过气刀法、辊拉深法,也能够进行涂布量的调整、外观的均匀化、膜厚的均匀化。
最高到达板温:50~180℃
涂布表面处理液后,通常不进行水洗而进行加热干燥。作为加热干燥手段,可以使用干燥器、热风炉、高频感应加热炉、红外线炉等。在表面处理液与锌系镀覆钢板表面接触时,在锌系镀层的表层,镀覆成分与作为表面处理液中的反应性成分的氟化合物(G)发生反应,生成镀覆成分与氟化物等的反应层,并且表面处理液干燥,由此形成表面处理被膜。其结果发明人等推测镀层与表面处理被膜的密合性提高。此时,如果(G)的量多,则没有被镀层与表面处理被膜的界面的反应所消耗的氟化合物残留在表面处理被膜中,形成表面处理被膜的成膜不充分的区域,形成了有机树脂被膜时的耐腐蚀性和沸水试验后的有机树脂被膜与表面处理被膜的密合性降低。但是,本发明人等推测在未被镀层与表面处理液的界面的反应所消耗的反应性成分作为可溶成分适度地残留在表面处理被膜中,能够在有机树脂被膜与表面处理被膜的界面形成混合层,能够提高有机树脂被膜与表面处理被膜的密合性。另外,认为表面处理被膜中也包含来自于润湿性提高剂的水溶性溶剂和来自于树脂化合物(A)或阳离子性聚氨酯树脂乳液(B)的表面活性剂等,因此即使形成有机树脂被膜的处理液为溶剂系,也有微量反应性成分混入有机树脂侧。为了得到上述效果,最高到达板温优选为50℃以上。在小于50℃的情况下,在表面处理被膜中残留的反应性成分变成过多,结果表面处理被膜的成膜不充分,在形成了有机树脂被膜后进行加工时,表面处理被膜被破坏,容易以该部分为起点,发生表面处理被膜和形成在其上的有机树脂被膜的剥离。优选为70℃以上。另一方面,如果超过180℃,则在表面处理被膜中残留的反应性成分变少,不会形成与形成在其上的有机树脂被膜的界面混合层,表面处理被膜与有机树脂被膜的界面的密合性提高效果降低。因此,最高到达板温优选为180℃以下,更优选为140℃以下,进一步优选为110℃以下。另外,在最高到达板温的保持小时优选为小于15秒。
表面处理被膜的每单面的附着量:0.005~0.18g/m2
在本发明中,表面处理被膜的每单面的附着量必须为0.005~0.18g/m2。在附着量小于0.005g/m2的情况下,上述(i)所示的耐腐蚀性与上述(ii)所示的密合性(特别是沸水试验后的密合性)劣化。因此,附着量为0.005g/m2以上,优选为0.010g/m2以上。另一方面,如果附着量超过0.18g/m2,则如果在形成了有机树脂被膜后进行加工时表面处理被膜被破坏,以该部分作为起点,发生表面处理被膜和在其上形成的有机树脂被膜的剥离。换句话说,上述(ii)所示的密合性(特别是沸水试验后的密合性)发生劣化。因此,附着量为0.18g/m2以下,优选为0.14g/m2以下。
应予说明,上述的表面处理被膜可以在锌系镀覆钢板的单面实施,也可以在两面实施。
[本发明的作用]
在本发明中使用的表面处理液中,推测各成分具有如下的作用,本发明并不受这些推测限制。
本发明中使用的表面处理液中,树脂化合物(A)、阳离子性聚氨酯树脂乳液(B)、硅烷偶联剂(C)为主成分,通过这些主成分形成表面处理被膜的骨架。
树脂化合物(A)具有双酚作为苯酚的骨架,因此不易溶解于极性溶剂(赋予耐溶剂性),并且提高上述(i)所示的耐腐蚀性。
然而,上述树脂化合物(A)具有使表面处理被膜变硬的趋势。其结果是如果在形成有机树脂被膜后进行加工,则表面处理被膜被破坏,以该部分作为起点,发生表面处理被膜和形成在其上的有机树脂被膜的剥离。因此,本发明中,通过配合阳离子性聚氨酯树脂乳液(B),能够缓和酚醛树脂的硬度,因此能够防止因加工而破坏表面处理被膜。
阳离子性聚氨酯树脂乳液(B)具有上述效果,另一方面,有机树脂被膜与表面处理被膜的密合性和表面处理被膜与镀层的密合性弱。因此,由于形成有机树脂被膜时的与有机树脂被膜的密合性和表面处理被膜与镀层的密合性不足,因此配合硅烷偶联剂(C)。硅烷偶联剂(C)由于末端的烷氧基水解而产生活性的硅烷醇基(Si-OH),因此与锌系镀覆钢板表面键合,有助于形成有机树脂被膜时的表面处理被膜与镀层的密合性提高。另外,硅烷偶联剂具有有机官能团,因此也有助于与有机树脂被膜的密合性提高。并且,硅烷偶联剂(C)的一部分发生脱水缩合而产生硅氧烷键(Si-O-Si),其连续聚合物化(聚硅氧烷化:-Si-O-Si-O-Si-)。由此,成为极其稳定的结构,上述(i)所示的耐腐蚀性与上述(ii)所示的密合性(特别是沸水试验后的密合性)提高。
因此,认为通过以适当的比例使用作为表面处理液的主成分的树脂化合物(A)、阳离子性聚氨酯树脂乳液(B)、硅烷偶联剂(C),能够得到平衡良好的各种性能。然而,仅利用上述主成分,如本发明那样在表面处理被膜的附着量少的情况下,无法确保有机树脂被覆后的耐腐蚀性。因此,在本发明中使用的表面处理液中,除了上述主成分之外,以有机钛螯合化合物(D)作为必需成分。推测有机钛螯合化合物(D)在对表面处理液进行干燥而形成表面处理被膜时,作为促进聚硅氧烷化的催化剂发生作用。由此,在表面处理被膜的附着量少的情况下,确保有机脂被覆后的耐腐蚀性。
为了得到上述效果,如上所述需要根据硅烷偶联剂(C)的量确定的规定量的有机钛螯合化合物(D)。在(D)的量少的情况下得不到所希望的效果,在(D)的量过量的情况下,聚硅氧烷过度增加,成为硬且脆的表面处理被膜,如果在形成了有机树脂被膜后进行加工,则表面处理被膜被破坏,以该部分作为起点发生表面处理被膜与在其上的有机树脂被膜的剥离。即上述(ii)所示的密合性(特别是沸水试验后的密合性)劣化。另外,由有机钛螯合化合物(D)进行的聚硅氧烷化在表面处理被膜形成时被促进是很理想的,但由于即使在表面处理液的储存时也促进聚硅氧烷化,因此在(D)的含量过量的情况下,储存稳定性(增粘·凝胶化的抑制)降低,储存后得不到与储存前同样的品质。
另外,本发明的表面处理液中,4价的钒化合物(E)也是必需成分。在本发明中推测4价的钒化合物(E)将镀覆中的锌钝化等作为腐蚀的抑制剂发挥作用。推测特别是具有一个氧的氧钒离子〔VO2+〕即使在湿润环境下也不易溶出,在表面处理被膜中停留并且发挥抑制剂效果,因此在表面处理被膜、镀覆表面本身被划伤的情况下,也防止该部分的耐腐蚀性的劣化。应予说明,本发明人等推测该效果是以具有阳离子性官能团的被膜骨架是合适的为前提,通过与同样作为阳离子存在的Ti的协同效果来实现。
并且,本发明中使用的表面处理液中,钼酸化合物(F)也是必需成分。锌系镀覆钢板中,无论是电镀钢板或是热浸镀钢板,在腐蚀环境下都易产生镀覆表面变黑的黑变现象。特别是在锌系热浸镀钢板中,为了提高耐腐蚀性或镀层与基底钢板的密合性而添加Mg、Al时,这些元素在镀层与基底钢板的界面、镀层的表层稠化而促进黑变,与纯锌镀覆钢板相比变得更黑。锌系镀覆钢板的黑变现象的原因尚不明确,据说在镀层的最表面生成的氧化锌失去氧而变为氧缺乏型的氧化锌、或锌的腐蚀(氧化)的过程中没有充分供给氧而在镀覆表面生成氧缺乏型的氧化锌,这些看起来都是黑色的。
本发明中,通过将钼酸化合物(F)导入到表面处理被膜中,能够得到优异的耐黑变性。钼是过渡金属,与氧键合而生成钼氧化物(MoO2,MOO3)、钼酸(MoO4 2-)。认为本发明中,钼酸(MOO4 2-)的一部分在高温高湿下或腐蚀环境下,通过变化为钼的氧化物(MoO2、MoO3)而向镀锌层的表面适度地供给氧,因此不易形成氧缺乏型的氧化锌。发明人等推断这样的机理使耐黑变性提高。
本发明中使用的表面处理液中,重要的是氟化合物(G)也是必需成分。发明人等推测这是因为通过添加氟化合物(G),表面处理液与锌系镀覆钢板表面接触时,在锌系镀层的表层生成镀覆成分与氟化物等的反应层,镀层与表面处理被膜的密合性提高。此时,如果(G)的量少,则不能均匀地在镀覆表层生成反应层,形成有机树脂被膜时,在镀层与表面处理被膜的界面,表面处理被膜剥离。另一方面,如果(G)的量多,则未被在镀层与表面处理被膜的界面的反应所消耗的氟化合物残留在表面处理被膜中,形成有机树脂被膜时的耐腐蚀性和沸水试验后的有机树脂被膜与表面处理被膜的密合性降低。然而,通过降低表面处理被膜的附着量,并且降低干燥温度(或者缩短时间),能够在镀层表面薄薄地均匀地形成反应层,使未反应的氟化合物适量地残留在表面处理被膜中。因此,能够确保上述(i)所示的耐腐蚀性和上述(ii)所示的密合性(特别是沸水试验后的密合性)。此时,容易产生F-离子的氢氟酸及其盐、氟化铵、氟化钠特别是表面处理被膜与镀层的密合性的提高效果大,容易在被膜中适量残留可溶成分,因此优选。
[有机树脂被覆钢板及其制造方法]
本发明的有机树脂被覆钢板在以上所述的表面处理钢板的表面处理被膜上形成有机树脂被膜。该有机树脂被膜的形成方法是任意的,例如可以使用使涂料组合物涂布·干燥的方法、层压有机树脂膜的方法等。作为涂料组合物,优选丙烯酸树脂、环氧树脂、聚氨酯树脂、酚醛树脂、聚酯树脂及它们的混合物。作为有机树脂膜,优选为选白聚氯乙烯膜、聚烯烃系膜、聚酯系膜以及氟树脂系膜中的一种以上的膜或者将这些层叠两种以上而成的层叠膜。有机树脂被膜的厚度优选为60μm以上,进一步优选为100μm以上。虽然上限没有特别限定,但该厚度优选为600μm以下。
另外,本发明的有机树脂被覆钢板的上述(i)所示的耐腐蚀性和上述(ii)所示的密合性(特别是沸水试验后的密合性)优异。
应予说明,在有机树脂被膜中可以配合以非铬系防锈添加剂、固体润润滑剂、着色颜料等为代表的各种添加剂。
实施例
作为表面处理液的成分,使用表1(表1a和表1b)所示的树脂化合物(A)、表2所示的聚氨酯树脂乳液(B)、表3所示的硅烷偶联剂(C)、表4所示的钛化合物(D)、表5所示的钒化合物(E)、表6所示的钼酸化合物(F)、表7所示的氟化合物(G)。另外,准备表8所示的各种锌系镀覆钢板。
以表9-1和表9-2所示的配合比例混合表1~7记载的各成分,利用乙酸或者氨将pH调整为表9-2所示的值后,以在110℃下干燥2小时时的固体成分浓度成为表10所示的值的方式添加去离子水,制备各种水平的表面处理液。应予说明,作为上述的去离子水,使用电导率为10μS/cm的离子交换水。应予说明,表9-2所示的质量比(X1)~(X6)分别是指由权利要求1规定的质量比(1)~(6)。
在表10所示的种类的锌系镀覆钢板的单面,通过辊涂机涂布各水平的表面处理液,不进行水洗,以最高到达板温(PMT)为表10所示的值的方式进行加热干燥,制造各水平的表面处理钢板。表面处理被膜的每单面的附着量通过涂布条件(辊的压下力、旋转速度等)和表面处理液的固体成分浓度,调整为表10所示的值。应予说明,表面处理被膜的附着量通过荧光X射线分析装置,对配合于表面处理被膜中的硅烷偶联剂(C)的Si量进行定量,由该Si量换算而求出。
并且,准备表11所示的有机树脂膜或者涂料。表11中的R1是伸长率大的膜厚200μm的聚氯乙烯膜,R2是伸长率小的膜厚100μm的聚酯系膜,R3是伸长率小的膜厚100μm的聚烯烃系膜。在各水平中,在表面处理被膜上以干燥膜厚为3μm的方式涂布粘接剂而形成粘接剂层后,进行加热干燥(最高到达板温80℃)。接着,通过在粘接剂层上在210℃下对表10所示的种类的有机树脂膜进行热压,使各膜(有机树脂被膜)粘接,制成有机树脂被覆钢板。另外,R4是聚烯烃系涂料组合物,涂布在表面处理被膜上后,在150℃下干燥30分钟,制成有机树脂被覆钢板。
对从各水平的表面处理钢板采取的样品,进行以下的(1)所示的耐黑变性的评价。另外,对从各水准的有机树脂被覆钢板采取的样品,进行以下的(2)~(6)所示的耐腐蚀性和密合性的评价。并且,对各水平的表面处理液进行以下的(7)所示的储存稳定性的评价。将其结果示于表12。
(1)耐黑变性
计算将各样品控制在温度:50℃、相对湿度:95%的气氛的恒温恒湿机中静置24小时时的亮度(L值)的变化(ΔL=试验后的L值一试验前的L值)。评价基准如下。L值使用日本电色工业(株)制的SR2000以SCE模式(除去正反射光)进行测定。
◎:-6≤ΔL
○:-10≤ΔL<-6
△:-14≤ΔL<-10
×:ΔL<-14
(2)有机树脂被覆钢板的耐腐蚀性
对50mm×100mm的样品表面进行十字划格,按照JIS-Z-2371-2000的规定进行1000小时的盐水喷雾试验。测定来自十字划格的单侧腐蚀宽度。该评价基准如下。
◎:从划格部开始的平均腐蚀宽度小于5mm
○:从划格部开始的平均腐蚀宽度为5mm以上且小于10mm
△:从划格部开始的平均腐蚀宽度为10mm以上且小于15mm
×:从划格部开始的平均腐蚀宽度为15mm以上
(3)有机树脂被覆钢板的密合性1
在样品表面利用切割刀具,以在后述的埃里克森加工时的中心部形成5mm见方的方格的方式(井型),划出达锌系镀覆钢板的切口,利用埃里克森试验机悬伸成6mm后,测定5mm方格内的有机树脂被膜的剥离面积。
◎:未剥离
○:小于剥离面积3%
△:剥离面积3%以上且小于10%
×:剥离面积10%以上
(4)沸水试验后的有机树脂被覆钢板的密合性1
将各样品浸渍在沸腾水中2小时并提起。然后,对各样品,利用与上述(3)同样的方法测定剥离面积。
◎:无剥离
○:小于剥离面积3%
△:剥离面积3%以上且小于10%
×:剥离面积10%以上
(5)有机树脂被覆钢板的密合性2
在样品表面利用切割刀具,以在后述的埃里克森加工时的中心部形成5mm见方的方格的方式(井型),划出到达锌系镀覆钢板的切口,利用埃里克森试验机悬伸成8mm后,测定5mm方格内的有机树脂被膜的剥离面积。
◎:无剥离
○:小于剥离面积3%
△:剥离面积3%以上且小于10%
×:剥离面积10%以上
(6)沸水试验后的有机树脂被覆后密合性2
将各样品浸渍在沸腾水中2小时提起。然后,对各样品,利用与上述(5)同样的方法测定剥离面积。
◎:没有剥离
○:小于剥离面积3%
△:剥离面积3%以上且小于10%
×:剥离面积10%以上
(7)储存稳定性
将各水平的表面处理液在40℃的恒温槽中保存30天后,目视观察各表面处理液的外观进行调查和评价。评价基准如下。
◎:没有变化
O:看到极微量的沉淀
△:看到微量的沉淀或者粘度略变高
×:看到大量的沉淀或者凝胶化
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[表2]
表2聚氨酯树脂(B)
No. | 聚氨酯树脂(B) | 离子性 | 制造商 |
B1 | ADEKA BONTIGHTER HUX-670 | 阳离子 | ADEKA株式会社 |
B2 | Super Flex 600 | 阳离子 | 第一工业制药株式会社 |
B3 | PERMARIN UC-20 | 阳离子 | 三洋化成工业株式会社 |
B4 | ADEKA BONTIGHTER UX-206 | 非离子 | ADEKA株式会社 |
B5 | HYDRAN AP-10阴离子 | 阴离子 | DIC株式会社 |
[表3]
表3硅烷偶联剂(C)
No. | 硅烷偶联剂(C) |
C1 | 3-巯基丙基三甲氧基硅烷 |
C2 | N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷 |
C3 | 3-缩水甘油氧基丙基三甲氧基硅烷 |
C4 | 3-甲基丙烯酰氧基丙基三甲氧基硅烷 |
C5 | 乙烯基三甲氧基硅烷 |
[表4]
表4钛化合物(D)
No. | 钛化合物(D) |
D1 | 乙酰丙酮钛(Ti:12.5质量%) |
D2 | 四乙酰丙酮钛(Ti:10.8质量%) |
D3 | 硝酸钛(Ti:16.2质量%) |
D4 | 氟钛酸(Ti:29.2质量%) |
[表5]
表5钒化合物(E)
No. | 钒化合物(E) |
E1 | 草酸氧钒(V:32.9质量%) |
E2 | 乙酰丙酮氧钒(V:19.2质量%) |
E3 | 硫酸氧钒(V:31.2质量%) |
E4 | 偏钒酸铵(V:43.5质量%) |
[表6]
表6钼酸化合物(F)
No. | 钼酸化合物(G) |
F1 | Na2MoO4·2H2O |
F2 | (NH4)6Mo7O24·4H2O |
F3 | (NH4)3[PMo12O40]·3H2O |
[表7]
表7氟化合物(G)
No. | 氟化合物(G) |
G1 | 氢氟酸 |
G2 | 氟硅酸 |
G3 | 氟钛酸 |
G4 | 酸性氟化铵 |
G5 | 氟化钠 |
[表8]
表8锌系镀覆钢板
*镀覆虽然在两个面实施,但上述表示每单面的镀覆附着量。
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[表11]
表11有机树脂被膜
No. | 膜或涂料 | 膜厚 |
R1 | 聚氯乙烯膜 | 200μm |
R2 | 聚酯系膜 | 100μm |
R3 | 聚烯烃系膜 | 100μm |
R4 | 聚烯烃系涂料 | 60μm |
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如表12所示,本发明例中,任一发明例均具有优异的耐黑变性、有机树脂被覆后的耐腐蚀性和密合性以及储存稳定性。
工业上的可利用性
由本发明的制造方法制造的带表面处理被膜的锌系镀覆钢板可以在汽车、家电、建材等领域中广泛利用。
Claims (8)
1.一种有机树脂被覆用表面处理钢板的制造方法,其特征在于,将以满足下述(1)~(6)的条件的范围含有(A)~(H)且pH为4~5的表面处理液涂布于锌系镀覆钢板的表面,使其干燥,形成每单面的附着量为0.005~0.18g/m2的表面处理被膜;
具有由下述的通式(I)表示的双酚骨架的树脂化合物(A)、
具有选自伯氨基、仲氨基、叔氨基和季铵盐基团中的至少一种阳离子性官能团的阳离子性聚氨酯树脂乳液(B)、
具有选自含活性氢的氨基、环氧基、巯基以及甲基丙烯酰氧基中的至少一种反应性官能团的硅烷偶联剂(C)、
有机钛螯合化合物(D)、
4价的钒化合物(E)、
钼酸化合物(F)、
氟化合物(G)、以及
水(H);
(1)所述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)相对于所述树脂化合物(A)的固体成分质量(AS)、所述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及所述硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(BS)/{(AS)+(BS)+(CS)}]为0.10~0.30
(2)所述硅烷偶联剂(C)的固体成分质量(CS)相对于所述树脂化合物(A)的固体成分质量(AS)、所述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及所述硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(CS)/{(AS)+(BS)+(CS)}]为0.60~0.85
(3)所述硅烷偶联剂(C)的固体成分质量(CS)相对于所述有机钛螯合化合物(D)的钛换算质量(DTi)的比{(CS)/(DTi)}为50~70
(4)所述4价的钒化合物(E)的钒换算质量(EV)相对于所述有机钛螯合化合物(D)的钛换算质量(DTi)的比{(EV)/(DTi)}为0.30~0.50
(5)所述钼酸化合物(F)的钼换算质量(FMo)相对于所述树脂化合物(A)的固体成分质量(AS)、所述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及所述硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(FMo)/{(AS)+(BS)+(CS)}]为0.003~0.030
(6)所述氟化合物(G)的氟换算质量(GF)相对于所述树脂化合物(A)的固体成分质量(AS)、所述阳离子性聚氨酯树脂乳液(B)的固体成分质量(BS)以及所述硅烷偶联剂(C)的固体成分质量(CS)的合计的比[(GF)/{(AS)+(BS)+(CS)}]为0.101~0.200
式(I)中,与苯环键合的Y1和Y2分别相互独立地为氢原子、或者以下的通式(II)或(III)表示的Z基团,每1个苯环的Z基团的取代数的平均值为0.2~1.0,n表示2~50的整数,
式(II)和(III)中,R1、R2、R3、R4和R5分别相互独立地表示氢原子、碳原子数1~10的烷基或者碳原子数1~10的羟基烷基,A-表示氢氧根离子或者酸根离子。
2.根据权利要求1所述的有机树脂被覆用表面处理钢板的制造方法,其中,在最高到达板温为50~180℃的条件下进行所述表面处理液的干燥。
3.一种有机树脂被覆用表面处理钢板,是由权利要求1或2所述的有机树脂被覆用表面处理钢板的制造方法制造的。
4.一种有机树脂被覆钢板的制造方法,包括:权利要求1或2所述的有机树脂被覆用表面处理钢板的制造方法;以及
在所述有机树脂被覆用表面处理钢板的所述表面处理被膜上形成有机树脂被膜的工序。
5.根据权利要求4所述的有机树脂被覆钢板的制造方法,其中,所述有机树脂被膜通过在所述表面处理被膜上层压有机树脂膜而形成。
6.根据权利要求5所述的有机树脂被覆钢板的制造方法,其中,所述有机树脂膜具有60μm以上的厚度。
7.根据权利要求5或6所述的有机树脂被覆钢板的制造方法,其中,所述有机树脂膜为选自聚氯乙烯膜、聚烯烃系膜、聚酯系膜以及氟树脂系膜中的1种以上的膜。
8.一种有机树脂被覆钢板,是由权利要求4~7中任一项所述的有机树脂被覆钢板的制造方法制造的。
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