CN105925152A - 一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺 - Google Patents

一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺 Download PDF

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CN105925152A
CN105925152A CN201610300942.0A CN201610300942A CN105925152A CN 105925152 A CN105925152 A CN 105925152A CN 201610300942 A CN201610300942 A CN 201610300942A CN 105925152 A CN105925152 A CN 105925152A
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resin
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耿凯
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JIANGSU KAITEER NEW TYPE DECORATIVE MATERIALS Co Ltd
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Abstract

本发明涉及金属印花板生产技术领域，特别是一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺，该生产工艺包括如下步骤：在金属板的表面涂覆聚酯成分的底漆，形成第一涂层；在所述第一涂层上涂覆氟碳涂料层，形成第二涂层；在所述第二涂层上涂覆印花油墨层，形成第三涂层；在所述第三涂层上涂覆纳米陶瓷涂料层，形成第四涂层。本发明的组分中特有的Si‑O结构具有高达101千卡/mol的结合能，在后期高温烘烤后可形成玻璃质化立体网状结构，从而使涂层表面漆膜不易划伤或形成磨损，具有优秀的不燃性和绝缘性，各涂覆层依次均具有良好的兼容性，依次附着力较佳，适宜进一步推广应用。

Description

一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺
技术领域
本发明涉及金属印花板生产技术领域，特别是一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺。
背景技术
目前，金属印花板材在建筑物幕墙、门板及保温板等领域具有广泛的应用。金属印花板是指金属基材经连续机组脱去表面油脂、表面钝化等表面处理后，在金属基材上涂覆特定成分的底漆后经过油墨的辊涂、喷涂或丝网印刷形成的具有印花层的一种复合板材。
现有市场上的金属印花板的印花涂层与底漆之间的附着力往往达不到要求，从而容易使得印花涂层在使用中出现脱落的情形，即“掉漆”现象，从而影响印花金属板的整体美观性，为克服“掉漆”现象，专利200810054117.2公开了一种喷码油墨及其制备方法，该油墨包括：松香改性树脂15-35，硝化棉3-15，颜料或染料2-10，丁酮20-50，异丙醇5-20，甲苯10-30，所得油墨墨性稳定，在聚烯烃材料表面具有较高的附着性能，但在聚乙烯和聚丙烯材料表面的附着力较小，附着牢固度较差。专利101698764公开了一种高附着力无苯环保通用喷码油墨及其制备方法，该喷码油墨包括:改性氯化聚丙烯树脂5-10，复配树脂1-5，丁酮70-89，染料2-6，导电助剂0.5-1.5；增塑剂1-3，液体石蜡0.5-1.5，其它助剂1-3。该油墨在聚乙烯、聚丙烯以及金属底材上具有较高的附着力，但该油墨与聚酯底材间的附着力较差。针对上述问题，开发一种附着力较好的金属印花板的生产工艺是本领域技术人员要解决的技术问题。
发明内容
本发明要解决的技术问题是：针对上述技术问题，提供一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺。
本发明解决其技术问题所采用的技术方案是：一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺，该生产工艺包括如下步骤：
(1)在金属板的表面涂覆聚酯成分的底漆，形成第一涂层；
(2)在所述第一涂层上涂覆氟碳涂料层，形成第二涂层；
(3)在所述第二涂层上涂覆印花油墨层，形成第三涂层；
(4)在所述第三涂层上涂覆纳米陶瓷涂料层，形成第四涂层；上述四涂层是采用改进的三辊涂网格滚筒进行带料，使用六涂六烘连续辊涂印花工艺，实现涂覆；按重量份数计，所述第一涂层包括如下组分：醇酸树脂4-9，不饱和聚酯树脂60-75，醋酸丁酯、苯乙烯的混合物5-15，聚硅氧烷0.1-0.3，聚醚改性聚二甲基硅氧烷0.05-0.1，过氧化甲乙酮0.1-0.5，不饱和聚氨基酰胺0.5-1.0，对苯二酚0.3-0.5；所述第二涂层包括如下组分：水性乙烯基氟碳乳液60-75，异佛尔酮二异氰酸酯15-25，丁酸乙酯3-6，聚丙烯酰胺0.2-0.7，聚硅氧烷0.1-0.6，立德粉10-15，去离子水20-25，纳米氧化镁1-3，纳米氢氧化锌2-4；第四涂层包括如下组分：纳米陶瓷树脂70-80份,固化剂10-15份，消光剂2-4份，氟碳表面活性剂0.5-3份，溶剂25-35份，添加剂1-5份；所述纳米陶瓷树脂包括如下组分：纳米级粉体10-20，无机硅酸盐水和物20-40，水性硅丙乳液5-12；无机硅酸盐水和物为通过水热法制成的平均粒径在50-100nm的水和物；所述固化剂为β-羟烷基酰胺类或三缩水甘油基异氰尿酸酯；添加剂为流平剂和消泡剂按照重量比(0.7-1):(0.8-1)形成的复合物。
进一步，上述技术方案中所述第一涂层中醋酸丁酯、苯乙烯混合物是醋酸丁酯和苯乙烯按照1:1.5形成的混合物。
进一步，上述技术方案中所述第二涂层的制备方法包括如下步骤：
(1)将纳米氧化镁和纳米氢氧化锌加入球磨机中球磨3h，过筛后自然冷却至室温得到混合粉体，将混合粉体加入去离子水中，搅拌分散4h pH调节为6-6.5后得到纳米混合液；
(2)将聚硅氧烷加入纳米混合液中，超声频率为70Hz下超声分散20min，依次加入丁酸乙酯、聚丙烯酰胺、立德粉，60℃下恒温水浴搅拌1h，再加入水性乙烯基氟碳乳液，搅拌速度为800r/min，搅拌均匀后用100目过滤网过滤与异佛尔酮二异氰酸酯分装，即得氟碳涂料。
进一步，上述技术方案中所述印花油墨层包括：聚氨酯树脂45-65，聚酯树脂15-25，氨改性丙烯酸树脂9-15，丙烯酸酯类单体11-21，氟碳表面改性剂1-4，引发剂BP 1-5，有机硅消泡剂1-3，有机硅聚醚改性流平剂1-4，膨润土1-4；该油墨配制流程如下：按照比例配备原料，先将引发剂BP与丙烯酸酯类单体进行混合，充分搅拌后放置30min，然后将其余各组分按比例与其混合，使用高速分散机高速搅拌并升温至70-80℃，使各组分混合均匀，再用三辊机研磨使细度小于5μm，即得印花油墨。
有益效果：与现有技术相比，本发明的组分中特有的Si-O结构具有高达101千卡/mol的结合能，在后期高温烘烤后可形成玻璃质化立体网状结构，从而使涂层表面漆膜不易划伤或形成磨损，具有优秀的不燃性和绝缘性，各涂覆层依次均具有良好的兼容性，依次附着力较佳，适宜进一步推广应用。
具体实施方式
下面结合具体实施例对本发明做进一步说明，但本发明不局限于下述实施例。
实施例一
一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺，该生产工艺包括如下步骤：
(1)在金属板的表面涂覆聚酯成分的底漆，形成第一涂层；其中，金属板包括依次进行的如下处理：热轧金属卷、盐酸酸洗金属卷、对酸洗后的金属卷进行冷轧处理形成金属板、对冷轧后的金属板连续热浸镀锌处理，从而形成所需金属板；
(2)在所述第一涂层上涂覆氟碳涂料层，形成第二涂层；
(3)在所述第二涂层上涂覆印花油墨层，形成第三涂层；
(4)在所述第三涂层上涂覆纳米陶瓷涂料层，形成第四涂层；上述四涂层是采用改进的三辊涂网格滚筒进行带料，使用六涂六烘连续辊涂印花工艺，实现涂覆；按重量份数计，所述第一涂层底漆包括如下组分：醇酸树脂9，不饱和聚酯树脂75，醋酸丁酯、苯乙烯的混合物14，聚硅氧烷0.3，聚醚改性聚二甲基硅氧烷0.08，过氧化甲乙酮0.5，不饱和聚氨基酰胺0.8，对苯二酚0.4；第一涂层中醋酸丁酯、苯乙烯混合物是醋酸丁酯和苯乙烯按照1:1.5形成的混合物；该底漆的制备方法如下：将不饱和聚酯树脂、醇酸树脂、醋酸丁酯、苯乙烯的混合物三者依次加入反应器中，在转速为400-450r/min条件下搅拌20min，再依次每隔10min加入聚醚改性聚二甲基硅氧烷、聚硅氧烷、不饱和聚氨基酰胺、过氧化甲乙酮和对苯二酚，完全加完后，在转速为500-550r/min条件下搅拌20min，停机自然降温，过筛即得第一涂层底漆；
所述第二涂层包括如下组分：水性乙烯基氟碳乳液75，异佛尔酮二异氰酸酯25，丁酸乙酯5.5，聚丙烯酰胺0.6，聚硅氧烷0.5，立德粉15，去离子水25，纳米氧化镁3，纳米氢氧化锌4；第二涂层的制备方法包括如下步骤：
(1)将纳米氧化镁和纳米氢氧化锌加入球磨机中球磨3h，过筛后自然冷却至室温得到混合粉体，将混合粉体加入去离子水中，搅拌分散4h pH调节为6-6.5后得到纳米混合液；
(2)将聚硅氧烷加入纳米混合液中，超声频率为70Hz下超声分散20min，依次加入丁酸乙酯、聚丙烯酰胺、立德粉，60℃下恒温水浴搅拌1h，再加入水性乙烯基氟碳乳液，搅拌速度为800r/min，搅拌均匀后用100目过滤网过滤与异佛尔酮二异氰酸酯分装，即得氟碳涂料，使用时将两组分在常温下混合搅拌，常温涂覆6h表干，24h实干；
所述印花油墨层包括：聚氨酯树脂65，聚酯树脂25，氨改性丙烯酸树脂15，丙烯酸酯类单体20，氟碳表面改性剂3.5，引发剂BP 4.5，有机硅消泡剂3，有机硅聚醚改性流平剂3.5，膨润土3.5；该油墨配制流程如下：按照比例配备原料，先将引发剂BP与丙烯酸酯类单体进行混合，充分搅拌后放置30min，然后将其余各组分按比例与其混合，使用高速分散机高速搅拌并升温至70-80℃，使各组分混合均匀，再用三辊机研磨使细度小于5μm，即得印花油墨；
第四涂层的制备方法包括如下制备步骤：
(1)按重量份数计，准备如下组分：纳米陶瓷树脂80份,固化剂15份，气相二氧化硅4份，氟碳表面活性剂2.5份，异氟尔酮35份，添加剂4份；
(2)将纳米陶瓷树脂和溶剂在反应器中采用分散机进行分散，在转速800-1000转/min，搅拌分散15-20min；
(3)向步骤(2)产物中加入氟碳表面活性剂、消光剂和添加剂依次加入反应器中混合搅拌30-40min,然后加入固化剂,降速20％搅拌20-30min，用200目筛网过滤，得预辊涂纳米陶瓷涂料。
其中，步骤(1)中纳米陶瓷树脂由纳米级粉体20，无机硅酸盐水和物40，水性硅丙乳液12按照水性硅丙乳液、无机硅酸盐水和物、纳米级粉体的添加顺序在反应器中搅拌形成；无机硅酸盐水和物为通过水热法制成的平均粒径在80nm的模数为1.8的硅酸钠水和物，纳米级粉体为纳米二氧化硅、纳米三氧化二铝和超细碳酸钙按照质量比1：0.6：0.5形成的复配物，水性硅丙乳液是上海丽邦化工科技有限公司的378；固化剂为β-羟烷基酰胺类；氟碳表面活性剂为3-四聚环氧九氟丁烷酰胺基丙基(2-亚硫酸)乙基二甲基铵，添加剂为流平剂BYK-358和消泡剂聚硅氧烷按照重量比0.8:0.9形成的复合物。
实施例二
一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺，该生产工艺步骤如实施例一，其中：
所述第一涂层底漆包括如下组分：醇酸树脂6.5，不饱和聚酯树脂70，醋酸丁酯、苯乙烯的混合物11，聚硅氧烷0.2，聚醚改性聚二甲基硅氧烷0.08，过氧化甲乙酮0.3，不饱和聚氨基酰胺0.75，对苯二酚0.4；第二涂层包括如下组分：水性乙烯基氟碳乳液65，异佛尔酮二异氰酸酯19，丁酸乙酯4.8，聚丙烯酰胺0.45，聚硅氧烷0.35，立德粉13，去离子水22，纳米氧化镁2.2，纳米氢氧化锌3.5；所述印花油墨层包括：聚氨酯树脂55，聚酯树脂21，氨改性丙烯酸树脂11，丙烯酸酯类单体15，氟碳表面改性剂3，引发剂BP 2.8，有机硅消泡剂2.5，有机硅聚醚改性流平剂3.2，膨润土2.8；第四涂层的制备方法包括如下制备步骤：
(1)按重量份数计，准备如下组分：纳米陶瓷树脂75份,固化剂13份，气相二氧化硅3份，氟碳表面活性剂2.0份，异氟尔酮30份，添加剂4份；其余步骤同实施例一。其中，步骤(1)中纳米陶瓷树脂由纳米级粉体15，无机硅酸盐水和物30，水性硅丙乳液8按照水性硅丙乳液、无机硅酸盐水和物、纳米级粉体的添加顺序在反应器中搅拌形成；无机硅酸盐水和物为通过水热法制成的平均粒径在80nm的模数为1.8的硅酸钠水和物，纳米级粉体为纳米二氧化硅、纳米三氧化二铝和硅酸镁按照质量比1：0.7：0.6形成的复配物，水性硅丙乳液是上海丽邦化工科技有限公司的378；固化剂为β-羟烷基酰胺类；氟碳表面活性剂为3-四聚环氧九氟丁烷酰胺基丙基甜菜碱，添加剂为流平剂聚醚改性聚二甲基硅氧烷共聚体和消泡剂BYK066按照重量比0.7:0.8形成的复合物。
实施例三
一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺，该生产工艺步骤如实施例一，其中：
所述第一涂层底漆包括如下组分：醇酸树脂4，不饱和聚酯树脂60，醋酸丁酯、苯乙烯的混合物5.5，聚硅氧烷0.1，聚醚改性聚二甲基硅氧烷0.055，过氧化甲乙酮0.1，不饱和聚氨基酰胺0.55，对苯二酚0.35；第二涂层包括如下组分：水性乙烯基氟碳乳液60，异佛尔酮二异氰酸酯15，丁酸乙酯3，聚丙烯酰胺0.25，聚硅氧烷0.15，立德粉11，去离子水21，纳米氧化镁2.2，纳米氢氧化锌3.5；所述印花油墨层包括：聚氨酯树脂45，聚酯树脂18，氨改性丙烯酸树脂10，丙烯酸酯类单体12，氟碳表面改性剂1.5，引发剂BP 1.5，有机硅消泡剂1.5，有机硅聚醚改性流平剂1.5，膨润土1.8。
采用上述实施例一到三的工艺得到三个金属印花板样品，分别做了铅笔硬度试验、180度弯曲试验及反向冲击试验，数据如下：
由上表可以看出，采用上述实施例的工艺所得的金属印花板的综合性能较佳，表层具有较好的耐磨性，各层之间具有较好的附着力，方便实用，适宜进一步推广应用。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并加以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围内。

Claims (4)

1.一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺，其特征是：该生产工艺包括如下步骤：
(1)在金属板的表面涂覆聚酯成分的底漆，形成第一涂层；
(2)在所述第一涂层上涂覆氟碳涂料层，形成第二涂层；
(3)在所述第二涂层上涂覆印花油墨层，形成第三涂层；
(4)在所述第三涂层上涂覆纳米陶瓷涂料层，形成第四涂层；上述四涂层是采用改进的三辊涂网格滚筒进行带料，使用六涂六烘连续辊涂印花工艺，实现涂覆；按重量份数计，所述第一涂层包括如下组分：醇酸树脂4-9，不饱和聚酯树脂60-75，醋酸丁酯、苯乙烯的混合物5-15，聚硅氧烷0.1-0.3，聚醚改性聚二甲基硅氧烷0.05-0.1，过氧化甲乙酮0.1-0.5，不饱和聚氨基酰胺0.5-1.0，对苯二酚0.3-0.5；
所述第二涂层包括如下组分：水性乙烯基氟碳乳液60-75，异佛尔酮二异氰酸酯15-25，丁酸乙酯3-6，聚丙烯酰胺0.2-0.7，聚硅氧烷0.1-0.6，立德粉10-15，去离子水20-25，纳米氧化镁1-3，纳米氢氧化锌2-4；
第四涂层包括如下组分：纳米陶瓷树脂70-80份,固化剂10-15份，消光剂2-4份，氟碳表面活性剂0.5-3份，溶剂25-35份，添加剂1-5份；所述纳米陶瓷树脂包括如下组分：纳米级粉体10-20，无机硅酸盐水和物20-40，水性硅丙乳液5-12；无机硅酸盐水和物为通过水热法制成的平均粒径在50-100nm的水和物；所述固化剂为β-羟烷基酰胺类或三缩水甘油基异氰尿酸酯；添加剂为流平剂和消泡剂按照重量比(0.7-1):(0.8-1)形成的复合物。
2.根据权利要求1所述的一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺，其特征是：所述第一涂层中醋酸丁酯、苯乙烯混合物是醋酸丁酯和苯乙烯按照1:1.5形成的混合物。
3.根据权利要求1所述的一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺，其特征是：所述第二涂层的制备方法包括如下步骤：
(1)将纳米氧化镁和纳米氢氧化锌加入球磨机中球磨3h，过筛后自然冷却至室温得到混合粉体，将混合粉体加入去离子水中，搅拌分散4h pH调节为6-6.5后得到纳米混合液；
(2)将聚硅氧烷加入纳米混合液中，超声频率为70Hz下超声分散20min，依次加入丁酸乙酯、聚丙烯酰胺、立德粉，60℃下恒温水浴搅拌1h，再加入水性乙烯基氟碳乳液，搅拌速度为800r/min，搅拌均匀后用100目过滤网过滤与异佛尔酮二异氰酸酯分装，即得氟碳涂料。
4.根据权利要求1所述的一种预辊涂纳米陶瓷涂料的金属印花板的生产工艺，其特征是：所述印花油墨层包括：聚氨酯树脂45-65，聚酯树脂15-25，氨改性丙烯酸树脂9-15，丙烯酸酯类单体11-21，氟碳表面改性剂1-4，引发剂BP 1-5，有机硅消泡剂1-3，有机硅聚醚改性流平剂1-4，膨润土1-4。
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