CN106519740B - 白色涂料组合物、绝缘基材表面选择性金属化的方法及复合制品 - Google Patents
白色涂料组合物、绝缘基材表面选择性金属化的方法及复合制品 Download PDFInfo
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Abstract
本发明提供了一种白色涂料组合物,所述白色涂料组合物中含有化学镀催化剂前驱体、粘结剂、溶剂,含或不含助剂;所述化学镀催化剂前驱体选自SnO2、ZnSnO3、ZnTiO3中的至少一种。本发明还提供了采用该白色涂料组合物在绝缘基材表面选择性金属化的方法以及由该方法得到的复合制品。本发明提供的白色涂料组合物,能满足白色产品的要求;同时采用该白色涂料组合物在绝缘基材表面形成白色涂层,不会对绝缘基材自身的各种性能产生任何影响,激光照射后即可实现涂层表面直接化学镀,从而实现选择性金属化,得到具有良好附着力的复合制品。
Description
本申请是申请日为2012年10月26日、申请号为201210416065.5、发明名称为“白色涂料组合物、绝缘基材表面选择性金属化的方法及复合制品”的中国专利申请的分案申请。
技术领域
本发明属于非金属材料表面金属化领域,具体涉及一种白色涂料组合物、采用该白色涂料组合物在绝缘基材表面选择性金属化的方法以及由该方法得到的复合制品。
背景技术
在塑料表面形成金属层,作为电磁信号传导的通路,目前已广泛用于汽车、工业、计算机、通讯等领域。塑料表面选择性地形成金属层是该类塑料制品制造的一个核心环节。塑料表面金属化生产线路有很多方法,现有技术中一般通过先在塑料基材表面形成金属核作为化学镀催化活性中心,然后进行化学镀。
例如,本申请人的专利申请CN101747650A、CN102071421A、CN102071423A、CN102071411A、CN102071424A和CN102071412A公开了可以在绝缘性基材的制备过程中,将化学镀催化剂预置在塑料基材内,在进行化学镀之前,先采用例如激光蚀刻的方法去掉所述塑料基体表面选定区域内的基材,以在该区域内裸露出化学镀催化剂,然后在该裸露的区域上进行化学镀,从而在所述绝缘性基材的表面上形成金属层,进而形成信号传导通路。但是,上述方法还存在以下不足:上述方法中所使用的化学镀催化剂均为彩色物质,如黑色、灰色、棕色、黄色、绿色等,无法做到白色,无法满足客户及市场对白色产品的要求。
发明内容
本发明针对上述方法中存在的无法制备白色产品的技术问题,提供了一种白色涂料组合物、采用该白色涂料组合物在绝缘基材表面选择性金属化的方法以及由该方法得到的复合制品。
具体地,本发明的技术方案为:
一种白色涂料组合物,所述白色涂料组合物中含有化学镀催化剂前驱体、粘结剂、溶剂,含或不含助剂;所述化学镀催化剂前驱体选自SnO2、ZnSnO3、ZnTiO3中的至少一种。
一种绝缘基材表面选择性金属化的方法,包括以下步骤:
S1、将本发明提供的白色涂料组合物施加于绝缘基材的表面,固化后在绝缘基材表面形成白色涂层;
S2、对绝缘基材表面的白色涂层的选定区域进行激光照射,裸露出的化学镀催化剂前驱体转变为化学镀催化剂;
S3、对经过步骤S2的绝缘基材表面进行化学镀,在选定区域形成金属层。
一种复合制品,所述复合制品包括绝缘基材和绝缘基材表面选定区域的金属层;所述复合制品由本发明提供的方法得到。
本发明提供的白色涂料组合物中,其中采用的化学镀催化剂前驱体为白色物质,能满足白色产品的要求。采用该白色涂料组合物在绝缘基材表面形成白色涂层,即该涂层仅覆盖于绝缘基材表面,不会对绝缘基材自身的各种性能产生任何影响,而该白色涂层中所含的白色化学镀催化剂前驱体在激光照射下能转变为化学镀催化剂,从而可实现涂层表面直接化学镀,从而实现选择性金属化,得到具有良好附着力的复合制品。
具体实施方式
本发明提供了一种白色涂料组合物,所述白色涂料组合物中含有化学镀催化剂前驱体、粘结剂、溶剂,含或不含助剂;所述化学镀催化剂前驱体选自SnO2、ZnSnO3、ZnTiO3中的至少一种。
本发明提供的白色涂料组合物中,其中采用的化学镀催化剂前驱体为白色物质,一方面能满足白色产品的要求,另一方面该白色涂料组合物在绝缘基材表面形成白色涂层,即该涂层仅覆盖于绝缘基材表面,不会对绝缘基材自身的各种性能产生任何影响,而该白色涂层中所含的白色化学镀催化剂前驱体在激光照射下能转变为化学镀催化剂,从而可实现涂层表面直接化学镀,从而实现选择性金属化,得到具有良好附着力的复合制品。
本发明的发明人通过大量实验发现,本发明采用的化学镀催化剂前驱体为一类在激光照射下具有较高活性的金属共价化合物,其在激光能量作用下很容易转变为具有氧空位等晶体缺陷的物质,该晶体缺陷物质即可以作为化学镀铜的催化剂,从而实现直接化学镀。
本发明中,所述化学镀催化剂的前驱体为白色的金属氧化物或金属盐,具体选自SnO2、ZnSnO3、ZnTiO3中的至少一种,可直接商购得到,本发明没有特殊限定。优选情况下,本发明中所采用的化学镀催化剂前驱体的平均粒径为1nm~1μm,更优选为1nm~500nm,最优选为1nm~100nm。其平均粒径可采用晶态激光测试仪进行测试,测试时以乙醇为分散介质。
本发明提供的白色涂料组合物中,化学镀催化剂前驱体和粘结剂是最主要的成分,粘结剂是涂料的液体成份之一。粘结剂的种类直接影响最终所形成涂层的光泽、干燥性、机械强度等性能。本发明中,所述粘结剂可以是空气固化的丙烯酸树脂,如三菱丽阳的HR-7004、HR-7008、HR-7000、HR-7100;也可以采用UV固化的丙烯酸树脂,如拜耳的U100、VP LS2396、VP LS 2266、XP2513;或者采用热固化的聚氨酯,如拜耳的PT355、XP2557;还可以采用水固化的聚氨酯,如拜耳的IL 1451、N 100、N 3390BA/SN、E 15。
所述溶剂可以直接采用水,也可采用现有技术中常见的各种有机溶剂,例如可以采用苯类溶剂、三氯乙烯、醇类溶剂、酮类溶剂、二酮溶剂或环酮溶剂。其中,苯类溶剂可以采用苯、甲苯、二甲苯。醇类溶剂的通式为CnH2n+2O,n≥1,且n为整数。优选情况下,n=1,2,3或4,例如可以为甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇。酮类溶剂的通式为CmH2mO,m≥3,且m为整数;例如可以采用丙酮、戊酮、甲乙酮。二酮溶剂的通式为CaH2a-2O2,a≥4,且a为整数。所述环酮溶剂的通式为CbH2b-2O,b=5、6、7或8;例如可采用环己酮,但不局限于此。
所述助剂为现有涂料中常用的各种助剂,例如可以选自分散剂、消泡剂、流平剂、粘性调节剂中的至少一种。
所述的分散剂可以采用德国BYK公司的ANTI-TERRA-U、DISPERBYK-101、BYK-220S、LACTIMON-WS、BYK-W 966、BYK-154、DISPERBYK-110、DISPERBYK-140、DISPERBYK-2150、DISPERBYK-2025;还可以是Akzo nobel的PHOSPHOLAN PS-236和Witco公司的PS-21A;还可以是鱼油、三油酸甘油酯、三正辛基氧膦、三正辛基膦、嘧啶、脂肪胺类、醇胺类;英国Croda公司Hypermer KD系列、Zephrym PD系列等。
所述消泡剂可以选自BYK-051、BYK-052、BYK-053、BYK-055、BYK-057、BYK-A555、BYK-071、BYK-060、BYK-018、BYK-044、BYK-094。所述流平剂可以选自BYK-333,BYK-306,BYK-358N,BYK-310,BYK-354,BYK-356。
所述粘性调节剂可以采用气相二氧化硅、聚酰胺蜡、有机膨润土、氢化蓖麻油、金属皂;也可以采用羟乙基纤维素等纤维素衍生物、聚乙烯醇、聚丙烯酸盐等水溶性树脂。
本发明提供的白色涂料组合物,其制备方法即包括将各组分混合均匀即可。具体地,可以先将化学镀催化剂前驱体和分散剂添加到溶剂中,采用行星球磨机球磨6-12hr,然后添加粘结剂、消泡剂、流平剂、粘性调节剂继续球磨6-12hr,球磨后既能得到均一稳定的白色涂料组合物。所述白色涂料组合物中,以100重量份的溶剂为基准,其中化学镀催化剂前驱体的含量为100~300重量份,粘结剂的含量为5~15重量份,助剂的含量为0.1~15重量份。优选情况下,所述白色涂料组合物中,以100重量份的溶剂为基准,分散剂的含量为0.5~4重量份,消泡剂的含量为0.3~3重量份,流平剂的含量为0.1~4重量份,粘性调节剂的含量为1~3重量份。
本发明还提供了一种绝缘基材表面选择性金属化的方法,包括以下步骤:
S1、将本发明提供的白色涂料组合物施加于绝缘基材的表面,固化后在绝缘基材表面形成白色涂层;
S2、对绝缘基材表面的白色涂层的选定区域进行激光照射,裸露出的化学镀催化剂前驱体转变为化学镀催化剂;
S3、对经过步骤S2的绝缘基材表面进行化学镀,在选定区域形成金属层。
本发明提供的表面选择性金属化的方法可适用于现有技术中常见的各种绝缘基材表面。
例如,所述绝缘基材可以为热固性塑料或热塑性塑料基材。其中,热塑性塑料可以选自聚烯烃、聚酯、聚酰胺、聚芳醚、聚酯酰亚胺、聚碳酸酯(PC)、聚碳酸酯/(丙烯腈-丁二烯-苯乙烯)合金(PC/ABS)、聚苯醚(PPO)、聚苯硫醚(PPS)、聚酰亚胺(PI)、聚砜(PSU)、聚醚醚酮(PEEK)、聚苯并咪唑(PBI)或液晶聚合物(LCP)中的一种或多种。优选情况下,聚烯烃可以为聚苯乙烯(PS)、聚丙烯(PP)、聚甲基丙烯酸甲酯或聚(丙烯腈-丁二烯-苯乙烯)。聚酯可以为聚对苯二甲酸环己烷对二甲醇酯(PCT)、聚间苯二甲酸二烯丙酯(PDAIP)、聚对苯二甲酸二烯丙酯(PDAP)、聚萘二酸丁醇酯(PBN)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)。聚酰胺可以为聚己二酰己二胺(PA-66)、聚壬二酰己二胺(PA-69)、聚丁二酰己二胺(PA-64)、聚十二烷二酰己二胺(PA-612)、聚癸二酰己二胺(PA-610)、聚癸二酰癸二胺(PA-1010)、聚十一酰胺(PA-11)、聚十二酰胺(PA-12)、聚辛酰胺(PA-8)、聚9-氨基壬酸(PA-9)、聚己内酰胺(PA-6)、聚对苯二甲酰苯二胺(PPTA)、聚间苯二甲酰己二胺(MXD6)、聚对苯二甲酰己二胺(PA6T)或聚对苯二甲酰壬二胺(PA9T)。液晶聚合物(LCP)是本领域技术人员公知的一种由刚性分子链构成的、在一定物理条件下既有液体流动性又有晶体物理性能各向异性状态(即液晶态)的高分子物质。热固性塑料可以选自酚醛树脂、脲醛树脂、三聚氰胺-甲醛树脂、环氧树脂、醇酸树脂、聚氨酯的一种或多种。
所述绝缘基材也可以是玻璃材料,例如可以为石英玻璃、高硅氧玻璃、钠钙玻璃、铅硅酸盐玻璃、铝硅酸盐玻璃或硼硅酸盐玻璃。
所述绝缘基材也可以是陶瓷材料,例如可以为氧化铝陶瓷、氮化硅陶瓷、氮化硼陶瓷、氧化铍陶瓷或氮化铝陶瓷。
所述绝缘基材也可以是水泥,例如可以为硅酸盐水泥、铝酸盐水泥、硫铝酸盐水泥、铁铝酸盐水泥、氟铝酸盐水泥或磷酸盐水泥。
所述绝缘基材也可以是木材,例如可以为胶合板、纤维板、刨花板、木丝板、木屑板或复合板。
根据本发明的方法,在绝缘基材表面施加本发明提供的白色涂料组合物,固化后即可在其表面形成白色涂层。施加过程中,涂料中的粘结剂携带着化学镀催化剂前驱体在绝缘基材表面形成墨膜,然后固着、干燥并粘附于基材表面。
本发明中,将白色涂料组合物施加于绝缘基材表面的方法可以为丝网印刷、喷涂、激光打印、喷墨打印、转印、凹版印刷、凸版印刷或平板印刷等各种方式,但不局限于此。
白色涂层的厚度无需过大,只需其能保证最终形成的金属层与绝缘基材具有良好的附着力即可。优选情况下,所述白色涂层的厚度为1-100μm。
根据本发明提供的方法,在绝缘基材表面形成白色涂层后,然后采用激光对涂层表面的选定区域进行照射,通过激光气化,在涂层表面形成图形。激光照射涂层表面的选定区域,该选定区域内涂层中的粘结剂气化,裸露出的化学镀催化剂前驱体(即SnO2、ZnSnO3、ZnTiO3中的至少一种)转变为氧空位等晶体缺陷化合物,该晶体缺陷化合物即为化学镀催化剂。
激光照射时所采用激光设备可为通用的红外激光器、紫外激光器、绿光激光器,优选绿光激光器。优选情况下,所述激光照射的条件包括:激光波长为157nm-10.6μm。另外,激光照射的条件还可包括:扫描速度为500-8000mm/s,步长为3-9μm,延时为30-100μs。激光照射时的激光频率为30-40KHz,功率为3-80W,填充间距为10-50μm。
所述选定区域可以为涂层的整个表面;也可根据实际需要为涂层表面的部分区域,激光照射完成后从而在该部分区域形成所需图形。
本发明中,涂层表面激光照射的选定区域,粘结剂气化产生烟雾。为防止烟雾落下来遮盖住化学镀催化剂,可为激光设备配置抽风装置,将烟雾尽量抽走,也可在激光气化完成后超声清洗制品表面。
根据本发明提供的方法,激光照射后,选定区域的涂层表面裸露出化学镀催化剂前驱体转变为晶格缺陷的化学镀催化剂,然后在该化学镀催化剂表面进行化学镀。所述进行化学镀的方法为本领域技术人员常用的化学镀方法,例如可以将经过激光气化的制品直接与化学镀液接触。
化学镀以镀铜为例,经过激光照射,化学镀催化剂前驱体转变为晶体缺陷型的化学镀催化剂,与化学镀铜液接触之后,化学镀催化剂能促进化学镀液中的铜离子发生还原反应,生成金属铜颗粒,包裹于化学镀催化剂表面,并互相连接形成一层致密的铜镀层,从而在涂料表面的选定区域快速形成第一层铜镀层。
为了提高镀层的表面装饰性、实用性以及耐腐蚀性,还可以在铜镀层表面继续进行至少一次化学镀和/或电镀,最后得到所述金属层。
本发明中,在化学镀催化剂表面进行化学镀铜,在涂层表面的选定区域形成铜镀层后,也可以采用现有技术常规的方法继续在铜镀层上继续形成其它金属镀层。优选情况下,为了防止涂层表面的铜镀层被氧化,可继续进行一次化学镀镍,在铜镀层表面形成一层镍镀层,得到的涂层表面的金属层从里向外具有Cu-Ni结构。更优选情况下,在Cu-Ni金属层表面通过闪镀金层,使涂层表面的金属层从里向外具有Cu-Ni-Au结构。
本发明中,形成的Cu-Ni或Cu-Ni-Au结构的金属层中,各种Ni层的厚度为0.1-50μm,优选为1-10μm,更优选为2-3μm;铜层厚度为0.1-100μm,优选为1-50μm,更优选为5-30μm;Au层的厚度为0.01-10μm,优选为0.01-2μm,更优选为0.1-1μm。
其中,所采用的化学镀铜液、化学镀镍液、电镀液铜液或电镀镍液、闪镀金层采用的镀金液均采用本领域技术人员常用的各种镀液。例如,所述化学镀铜液含有铜盐和还原剂,pH值为12-13,所述还原剂能够将铜盐中铜离子还原为铜单质,还原剂可以为乙醛酸、肼和次亚磷酸钠中的一种或几种。所述化学镀铜也还可直接采用现有技术中公开的镀铜液,例如《表面技术》2002年12月,第31卷第6期中公开的一种镀液:CuSO4·5H2O 0.12mol/L,Na2EDTA·2H2O0.14mol/L,亚铁氰化钾10mg/L,2,2’-联吡啶10mg/L,乙醛酸(HCOCOOH)0.10mol/L,并用NaOH和H2SO4调节镀液的pH值为12.5-13。另外,化学镀铜后如果觉得铜镀层厚度不足,还可进行电镀铜。化学镀镍也可采用现有技术中的镀镍液,例如其组成为:硫酸镍:23g/l,次亚磷酸钠:18g/l,乳酸:20g/l,苹果酸:15g/l,用NaOH调节pH为5.2,温度:85-90℃。
本发明中,在化学镀催化剂表面进行化学镀铜的时间没有限制,优选情况下,在化学镀催化剂表面化学镀铜的时间为10-240分钟。
在镍镀层上闪镀金层的方法也为本领域技术人员所公知,本发明中不再赘述。其中闪镀金层时采用的镀金液可直接采用深圳精研创化工公司的BG-24中性镀金液。
涂层表面未被激光照射的区域,化学镀催化剂前驱体分布于涂层的粘结剂中,不会转变为晶格缺陷型化合物,因此在化学镀铜过程中该区域不会有铜颗粒的沉积。另外,该区域表面远不如激光照射的选定区域表面粗糙,所以即使有少部分铜颗粒沉积,由于结合力较差也可轻易擦拭掉,从而实现基材表面选择性金属化。
最后,本发明提供了一种复合制品,所述复合制品包括绝缘基材和绝缘基材表面选定区域的金属层;所述复合制品由本发明提供的方法得到。所述金属层从里到外可以为Cu-Ni层或Cu-Ni-Au层,但不局限于此。
以下将结合实施例对本发明进行更详细地说明。实施例中所用原料均由商购得到。
实施例1
(1)将200质量份平均粒径为50nm的SnO2和2.9质量份分散剂DISPERBYK-110添加到100质量份溶剂乙醇中,采用行星球磨机球磨8h;然后添加10质量份粘结剂HR-7004、2.3质量份消泡剂BYK-053、3.27质量份流平剂BYK-306、2.95质量份粘性调节剂气相二氧化硅,继续球磨9h,获得均一稳定的白色涂料组合物S10;
(2)将白色涂料组合物S10喷涂到LED灯电路板载体表面,得到白色LED灯电路板载体(其表面白色涂层厚度为17.6μm);
(3)采用红外激光器(泰德,DPF-M12)对白色LED灯电路板载体的选定区域进行照射,在其表面打印出金属线路图形,激光照射条件包括:波长1064nm,扫描速度1000mm/s,步长9μm,延时30μs,频率40KHz,功率3W,填充间距50μm;激光照射完成后,超声清洗;
(4)将清洗后的制品整体浸入化学镀铜液中4h,形成厚度为15μm的铜层;再浸入化学镀镍液10min,形成厚度为5μm的镍层;最后闪镀0.03μm厚的金层。其中,化学镀铜液:CuSO4·5H2O 0.12mol/L,Na2EDTA·2H2O 0.14mol/L,亚铁氰化钾10mg/L,2,2’-联吡啶10mg/L,乙醛酸(HCOCOOH)0.10mol/L,并用NaOH和H2SO4调节镀液的pH值为12.5-13;化学镀镍液:硫酸镍:23g/l,次亚磷酸钠:18g/l,乳酸:20g/l,苹果酸:15g/l,用NaOH调节pH为5.2;闪镀金液采用深圳精研创化工公司公司的BG-24中性镀金液。
通过上述步骤,得到本实施例的白色LED灯电路板载体,记为A1。
实施例2
采用与实施例1相同的方法制备本实施例的复合制品,不同之处在于:
步骤(1)中,将275质量份平均粒径为20nm的ZnTiO3和3.4质量份分散剂DISPERBYK-2150添加到100质量份溶剂甲乙酮中,采用行星球磨机球磨12h;然后添加13质量份粘结剂XP 2513、2.65质量份消泡剂BYK-018、3.44质量份流平剂BYK-356、2.3质量份粘性调节剂聚酰胺蜡,继续球磨12h,获得均一稳定的白色涂料组合物S20;
步骤(2)中,采用凹版印刷将白色涂料组合物S20印刷到汽车发动机电子连接器外壳表面,得到白色汽车发动机电子连接器外壳(其表面白色涂层厚度为29.4μm);
步骤(3)中,采用红外激光器(泰德,DPF-M12)对白色汽车发动机电子连接器外壳的选定区域进行照射,在其表面打印出金属线路图形,激光照射条件为:波长1064nm,扫描速度1000mm/s,步长9μm,延时30μs,频率40KHz,功率3W,填充间距50μm;激光照射完成后,超声清洗该汽车发动机电子连接器外壳表面;
步骤(4)中,化学镀的顺序为:先化学镀铜4h形成15μm的铜层,再化学镀镍10min形成5μm厚的镍层,最后闪镀0.03μm的金层。
通过上述步骤,得到本实施例的用作汽车发动机电子连接器外壳的白色塑料复合制品,记为A2。
实施例3
采用与实施例1相同的方法制备本实施例的复合制品,不同之处在于:
步骤(1)中,将110质量份平均粒径为90nm的ZnSnO3和0.7质量份分散剂DISPERBYK-140添加到100质量份溶剂水中,采用行星球磨机球磨7h;然后添加6质量份粘结剂XP2557、0.45质量份消泡剂BYK-051、0.16质量份流平剂BYK-333、1.64质量份粘性调节剂聚乙烯醇,继续球磨8h,获得均一稳定的白色涂料组合物S30;
步骤(2)中,采用转印技术将白色涂料组合物S30施加到陶瓷集成电路基座表面,形成的白色涂层的厚度为87μm;
步骤(3)中,采用绿光激光器(大族,EP-25-THG-D)对陶瓷集成电路基座的选定区域进行照射,在其表面打印出金属线路图形,激光照射条件为:波长532nm,扫描速度2000mm/s,步长9μm,延时30μs,频率40KHz,功率4W,填充间距50μm;激光照射完成后,超声清洗该集成电路基座陶瓷件表面;
步骤(4)中,化学镀的顺序为:先化学镀铜3h形成7μm的铜层,再化学镀镍10min形成5μm厚的镍层。
通过上述步骤,得到本实施例的用作集成电路基座的白色陶瓷复合制品,记为A3。
实施例4
采用与实施例1相同的方法制备本实施例的复合制品,不同之处在于:
步骤(1)中,将100质量份平均粒径为20nm的SnO2、146质量份平均粒径为70nm的ZnSnO3和3.15质量份分散剂BYK-W 966添加到100份溶剂甲苯中,采用行星球磨机球磨11h;然后添加11.5质量份粘结剂U100、2.44质量份消泡剂BYK-071、2.67质量份流平剂BYK-358N、2.05质量份粘性调节剂气相二氧化硅,继续球磨10h,获得均一稳定的白色涂料组合物S40;
步骤(2)中,采用平板印刷技术将白色涂料组合物S40施加到石英玻璃基板表面,制成白色石英玻璃基板(其表面白色涂层厚度为65μm);
步骤(3)中,采用绿光激光器(大族,EP-25-THG-D)对白色石英玻璃基板的选定区域进行照射,在其表面打印出金属线路图形,激光照射条件为:波长532nm,扫描速度2000mm/s,步长9μm,延时30μs,频率40KHz,功率4W,填充间距50μm;激光照射完成后,超声清洗该石英玻璃基板表面;
步骤(4)中,化学镀的顺序为:先化学镀铜4h形成12μm的铜层,再化学镀镍10min形成5μm厚的镍层,最后闪镀0.03μm的金层。
通过上述步骤,得到本实施例用作石英玻璃基板的白色玻璃复合制品,记为A4。
实施例5
采用与实施例1相同的方法制备本实施例的复合制品,不同之处在于:
步骤(1)中,将30质量份平均粒径为20nm的SnO2、55质量份平均粒径为60nm的ZnSnO3、70质量份平均粒径为60nm的ZnTiO3和1.96质量份分散剂BYK-154添加到100份溶剂甲醇中,采用行星球磨机球磨11h;然后添加9.7质量份粘结剂HR-7100、1.93质量份消泡剂BYK-057、2.98质量份流平剂BYK-354、2.34质量份粘性调节剂羟乙基纤维素,继续球磨9h,获得均一稳定的白色涂料组合物S50;
步骤(2)中,采用转印技术将白色涂料组合物S50施加到电子连接器壳体表面,制成白色电子连接器壳体(其表面白色涂层厚度为37μm);
步骤(3)中,采用红外激光器(泰德,DPF-M12)对白色电子连接器壳体的选定区域进行照射,在其表面打印出金属线路图形,激光照射条件为:波长1064nm,扫描速度1000mm/s,步长9μm,延时30μs,频率40KHz,功率3W,填充间距50μm;激光照射完成后,超声清洗该电子连接器壳体表面;
步骤(4)中,化学镀的顺序为:先化学镀铜4h形成15μm的铜层,再化学镀镍10min形成5μm厚的镍层,最后闪镀0.03μm的金层。
通过上述步骤,得到本实施例的用作电子连接器壳体的白色塑料复合制品,记为A5。
性能测试
采用GB9286-88公开的方法对实施例1-5得到的复合制品A1-A5进行结合力测试,记录各复合制品表面镀层的结合力级别。测试结果如表1所示。0级结合力最佳,一般超过2级在防腐涂料中即认为结合力达不到要求。
0级切割边缘完全平滑,无一格脱落;
1级在切口交叉处涂层有少许薄片分离,但划格区受影响明显不超过5%;
2级切口边缘或交叉处涂层脱落明显大于5%,但受影响不大于15%;
3级涂层边缘部分或全部大碎片脱落,在15%-35%之间。
表1
样品 | 镀层结合力(级) |
A1 | 1 |
A2 | 1 |
A3 | 0 |
A4 | 0 |
A5 | 0 |
从表1的测试结果可以看出,采用本发明所提供的白色涂料在绝缘基材表面形成白色涂层后,激光活化并选择性化学镀后形成的复合制品,其表面镀层结合力均较好。
Claims (11)
1.一种绝缘基材表面选择性金属化的方法,其特征在于,包括以下步骤:
S1、将白色涂料组合物施加于绝缘基材的表面,固化后在绝缘基材表面形成白色涂层;
S2、对绝缘基材表面的白色涂层的选定区域进行激光照射,裸露出的化学镀催化剂前驱体转变为化学镀催化剂;
S3、对经过步骤S2的绝缘基材表面进行化学镀,在选定区域形成金属层;其中,所述白色涂料组合物中含有化学镀催化剂前驱体、粘结剂、溶剂,含或不含助剂;所述化学镀催化剂前驱体选自SnO2、ZnSnO3、ZnTiO3中的至少一种。
2.根据权利要求1所述的方法,其特征在于,以100重量份的溶剂为基准,所述白色涂料组合物中化学镀催化剂前驱体的含量为100~300重量份,粘结剂的含量5~15重量份,助剂的含量为0.1~15重量份。
3.根据权利要求1或2所述的方法,其特征在于,所述化学镀催化剂前驱体的平均粒径为1nm~1μm。
4.根据权利要求1或2所述的方法,其特征在于,所述粘结剂选自空气固化的丙烯酸树脂、UV固化的丙烯酸树脂、热固化聚氨酯和水固化聚氨酯中的任意一种;
所述溶剂选自水、苯类溶剂、三氯乙烯、通式为CnH2n+2O的醇类、通式为CmH2mO的酮类、通式为CaH2a-2O2的二酮或通式为CbH2b-2O的环酮,其中n≥1,m≥3,a≥4,n、m、a均为整数,b=5、6、7或8。
5.根据权利要求1或2所述的方法,其特征在于,所述助剂选自分散剂、消泡剂、流平剂、粘性调节剂中的至少一种。
6.根据权利要求1所述的方法,其特征在于,所述绝缘基材选自塑料、玻璃、陶瓷、水泥或木材。
7.根据权利要求1所述的方法,其特征在于,步骤S1中,所述白色涂层的厚度为1-100μm。
8.根据权利要求1所述的方法,其特征在于,步骤S2中,所述激光照射的条件包括:激光波长为157nm-10.6μm。
9.根据权利要求1或8所述的方法,其特征在于,步骤S2中,所述激光照射的条件包括:扫描速度为500-8000mm/s,步长为3-9μm,延时为30-100μs。
10.根据权利要求1或8所述的方法,其特征在于,步骤S2中,所述激光照射的条件包括:激光频率为30-40KHz,功率为3-80W,填充间距为10-50μm。
11.一种复合制品,其特征在于,所述复合制品包括绝缘基材和绝缘基材表面选定区域的金属层;所述复合制品由权利要求1-10任一项所述的方法得到。
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EP2912211B1 (en) | 2018-09-26 |
US10085351B2 (en) | 2018-09-25 |
WO2014063636A1 (en) | 2014-05-01 |
US20150189762A1 (en) | 2015-07-02 |
CN103773143B (zh) | 2017-02-22 |
JP2016500733A (ja) | 2016-01-14 |
CN106519740A (zh) | 2017-03-22 |
CN103773143A (zh) | 2014-05-07 |
EP2912211A1 (en) | 2015-09-02 |
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