CN115010977A - 一种mlcc用离型材料及其制备方法 - Google Patents

一种mlcc用离型材料及其制备方法 Download PDF

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CN115010977A
CN115010977A CN202210663106.4A CN202210663106A CN115010977A CN 115010977 A CN115010977 A CN 115010977A CN 202210663106 A CN202210663106 A CN 202210663106A CN 115010977 A CN115010977 A CN 115010977A
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张庆杰
麦启波
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Jiangsu Huangguan New Material Technology Co ltd
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Abstract

本发明涉及一种MLCC用离型材料及其制备方法,属于离型材料技术领域。包括防黏连层、离型层和设置于所述防黏连层和离型层之间的基材层,按质量分数计,所述防黏连层包括:低聚物20‑30%、丙烯酸酯类单体10‑20%、纳米微球I 4‑10%、纳米微球II 2‑5%、光引发剂2‑5%、流平剂1‑2%和有机溶剂40‑60%;所述离型层包括:有机硅聚合物30‑40%、架桥剂1‑5%、锚固剂1‑3%、铂族金属催化剂1‑5%、稀释剂40‑60%,纳米微球I 3‑5%,纳米微球II 1‑3%和抗静电剂1‑5%;所述低聚物为聚氨酯丙烯酸酯低聚物和/或聚丙烯酸酯低聚物。所述的离型材料不仅具有离型材料的MLCC流延用性能,同时具有离型层面平整、洁净度高,可用于光学胶黏材料的粘结贴附,而且背面采用防黏连层处理,收卷平整,外观整洁。

Description

一种MLCC用离型材料及其制备方法
技术领域
本发明属于离型材料技术领域,尤其涉及一种MLCC用离型材料及其制备方法。
背景技术
随着5G时代的到来,人们对多层陶瓷电容(Multi-layer Ceramic Capacitors,MLCC)的需求量越来越迫切。在多层陶瓷电容的制造过程中,人们需要对陶瓷浆料进行流延涂布,而流延涂布过程则需要利用到性能优异的专用MLCC离型膜材料(俗称流延载膜)。MLCC离型膜要求具备平整度高、低粗糙度、离型力稳定、高残余、浆料适配性强、高拉伸强度、无针尖、无异物点、无彩虹纹、无排骨纹、无纵纹和高透光率等特点。目前,国内的MLCC制造厂商几乎只能依赖于日韩企业所生产的流延载膜,这一点极大地限制了我国MLCC行业的国产化和成本降低,因此,制备出满足需求的MLCC用离型膜至关重要。通常采用的技术方案是选用高平整度基膜,进本以日韩进口为主,或者采用表面处理实现一定的平整度(CN112280085 A),这些技术方案确实可以实现一定的平整度,但是对基膜材料依赖性非常强或者过多的工艺处理都会影响基膜材料的平整度,从而影响MLCC流延过程易出现表面瑕疵或者堆叠后分层时易出现剥离不良等问题。
发明内容
为此,本发明所要解决的技术问题在于克服现有技术中MLCC流延用离型膜的平整度差、不易剥离的问题。
为解决上述技术问题,本发明提供了一种MLCC用离型材料及其制备方法。
本发明的第一个目的是提供一种MLCC用离型材料,包括防黏连层、离型层和设置于所述防黏连层和离型层之间的基材层,按质量分数计,所述防黏连层包括:低聚物20-30%、丙烯酸酯类单体10-20%、纳米微球I 4-10%、纳米微球II 2-5%、光引发剂2-5%、流平剂1-2%和有机溶剂40-60%;所述离型层包括:有机硅聚合物30-40%、架桥剂1-5%、锚固剂1-3%、铂族金属催化剂1-5%、稀释剂40-60%,纳米微球I 3-5%,纳米微球II 1-3%和抗静电剂1-5%;所述低聚物为聚氨酯丙烯酸酯低聚物和/或聚丙烯酸酯低聚物。
在本发明的一个实施例中,所述聚氨酯丙烯酸酯低聚物为3官能度以上的聚氨酯丙烯酸酯低聚物。
在本发明的一个实施例中,所述聚丙烯酸酯低聚物为3官能度以上的聚丙烯酸酯低聚物。
在本发明的一个实施例中,所述丙烯酸酯类单体为2官能度以上的丙烯酸酯类化合物。
在本发明的一个实施例中,所述纳米微球I和所述纳米微球II独立选自纳米氧化铝、纳米二氧化硅和纳米氧化锌中的一种或多种;所述纳米微球I的粒径为150-200nm;所述纳米微球II的粒径为50-100nm。
在本发明的一个实施例中,所述光引发剂选自1-羟基环己基苯基甲酮、2-甲基-1-(4-甲巯基苯基)-2-吗啉基-1-丙酮、2,4,6-三甲基苯基甲酰基-二苯基氧化膦、二甲苯酮和2-羟基-2-甲基苯基丙烷-1-酮中的一种或多种。
在本发明的一个实施例中,所述流平剂选自丙烯酸酯流平剂和/或有机硅聚醚流平剂。
在本发明的一个实施例中,所述有机溶剂是由酮类溶剂和酯类溶剂混合所得;所述酮类溶剂和所述酯类溶剂的体积比为1.5-2.5:1。
在本发明的一个实施例中,所述有机硅聚合物为分子内含有2个以上乙烯基的有机硅聚合物。
优选地,所述有机硅聚合物为端乙烯基硅油,所述端乙烯基硅油结构式如下所示:
Figure BDA0003691832040000031
其中,R1为1-8个碳原子的烷烃,R3为乙烯基,p为100-2000,q为0-100,乙烯基含量为0.01-0.3%,粘度为1000-100000mpa.s。
优选地,R1为甲基,p为200-2000,粘度为2000-50000mpa.s。更优选地,粘度为5000-20000mpa.s。
优选地,所述有机硅聚合物为陶氏化学LTC759、LTC310、LTC752系列硅油。
在本发明的一个实施例中,所述架桥剂为分子内含有2个以上Si-H键的含氢有机硅聚合物。
优选地,所述架桥剂为陶氏交联剂7672。
在本发明的一个实施例中,所述锚固剂选自环氧丙基三乙氧基硅烷、锚固剂DOWSyl-OffSL9106和锚固剂SL297中的一种或多种。
在本发明的一个实施例中,所述稀释剂选自甲苯、二甲苯、己烷、庚烷、丙酮、甲基异丁基酮、乙酸乙酯和乙酸丁酯中的一种或多种。
在本发明的一个实施例中,所述抗静电剂选自烷基磺酸类化合物、乙氧基化脂肪族烷基胺、聚噻吩类化合物、镍粉、铜粉、银粉、碳纳米管颗粒和季铵盐中的一种或多种。
在本发明的一个实施例中,所述防黏连层的厚度为1-2μm。所述防黏连层具有防黏连功能,同时有一定防刮伤效果。
在本发明的一个实施例中,所述基材层为PET膜、PE膜或PP膜。
本发明的第二个目的是提供一种所述MLCC用离型材料的制备方法,包括以下步骤,
将防黏连层材料涂布在基材层一侧上,75-85℃光照1-3min烘干,后在基材层另一侧上涂布离型层材料,100-130℃热固化得到所述MLCC用离型材料。
在本发明的一个实施例中,所述涂布离型层材料的涂布量为0.1-0.3g/m2
本发明的技术方案相比现有技术具有以下优点:
(1)本发明所述的MLCC用离型材料不仅具有离型材料的MLCC流延用性能,同时具有离型层面平整、洁净度高,可用于光学胶黏材料的粘结贴附,而且背面采用防黏连层处理,收卷平整,外观整洁。
(2)本发明所述的MLCC用离型材料背面的防黏连层处理,不仅具有防止材料多层堆叠后出现黏连吸附不易剥离问题,同时也可具有一定防刮伤效果,以免出现局部刮伤不良。
(3)本发明所述的MLCC用离型材料离型层采用有机硅处理,具有耐高温性,离型力稳定,同时具有防静电效果,防止自吸附及吸附灰尘,保证了表面的平整度和洁净度。
(4)本发明所述的MLCC用离型材料离型层在有机硅中添加纳米微球,具有防止多层堆叠后出现黏连吸附不易剥离的问题,同时也具有一定的防刮伤效果,以避免出现局部离型不良。
具体实施方式
下面结合具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
实施例1
一种MLCC用离型材料及其制备方法,具体包括以下步骤:
(1)首先在基材PET膜的一面涂覆防黏连层材料:
聚丙烯酸酯低聚物(20质量份),沙多玛CN8200NS(聚酯丙烯酸酯);
丙烯酸酯类单体(15质量份),沙多玛SR444NS(季戊四醇三丙烯酸酯);
纳米微球I(150-200nm)(5质量份),纳米氧化铝;
纳米微球II(50-100nm)(3质量份),纳米氧化铝;
光引发剂(3质量份),1-羟基环己基苯基甲酮;
流平剂(2质量份),丙烯酸酯流平剂BYK-354;
有机溶剂(52质量份),为丁酮和乙酸乙酯的混合物,其中,丁酮和乙酸乙酯的体积比为2:1;
经UV照射80℃*2min后,形成厚度1-2μm防黏连层,具有防黏连功能,同时有一定防刮伤效果;
(2)然后再在基材PET膜的另一面涂覆可流延离型层材料:
有机硅聚合物(30质量份),陶氏LTC759;
架桥剂(1质量份),陶氏交联剂7672;
锚固剂(1质量份),环氧丙基三乙氧基硅烷;
催化剂(1质量份),陶氏催化剂4000;
稀释剂(60质量份),甲苯;
纳米微球I(150nm-200nm)(4质量份),纳米二氧化硅;
纳米微球II(50-100nm)(2质量份),纳米二氧化硅;
抗静电剂(1质量份),无锡畅宏ASA3010-ISO;
经辊式涂布,涂布量控制在0.2g/m2,120℃*1min热固化后收卷制备而成。
实施例2
一种MLCC用离型材料及其制备方法,具体包括以下步骤:
(1)首先在基材PE膜的一面涂覆防黏连层材料:
聚氨酯丙烯酸酯低聚物(25质量份),沙多玛CN8009NS(脂肪族聚氨酯丙烯酸酯);
丙烯酸酯类单体(10质量份),SR344(聚乙二醇二丙烯酸酯);
纳米微球I(150)(8质量份),纳米二氧化硅;
纳米微球II(100nm)(3质量份),纳米二氧化硅;
光引发剂(5质量份),1-羟基环己基苯基甲酮;
流平剂(2质量份),有机硅聚醚流平剂,毕克化学BYK333;
有机溶剂(47质量份),有机溶剂为丙酮和乙酸丁酯的混合物,其中,丙酮和乙酸丁酯的体积比为2:1;
经UV照射80℃*2min后,形成厚度1-2μm防黏连层,具有防黏连功能,同时有一定防刮伤效果;
(2)然后再在基材PE膜的另一面涂覆可流延离型层材料:
有机硅聚合物(35质量份),陶氏LTC310;
架桥剂(3质量份),陶氏7672;
锚固剂(2质量份),锚固剂DOW Syl-OffSL9106;
催化剂(3质量份),陶氏催化剂4000;
稀释剂(50质量份),二甲苯;
纳米微球I(150nm-200nm)(4质量份),纳米二氧化硅;
纳米微球II(50-100nm)(2质量份),纳米二氧化硅;
抗静电剂(1质量份),信越SAS-F16(溶剂型硅系添加型);
经辊式涂布,涂布量控制在0.2g/m2,120℃*1min热固化后收卷制备而成。
实施例3
一种MLCC用离型材料及其制备方法,具体包括以下步骤:
(1)首先在基材一面PP膜的涂覆防黏连层材料:
聚氨酯丙烯酸酯低聚物(25质量份),CN8000NS(脂肪族聚氨酯丙烯酸酯);
丙烯酸酯类单体(10质量份),SR344(聚乙二醇二丙烯酸酯);
纳米微球I(150)(8质量份),纳米二氧化硅;
纳米微球II(100nm)(3质量份),纳米二氧化硅;
光引发剂(5质量份),1-羟基环己基苯基甲酮;
流平剂(2质量份),有机硅聚醚流平剂毕克化学BYK333;
有机溶剂(47质量份),为丁酮和乙酸乙酯的混合物,其中,丁酮和乙酸乙酯的体积比为2:1;
经UV照射80℃*2min后,形成厚度1-2μm防黏连层,具有防黏连功能,同时有一定防刮伤效果;
(2)然后再在基材PP膜的另一面涂覆可流延离型层材料:
有机硅聚合物(35质量份),陶氏LTC752;
架桥剂(3质量份),陶氏7672;
锚固剂(2质量份),锚固剂DOW Syl-OffSL9106;
催化剂(3质量份),陶氏催化剂4000;
稀释剂(50质量份),己烷;
纳米微球I(150nm-200nm)(5质量份),纳米二氧化硅;
纳米微球II(50-100nm)(1质量份),纳米二氧化硅;
抗静电剂(1质量份),信越SAS-F16(溶剂型硅系添加型);
经辊式涂布,涂布量控制在0.2g/m2,120℃*1min热固化后收卷制备而成。
实施例4
一种MLCC用离型材料及其制备方法,具体包括以下步骤:
(1)首先在基材PET膜的一面涂覆防黏连层材料:
聚氨酯丙烯酸酯低聚物(30质量份),CN8000NS(脂肪族聚氨酯丙烯酸酯);
丙烯酸酯类单体(10质量份),SR444D NS;
纳米微球I(150-200nm)(8质量份),纳米二氧化硅;
纳米微球II(50-100nm)(2质量份),纳米氧化锌;
光引发剂(4质量份),2-羟基-2-甲基苯基丙烷-1-酮;
流平剂(2质量份),有机硅聚醚流平剂,毕克化学BYK310;
有机溶剂(44质量份),为丁酮和乙酸乙酯的混合物,其中,丁酮和乙酸乙酯的体积比为2:1;
经UV照射80℃*2min后,形成厚度1-2μm防黏连层,具有防黏连功能,同时有一定防刮伤效果;
(2)然后再在基材PET膜的另一面涂覆可流延离型层材料:
有机硅聚合物(40质量份),陶氏LTC752;
架桥剂(5质量份),陶氏7672;
锚固剂(3质量份),锚固剂SL297。
催化剂(3质量份),陶氏催化剂4000;
稀释剂(40质量份),庚烷;
纳米微球I(150nm-200nm)(5质量份),纳米氧化铝;
纳米微球II(50-100nm)(3质量份),纳米二氧化硅;
抗静电剂(1质量份),碳纳米管颗粒;
经辊式涂布,涂布量控制在0.2g/m2,120℃*1min热固化后收卷制备而成。
对比例1
只在基材PET膜的一面涂覆一层离型层:
有机硅聚合物(40质量份),陶氏7458;
架桥剂(5质量份),陶氏7672;
锚固剂(3质量份),锚固剂SL297;
催化剂(3质量份),陶氏催化剂4000;
稀释剂(40质量份),庚烷;
经辊式涂布,涂布量控制在0.2g/m2,采用150℃*2min加热固化后收卷制备而成。
对比例2
(1)首先在基材PET膜涂覆一层聚噻吩溶液抗静电层,经高温120℃*2min热固化后收卷制备而成。
(2)然后再在基材PET膜的抗静电层面涂覆可流延离型层材料:
有机硅聚合物(40质量份),陶氏7468;
架桥剂(5质量份),陶氏7672;
锚固剂(3质量份),锚固剂SL297;
催化剂(3质量份),陶氏催化剂4000;
稀释剂(40质量份),庚烷;
经辊式涂布,涂布量控制在0.2g/m2,采用150℃*2min固化后收卷制备而成。
测试例
对本发明实施例1-4和对比例1-2的材料的离型力、残余接着率、透过率、雾度、阻抗值等性能进行测试,具体相关性能的测试方法如下;
(1)24h离型力(gf/25mm):参照GB/T 25256-2010标准测试;
(2)20h老化离型力(gf/25mm):参照GB/T 25256-2010标准测试;
(3)残余接着率%:参照GB/T 25256-2010标准测试;
(4)透过率%:参照GB/T 2410-2008执行;
(5)雾度%:参照GB/T 2410-2008执行;
(6)阻抗值(Ω):参照GB/T 33375-2016执行;
(7)离型层面粗糙度(Ra)nm:参照GB/T 1031-2009执行;
(8)AB面粗糙度(Ra)nm:参照GB/T 1031-2009执行;
(9)AB面铅笔硬度:参照GB/T 6739-2006执行。
表1所示为最终测得的相关参数:
表1
试样 实施例1 实施例2 实施例3 实施例4 对比例1 对比例2
24离型力 15 12 12 10 20 28
20h老化离型力 17 15 14 12 27 30
残余接着率 85 87 90 90 85 85
透过率 89 90 89 90 85 89
雾度 1.2 1.1 1.1 1.0 3.2 5.2
阻抗值 10<sup>9</sup> 10<sup>9</sup> 10<sup>9</sup> 10<sup>9</sup> 10<sup>12</sup> 10<sup>10</sup>
离型层面粗糙度 45 30 20 40 100 150
防黏连层面粗糙度 100 80 80 100 40 50
防黏连层面铅笔硬度 H H H H 5B 5B
从表1可以看出,通过本发明方案实施例1-4制备的MLCC用离型材料离型层粗糙度低,平整度高,具有优异的离型剥离性能,同时防黏连层有一定的粗糙度和铅笔硬度,可防止MLCC堆叠过程产生黏连和刮伤的问题,而对比例1-2采用了普通离型层粗糙度偏高表面发涩,会对MLCC层有吸附性不易剥离,同时背面没有做防黏连层处理,MLCC堆叠过程容易产生黏连和刮伤,影响产品质量。
显然,上述实施例仅仅是为清楚地说明所作的举例,并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

1.一种MLCC用离型材料,包括防黏连层、离型层和设置于所述防黏连层和离型层之间的基材层,其特征在于,按质量分数计,所述防黏连层包括:低聚物20-30%、丙烯酸酯类单体10-20%、纳米微球I 4-10%、纳米微球II 2-5%、光引发剂2-5%、流平剂1-2%和有机溶剂40-60%;所述离型层包括:有机硅聚合物30-40%、架桥剂1-5%、锚固剂1-3%、铂族金属催化剂1-5%、稀释剂40-60%,纳米微球I 3-5%,纳米微球II 1-3%和抗静电剂1-5%;所述低聚物为聚氨酯丙烯酸酯低聚物和/或聚丙烯酸酯低聚物。
2.根据权利要求1所述的MLCC用离型材料,其特征在于,所述纳米微球I和所述纳米微球II独立选自纳米氧化铝、纳米二氧化硅和纳米氧化锌中的一种或多种;所述纳米微球I的粒径为150-200nm;所述纳米微球II的粒径为50-100nm。
3.根据权利要求1所述的MLCC用离型材料,其特征在于,所述光引发剂选自1-羟基环己基苯基甲酮、2-甲基-1-(4-甲巯基苯基)-2-吗啉基-1-丙酮、2,4,6-三甲基苯基甲酰基-二苯基氧化膦、二甲苯酮和2-羟基-2-甲基苯基丙烷-1-酮中的一种或多种。
4.根据权利要求1所述的MLCC用离型材料,其特征在于,所述流平剂选自丙烯酸酯流平剂和/或有机硅聚醚流平剂。
5.根据权利要求1所述的MLCC用离型材料,其特征在于,所述有机溶剂是由酮类溶剂和酯类溶剂混合所得;所述酮类溶剂和所述酯类溶剂的体积比为1.5-2.5:1。
6.根据权利要求1所述的MLCC用离型材料,其特征在于,所述架桥剂为分子内含有2个以上Si-H键的含氢有机硅聚合物。
7.根据权利要求1所述的MLCC用离型材料,其特征在于,所述锚固剂选自环氧丙基三乙氧基硅烷、锚固剂DOW Syl-OffSL9106和锚固剂SL297中的一种或多种。
8.根据权利要求1所述的MLCC用离型材料,其特征在于,所述稀释剂选自甲苯、二甲苯、己烷、庚烷、丙酮、甲基异丁基酮、乙酸乙酯和乙酸丁酯中的一种或多种。
9.根据权利要求1所述的MLCC用离型材料,其特征在于,所述抗静电剂选自烷基磺酸类化合物、乙氧基化脂肪族烷基胺、聚噻吩类化合物、镍粉、铜粉、银粉、碳纳米管颗粒和季铵盐中的一种或多种。
10.权利要求1-9任一项所述MLCC用离型材料的制备方法,其特征在于,包括以下步骤,
将防黏连层材料涂布在基材层一侧上,烘干后在基材层另一侧上涂布离型层材料,固化得到所述MLCC用离型材料。
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