CN117511127A - 一种环氧树脂组合物及其制备方法与应用 - Google Patents
一种环氧树脂组合物及其制备方法与应用 Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
- C08G59/186—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract
本申请公开了一种环氧树脂组合物及其制备方法与应用,属于环氧树脂组合物技术领域。本发明提供的环氧树脂组合物制得的绝缘保护浆料具有印刷性能优异、低吸湿性的优点,固化后浆料具有合适的硬度与韧性,能够避免电阻生产过程中出现保护层损坏现象;浆料固化后形成之致密的绝缘保护膜,和氧化铝基片具有较强的结合力,能够提升片式电阻在高温高湿环境下的可靠性。
Description
技术领域
本申请属于环氧树脂组合物技术领域,具体涉及一种环氧树脂组合物及其制备方法与应用。
背景技术
随着车规级电子产品的性能要求愈来愈严格,对电子元器件可靠性的要求也越来越高,尤其是应用在高温高湿且通额定电压环境下的电子产品,需要电子元器件在高温、高湿环境下无失效发生。本领域常用环氧树脂当保护材料或填充无机材料形成复合材料组方黏着剂,广泛应用于消费性电子、通讯电子设备、汽车电子等领域中。
现有技术常采用环氧氯丙烷、双酚-A、双酚-F或羟基酚醛树脂合成环氧树脂,采用该方法制得的成品的副产物是HCl,其中的氯离子很难通过化学或物性处理法被完全去除,利用XRF仪器分析总氯含量约有500~1000ppm,而由于氯离子容易和金属电阻材料(例如:铜、银、镍铬、锡等等)形成金属氯化物,在潮湿环境通额定电压下电阻容易离子迁移,导极产品失效,且氯离子极性较高,所以容易和水分子形成分子间作用力的氢键的特性,例如:片式电阻在85℃/85%RH,60℃/95%RH,40℃/95%RH常见测试规范高温潮湿环境且通10%额定功率下电阻体容易形成离子迁移,造成阻值变化大于AEC-Q200规范范围甚至发生开路形式的失效模式,导致电阻失效。
针对上述环氧树脂组合物中存在的问题,寻找一种卤素含量为0、耐湿热能力优异的环氧树脂组合物是本领域研究的重点。
发明内容
本申请的目的在于克服上述现有技术的不足之处而提供一种环氧树脂组合物及其制备方法与应用,所述环氧树脂组合物的总卤素含量为0ppm,且可大幅度提升片式电阻在高温高湿环境下的可靠性与稳定性。
为实现上述目的,本申请采取的技术方案为:
一种环氧树脂组合物,所述环氧树脂组合物包括A组分和B组分,所述A组分包括环氧树脂、二羧酸和促进剂,所述B组分包括固化剂和促进剂;所述环氧树脂包括二官能基脂环族环氧树脂及其衍生物、三官能基脂环族环氧树脂及其衍生物中的至少两种;所述固化剂包括甲基六氢苯酐及其衍生化合物、羟基酚醛衍生化合物、苯并恶嗪衍生化合物中的至少一种。
由于环氧树脂的化学结构式较刚硬,且常用的甲基六氢苯酐固化剂固化后较硬脆,因此极大影响了此类环氧树脂的应用;针对此,本发明采用二羧酸与环氧树脂在特定促进剂下加热形成加成反应,改善环氧树脂的脆性,并提高对基板的黏结性,使用前再将A组分和B组分进行固化反应,固化后可改善固化剂的脆性,并提高最终制得的浆料对氧化铝基板的黏结性,有效提升了片式电阻的耐湿热性能。
所述甲基六氢苯酐的结构式如下式所示:
所述R为甲基。
作为本申请环氧树脂组合物的优选实施方式,以环氧树脂组合物计,所述环氧树脂的重量份为10-60份,所述二羧酸的重量份为5-50份,所述固化剂的重量份为5-55份,所述环氧树脂的重量份为0.1-10份;发明人通过大量实验发现,各组分在上述重量份条件下,可使最终制得的产品性能更优异。
作为本申请环氧树脂组合物的优选实施方式,所述促进剂选自三级胺、咪唑衍生物、阴阳离子型触媒、脲、取代的脲、改性咪唑中的至少一种。
作为本申请环氧树脂组合物的更优选实施方式,所述促进剂包括甲苯双-二甲基脲、3-苯基-1,1-二甲基脲、叔丙烯酰胺、亚烷基胺、2,4,6-三(二甲基氨基甲基)-苯酚、2-苯基-咪唑、2-甲基咪唑、1-甲基咪唑、2-乙基-4-甲基咪唑、4,4'-亚甲基-双(2-乙基-5-甲基咪唑)2-乙基-2-甲基咪唑、N-丁基咪唑、6-己内酰胺中的至少一种。
作为本申请环氧树脂组合物的优选实施方式,所述环氧树脂组合物还包括下述重量份的组分:黑色颜料3-7份,无机填料10-65份,助剂0.2-10份。
作为本申请环氧树脂组合物的更优选实施方式,所述黑色颜料包括绝缘无机炭黑、体质颜料中的至少一种。
作为本申请环氧树脂组合物的更优选实施方式,所述无机填料包括二氧化硅、氧化铝、氢氧化铝、硫酸钡、石英粉、滑石粉、氮化铝中的至少一种;发明人通过大量实验发现,上述无机填料能够改变浆料的流动性能,增强浆料印刷性能,浆料的绝缘性能和强度。
作为本发明的最优选实施方式,所述二氧化硅为疏水球形或不规则形状的二氧化硅,粒径为1nm-10um;疏水二氧化硅在环氧体系中流动性较好,易于分散,可降低树脂的吸水率;且不同粒径二氧化硅的同时使用能够降低浆料的热膨胀系数,增加制得的浆料的致密性,降低树脂体系的收缩率,从而提高浆料抵抗湿热的能力,使浆料印刷后表面光滑,固化后硬度高,粗糙度小,绝缘电阻高。
作为本申请环氧树脂组合物的更优选实施方式,所述助剂包括流平剂、消泡剂、润湿分散剂、硅烷偶联剂中的至少一种。
优选地,所述助剂中,以环氧树脂组合物计,所述流平剂的重量份为0.5-5份,所述消泡剂的重量份为0.5-5份,所述润湿分散剂的重量份为0.1-5份,所述硅烷偶联剂的重量份为0.5-5份。
作为本申请环氧树脂组合物的优选实施方式,采用如下中的至少一项:
A、所述流平剂为聚醚改性二甲基聚硅氧烷;
B、所述消泡剂为有机硅类或亚克力类消泡剂;
C、所述润湿分散剂为高度枝化结构的聚酯、改性聚丙烯酸酯、改性苯乙烯马来酸共聚物中的至少一种;
D、所述硅烷偶联剂为环氧基、酸酐基、羧酸基硅烷偶联剂中的至少一种。
发明人通过大量实验发现,本发明配方中添加无机填料和助剂,形成有机-无机混成物,具有对基板高黏结力、低脆性降低了固化物的CTE值,改善了电阻因高低温工艺和测试的稳定性;且整体配方都选用无卤素化合物,改善了电阻高温高湿条件下的不稳定问题,且通10%额定功率下可保证长时间阻值稳定性。
由于目前保护胶对提高车规片式电阻在高温高湿环境下的稳定性成为其应用的关键问题;贴片电阻、半导体、被动元件的绝缘保护层或有机-无机混成复合材料对于电子组件的保护期稳定性至关重要,耐高温黏结力、高湿黏结力强的保护浆料是提升片式电阻、半导体、被动组件耐湿热能力的关键,本发明使用不同粒径的二氧化硅粉体,滑石粉和其他助剂使整体配方可以达到有机-无机复合材料间的分子间作用力增加,使配方长期储放有较高的稳定性,并且达成车规片式电阻、半导体、被动元件AEC-Q200所有测试规范。
作为本申请环氧树脂组合物的优选实施方式,所述环氧树脂组合物还包括重量份为0.5-9份的触变剂。
作为本申请环氧树脂组合物的更优选实施方式,所述触变剂选自气象二氧化硅、滑石粉、聚酰胺蜡中的至少一种;发明人通过大量实验发现,上述触变剂能够改善浆料印刷的触变性,使浆料在印刷过程无流挂、渗边和扩散现象,增强了印刷图形的完整性、密封性;同时,触变剂的加入有效提升了浆料室温存储的稳定性,延长了浆料的使用时间。
作为本申请环氧树脂组合物的优选实施方式,所述环氧树脂组合物还包括重量份为1-35份的溶剂。
作为本申请环氧树脂组合物的更优选实施方式,所述溶剂选自丁基卡必醇、丁基卡必醇醋酸酯中的至少一种。
第二方面,本申请提供了一种绝缘电阻保护浆料,所述绝缘电阻保护浆料采用如第一方面所述的环氧树脂组合物制得。
作为本申请所述绝缘电阻保护浆料的优选实施方式,所述绝缘电阻保护浆料的制备方法包括如下步骤:
S1、将促进剂、二羧酸和环氧树脂混合并进行加成反应,反应3-6h后,混合体系的酸值<0.1(mgKOH/g)停止反应,得改性环氧树脂,
S2、将步骤S1所述改性环氧树脂、黑色颜料和无机填料加入到溶剂中,在30-40℃条件下加热搅拌至溶解,过滤,形成细度<8μm的浆料;
S3、将固化剂和促进剂在溶剂中进行加成反应,反应结束后加入触变剂、无机填料和硅烷偶联剂,混合均匀,并进行分散,形成细度<8μm的浆料;
S4、将步骤S2所述浆料和步骤S3所述浆料搅拌至充分混合,并分散、脱泡,即得绝缘保护浆料。
作为本申请所述绝缘电阻保护浆料的制备方法的优选实施方式,所述步骤S1中,促进剂为阴阳离子型触媒。
作为本申请所述绝缘电阻保护浆料的制备方法的优选实施方式,所述步骤S1中,加成反应的温度为100-130℃。
作为本申请所述绝缘电阻保护浆料的制备方法的优选实施方式,所述步骤S3中,加成反应的温度为80-100℃,时间为2-4h。
作为本申请所述绝缘电阻保护浆料的制备方法的优选实施方式,所述步骤S3中,加成反应结束后降温至25-40℃后再加入触变剂、无机填料和硅烷偶联剂。
与现有技术相比,本申请的有益效果在于:
本发明提供的环氧树脂组合物制得的绝缘保护浆料具有优异的印刷性能和低吸湿性,固化后浆料具有合适的硬度与韧性,能够避免电阻生产过程中出现保护层损坏现象;浆料固化后形成之致密的绝缘保护膜,和氧化铝基片具有较强的结合力,能够提升片式电阻在高温高湿环境下的可靠性。
具体实施方式
为更好地说明本申请的目的、技术方案和优点,下面将结合具体实施例对本申请作进一步说明。
本申请所采用的试剂、方法和设备,如无特殊说明,均为本技术领域常规试剂、方法和设备。
实施例1-6
本申请实施例1-6所述绝缘电阻浆料的配方如表1所示,所述绝缘电阻浆料的制备方法包括以下步骤:
S1、将促进剂、二羧酸和环氧树脂在110-130℃条件下加热进行加成反应,反应3~6h后,混合体系的酸值<0.1(mgKOH/g)停止反应,得改性环氧树脂;
S2、将步骤S1所述改性环氧树脂、黑色颜料和无机填料加入到溶剂中,在30-40℃条件下加热搅拌至溶解,过滤,形成细度<8μm的浆料;
S3、将固化剂和促进剂在溶剂中进行加成反应,加成反应的温度为80-100℃,反应2-4h,反应结束后加入触变剂、无机填料和硅烷偶联剂,混合均匀,并进行分散,形成细度<8μm的浆料;
S4、将步骤S1所述浆料和步骤S2所述浆料搅拌至充分混合,并分散、脱泡,即得绝缘保护浆料。
对比例1-2
本申请对比例1-2所述绝缘电阻浆料的配方如表1所示,所述绝缘电阻浆料的制备方法包括以下步骤:
S1、将促进剂、二羧酸和环氧树脂在110-130℃条件下加热进行加成反应,反应3~6h后,混合体系的酸值<0.1(mgKOH/g)停止反应,得改性环氧树脂;
S2、将步骤S1所述改性环氧树脂、黑色颜料和无机填料加入到溶剂中,在30-40℃条件下加热搅拌至溶解,过滤,形成细度<8μm的浆料;
S3、将固化剂和促进剂在溶剂中进行加成反应,加成反应的温度为80-100℃,反应2-4h,反应结束后加入触变剂、无机填料和硅烷偶联剂,混合均匀,并进行分散,形成细度<8μm的浆料;
S4、将步骤S1所述浆料和步骤S2所述浆料搅拌至充分混合,并分散、脱泡,即得绝缘保护浆料。
表1
性能指标和测试方法
车规电阻重点测试项目-高温高湿(双85):将实施例和对比例的测试样品置于85℃、湿度85%环境中,10%额定功率通电1000h,阻值变化△R≤±(0.2%R+0.05Ω)记为合格,否则记录失效,结果如下表2所示:
表2
根据表2结果可知,实施例1-6所述绝缘电阻浆料的卤素含量为0ppm,浆料与氧化铝基板的黏结性较好,且脆性较低,同时具有较低的吸湿性;能够提升片式电阻在高温高湿环境下的可靠性。
而对比例1、2由于未按照本发明配方,导致Cl含量较大,电阻层容易和保护胶里的卤素在高温高湿下形成化学反应,因此造成阻值变化,微量卤素集中在某区域故时常有77分之1粒失效发生;同时,保护胶和基板黏结性差,电镀液、水气或氧氧容易入侵电阻体,在高温高湿下形成化学反应,因此造成阻值变化;保护胶脆性高,工艺过程中造成暗裂使得电镀液、水气或氧氧容易入侵电阻体,在高温高湿下形成化学反应,造成阻值变化。
最后所应当说明的是,以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制,尽管参照较佳实施例对本申请作了详细说明,本领域的普通技术人员应当理解,可以对本申请的技术方案进行修改或者等同替换,而不脱离本申请技术方案的实质和范围。
Claims (10)
1.一种环氧树脂组合物,其特征在于,所述环氧树脂组合物包括A组分和B组分,所述A组分包括环氧树脂、二羧酸和促进剂,所述B组分包括固化剂和促进剂;所述环氧树脂包括二官能基脂环族环氧树脂及其衍生物、三官能基脂环族环氧树脂及其衍生物中的至少两种;所述固化剂包括甲基六氢苯酐及其衍生化合物、羟基酚醛衍生化合物、苯并恶嗪衍生化合物中的至少一种。
2.如权利要求1所述的环氧树脂组合物,其特征在于,以环氧树脂组合物计,所述环氧树脂的重量份为10-60份,所述二羧酸的重量份为5-50份,所述固化剂的重量份为5-55份,所述环氧树脂的促进剂重量份为0.1-10份。
3.如权利要求1所述的环氧树脂组合物,其特征在于,所述促进剂选自三级胺、咪唑衍生物、阴阳离子型触媒、脲、取代的脲、改性咪唑中的至少一种;
优选地,所述促进剂包括甲苯双-二甲基脲、3-苯基-1,1-二甲基脲、叔丙烯酰胺、亚烷基胺、2,4,6-三(二甲基氨基甲基)-苯酚、2-苯基-咪唑、2-甲基咪唑、1-甲基咪唑、2-乙基-4-甲基咪唑、4,4'-亚甲基-双(2-乙基-5-甲基咪唑)2-乙基-2-甲基咪唑、N-丁基咪唑、6-己内酰胺中的至少一种。
4.如权利要求1所述的环氧树脂组合物,其特征在于,所述环氧树脂组合物还包括下述重量份的组分:黑色颜料3-7份,无机填料10-65份,助剂0.2-10份。
5.如权利要求4所述的环氧树脂组合物,其特征在于,所述无机填料包括二氧化硅、氧化铝、氢氧化铝、硫酸钡、石英粉、滑石粉、氮化铝中的至少一种。
6.如权利要求4所述的环氧树脂组合物,其特征在于,所述助剂包括流平剂、消泡剂、润湿分散剂、硅烷偶联剂中的至少一种。
7.如权利要求6所述的环氧树脂组合物,其特征在于,所述流平剂的重量份为0.5-5份,所述消泡剂的重量份为0.5-5份,所述润湿分散剂的重量份为0.1-5份,所述硅烷偶联剂的重量份为0.5-5份。
8.如权利要求6所述的环氧树脂组合物,其特征在于,采用如下中的至少一项:
A、所述流平剂为聚醚改性二甲基聚硅氧烷;
B、所述消泡剂为有机硅类或亚克力类消泡剂;
C、所述润湿分散剂为高度枝化结构的聚酯、改性聚丙烯酸酯、改性苯乙烯马来酸共聚物中的至少一种;
D、所述硅烷偶联剂为环氧基、酸酐基、羧酸基硅烷偶联剂中的至少一种。
9.一种绝缘电阻保护浆料,其特征在于,所述绝缘电阻保护浆料采用如权利要求1-8任一项所述的环氧树脂组合物制得。
10.如权利要求9所述的绝缘电阻保护浆料,其特征在于,所述绝缘电阻保护浆料的制备方法包括如下步骤:
S1、将促进剂、二羧酸和环氧树脂混合并进行加成反应,反应3-6h后,混合体系的酸值<0.1(mgKOH/g)停止反应,得改性环氧树脂,
S2、将步骤S1所述改性环氧树脂、黑色颜料和无机填料加入到溶剂中,在30-40℃条件下加热搅拌至溶解,过滤,形成细度<8μm的浆料;
S3、将固化剂和促进剂在溶剂中进行加成反应,反应结束后加入触变剂、无机填料和硅烷偶联剂,混合均匀,并进行分散,形成细度<8μm的浆料;
S4、将步骤S2所述浆料和步骤S3所述浆料搅拌至充分混合,并分散、脱泡,即得绝缘保护浆料。
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