CN107109059A - 用于电子电路的导热聚合物制品 - Google Patents
用于电子电路的导热聚合物制品 Download PDFInfo
- Publication number
- CN107109059A CN107109059A CN201580053880.1A CN201580053880A CN107109059A CN 107109059 A CN107109059 A CN 107109059A CN 201580053880 A CN201580053880 A CN 201580053880A CN 107109059 A CN107109059 A CN 107109059A
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- polymer product
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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- H01L33/641—Heat extraction or cooling elements characterized by the materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
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- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2003/385—Binary compounds of nitrogen with boron
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2203/20—Applications use in electrical or conductive gadgets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L2933/0075—Processes relating to semiconductor body packages relating to heat extraction or cooling elements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本文公开了一种导热聚合物制品,其由聚合物树脂和导热添加剂制成,其中所述制品经过激光成型和等离子体金属化,并且优选通过无铅回流焊实施表面装配技术(SMT),从而提供集成电路。所述制品可以是印刷电路板或LED照明组件及其他形式。导热添加剂可以是绝缘或导电的,也可以同时采用两种类型。导热聚合物配混物能够挤出、模塑、压延、热成型或3D打印,然后形成散热、激光成型和等离子体金属化聚合物制品的形式。
Description
优先权声明
本申请要求2014年10月7日提交的美国临时专利申请系列第62/060,707号的优先权,该申请的代理机构案卷号为12014015,其内容通过参考结合于此。
技术领域
本发明涉及热塑性聚合物配混物,其具有导热性,能够激光成型和等离子体金属化。
背景技术
现代社会中任何通电产品都不具有理想的效率因此,能量的消耗伴随着放热。通电产品的散热是工业工程普遍关心的问题。电子产品特别容易过热。个人计算机包含风扇,通过对流散热使敏感电子部件大致保持在环境温度。
PCT专利申请公开WO200714978(Barber等)披露了聚苯硫醚(PPS)及其他热塑性树脂在导热型热塑性配混物中的应用。
可制备聚合物制品用于电子电路,利用所谓的“激光直写成型”工艺,通过直接金属化可以在任何形状的聚合物制品表面中制作集成电路迹线。根据Ranft等人的“导热聚合物的激光直写成型:新型热管理方法”(LASER DIRECT STRUCTURING OF THERMALLYCONDUCTIVE POLYMERS:AN INNOVATIVE THERMAL MANAGEMENT APPROACH)(ANTEC,2012),激光直写成型工艺(LDS)是通过直接金属化在三维热塑性部件(所谓的模塑互连器件)(3D-MID)上形成集成电路迹线的成熟技术。从1990年代晚期开始,LDS技术从汽车和通信应用中的少量商业化产品起步。最近,此技术的最大市场是制造集成式手机天线,主要位于亚洲国家。
Ranft等人还报告,照明技术领域的另一快速成长的市场和重要的经济因素是基于高亮度发光二极管(LED)的应用在数量上暴涨。特别是与节能的迫切需求相关的发光效率的改善导致它们越来越多地用于普通照明(民用、工业和户外)、交通信号灯、汽车照明及其他光电子应用。
发明内容
本领域需要具有导热性并且还能进行激光成型的导热聚合物配混物,用来在由该配混物制成的聚合物制品表面上的激光成型部分上通过直接金属化产生集成电路迹线。较佳的是,这些聚合物制品是印刷电路板或LED照明组件,它们是两种需要突出的散热管理的聚合物制品。因为聚合物配混物导热,所以聚合物制品,特别是印刷电路板或LED照明组件,能够作为从热源散热的机构,所述热源是集成电路或者与集成电路相连的电子器件。
本发明采用一种或多种导热添加剂为已进行激光成型和等离子体金属化的聚合物制品提供导热性,从而解决了该问题。此外,导热塑料制品可以是绝缘的或者导电的。
因此,本发明的一个方面是已进行激光成型和等离子体金属化的聚合物制品,其包含导热聚合物配混物,所述导热聚合物配混物包含能够进行激光成型和等离子体金属化的聚合物树脂和选自下组的导热添加剂,该组由以下各项组成:导热绝缘添加剂和导热导电添加剂。
较佳的是,聚合物树脂能够通过无铅回流焊实施表面装配技术(SMT)。
下面将探讨本发明的各种特征。
附图说明
图1是由导热聚合物配混物制成的聚合物制品照片,其已激光成型,用来制备用于电子电路的平坦表面。
图2是图1所示聚合物制品的照片,其已等离子体金属化,用来提供电子电路。
图3是在电子电路上焊有LED的聚合物制品的照片。
具体实施方式
热塑性聚合物基体
只要能够进行激光成型和等离子体金属化而不对其结构性质如耐久性、韧性、耐热性造成不利影响,任何常规热塑性聚合物都是用作本发明的配混物基体的候选对象。无需过多实验,本领域普通技术人员能够在考虑成本、制造技术、物理性质、化学性质等因素的基础上选择基体。合适的热塑性聚合物的非限制性例子有聚烯烃、聚卤代烯烃、聚酰胺、聚酯、聚氨酯、聚碳酸酯、聚亚芳基类聚合物(polyarylene)(聚亚芳基硫醚类(sulfides)、聚亚芳基醚(ethers)等)及其混合物。所述聚合物可以是均聚物或共聚物。
在这许多候选对象中,优选使用聚苯硫醚,因为它具有耐久性、高温耐受性,存在合适的导热性和热变形温度。聚苯硫醚是含有苯基部分和与之键合的一种或多种硫化物的聚合物。本领域技术人员会认识到,各种市售聚苯硫醚适用于本发明。这种市售聚苯硫醚(“PPS”)的非限制性例子包括可以各种级别购自德克萨斯州伍德兰市雪佛龙菲利普化学公司(Chevron Phillips Chemical Co.of The Woodlands,Texas)的Ryton牌PPS粉末。为本领域技术人员所知的文献中的任何专利都适合用来确定合适的选择,而无需过多实验。
导热添加剂
导热绝缘添加剂
氮化硼
有潜力用于所述配混物的导热绝缘添加剂是氮化硼,可以立方氮化硼或六方氮化硼商购。本领域熟知,六方氮化硼比立方氮化硼提供更高的导热性,因而是优选的。六方氮化硼还有助于得到高表面电阻率。
购自坎普顿市(Kempten)ESK陶瓷股份有限公司(ESK Ceramic GmbH)(德国)的氮化硼粉末是目前优选的。
铝硅酸盐
另一种有潜力用于所述配混物的导热绝缘添加剂是铝硅酸盐。购自弗雷辛市(Frechen)Quarzwerke Gruppe公司(德国)的基于天然铝硅酸盐的Silatherm 1360-100AST化合物是目前优选的。
氧化锌
另一种有潜力用于所述配混物的导热绝缘添加剂是氧化锌。购自昂格勒尔市优美科公司(Umicore of Angleur)(比利时)的NEIGE B氧化锌是目前优选的。
二氧化钛
另一种有潜力用于所述配混物的导热绝缘添加剂是二氧化钛,可以金红石或锐钛矿商购。
购自达拉斯市克罗诺斯公司(Kronos of Dallas)(美国)的KRONOS 2220二氧化钛是目前优选的。
尽管氮化硼、铝硅酸盐、氧化锌和二氧化钛具有不同的导热性质,但它们各自有可能能够单独用作导热绝缘添加剂,具体取决于在配混物中的利用率。在本发明的实验中已经发现,它们当中的氮化硼或铝硅酸盐能够单独用作这种类型的添加剂。在本发明的实验中还发现,氮化硼、氧化锌和二氧化钛能够一起使用,用作该类型的导热绝缘添加剂。无需过多实验,本领域普通技术人员能够从这四种导热绝缘添加剂中进行选择,以各种组合和数量使用,从而实现能够进行激光成型和等离子体金属化以制备本发明的聚合物制品的导热绝缘聚合物配混物。
既导热又绝缘的其他添加剂也是适用于本发明的候选对象,因为本领域普通技术人员在制备导热聚合物制品如导热印刷电路板或LED照明组件时可能发现它们。
导热导电添加剂
石墨
一种有潜力用于所述配混物的导热导电添加剂是石墨,可以天然或合成形式商购。
购自伯恩市埃德尔石墨公司(Edelgraphit of Bonn)(德国)的NFL98天然六方石墨是目前优选的。
既导热又导电的其他添加剂也是适用于本发明的候选对象,因为本领域普通技术人员在制备导热聚合物制品如沥青碳纤维或碳纳米管时可能发现它们。
可选的填料增强
利用增强填料可以提高由本发明的配混物制成的聚合物制品(如印刷电路板)的结构整体性。这些填料优选呈化学惰性,绝缘,具有纤维形状。
非传导性增强填料的非限制性例子有氧化硅、玻璃纤维、芳香族聚酰胺纤维、矿物纤维等。优选使用玻璃纤维,因为它比其他类型的填料易得且成本低。
其他可选添加剂
本发明的配混物可包含常规塑料添加剂,其含量足以获得配混物所需的加工性或性能。添加量不应造成添加剂浪费,也不应损害配混物的加工或性能。热塑性塑料配制领域的技术人员无需过多实验,只需参考诸如来自“塑料设计库”(Plastics Design Library)(elsevier.com)的《塑料添加剂数据库》(Plastics Additives Database)(2004)这样的专著即可选择许多不同类型的添加剂加入本发明的配混物中。
可选添加剂的非限制性例子包括粘合促进剂;杀生物剂(杀细菌剂、杀真菌剂和杀霉菌剂);抗雾化剂;抗静电剂;粘结、发泡和起泡剂;分散剂;填料和增容剂,如滑石和玻璃纤维;阻燃剂;烟雾抑制剂;抗冲击改性剂;引发剂;润滑剂;云母;颜料、着色剂和染料;增塑剂如核/壳抗冲改性剂;加工助剂;脱模剂;硅烷、钛酸盐(酯)和锆酸盐(酯);滑爽和抗粘连剂;稳定剂;硬脂酸盐(酯);紫外光吸收剂;粘度改性剂;石蜡;催化剂失活剂;及其组合。
在本发明的实验中已经发现,在这些可选添加剂中,硬脂酸金属盐在配混及其他加工操作中提供润滑辅助作用,所述其他操作包括将聚合物配混物从球粒转化为最终的聚合物制品。
表1显示了含有导热绝缘添加剂的聚合物制品中各成分的可接受的、有利的和优选的用量范围,均表达为基于整个配混物的重量(重量%)。所述配混物可以包含这些成分、基本上由这些成分组成或者由这些成分组成。这些范围的端点之间的任何数值也视为一个范围的端点,因而所有可能的组合均视为在表1的可能性之内,作为用于本发明的候选配混物。
表2显示了含有导热导电添加剂的聚合物制品中各成分的可接受的、有利的和优选的用量范围,均表达为基于整个配混物的重量(重量%)。所述配混物可以包含这些成分、基本上由这些成分组成或者由这些成分组成。这些范围的端点之间的任何数值也视为一个范围的端点,因而所有可能的组合均视为在表2的可能性之内,作为用于本发明的候选配混物。
在这两种配混物中,还能想到可任选添加相反类型的导热添加剂。表1中用于配混物的可选的导热添加剂的类型可从表2中用于配混物的添加剂中选择,反之亦然。因此,对表1和表2中配混物的导热性的增强效果可不同于分别对导电性或绝缘性的影响。
加工
本发明的配混物的制备不复杂。本发明的配混物可通过间歇或连续操作制备。
连续工艺中的混合通常在单螺杆或双螺杆挤出机中进行,挤出机升温到足以熔化聚合物基体,其他成分在挤出机头或下游加入挤出机。挤出机速度可在约50-500转/分钟(rpm)、优选约100-300rpm的范围内。通常对挤出机的输出物进行造粒,供后续挤出或模型成聚合物制品。
间歇工艺中的混合通常在班伯里(Banbury)混合机中进行,该混合机能够在足以熔化聚合物基体的温度下操作,以允许添加固体成分添加剂。混合速度在60-1000rpm的范围内。同样,将混合机的输出物切成较小尺寸,供后续挤出或模型成聚合物制品。
后面的挤出或模塑技术是热塑性塑料聚合物工程领域的技术人员所熟知的。不需要过多实验,利用参考文献,如均由“塑料设计库”(Elsevier.com)出版的《挤出:限定性操作指南和手册》(Extrusion,The Definitive Processing Guide and Handbook)、《模塑部件收缩和翘曲手册》(Handbook of Molded Part Shrinkage and Warpage)、《专用模塑技术》(Specialized Molding Techniques)、《旋转模塑技术》(Rotational MoldingTechnology)和《模具、工具和模头修复焊接手册》(Handbook of Mold,Tool and DieRepair Welding),技术人员能够使用本发明的配混物制备具有可想到的任何形状和外观的制品。
本发明的实用性
本发明的配混物能够非常有效地散热,使其适用于挤出、模塑、压延、热成型或3D打印的制品,所述制品设计为接触受热的物体,并将热从该物体传导走,或者接触受热的物体,并将热传导到也需要热的第二个物体。无论是哪种方式,本发明的配混物都能够将热从热源送走,要么从该物体分配到远处(住宅里的暖气片)或者从该物体散发到远处(散热器)。
由于能够激光成型、等离子体金属化以及优选通过无铅回流焊实施表面装配技术(SMT),聚合物制品(不管如何形成)能够进行激光加工和等离子体金属化,为制品提供电路迹线,使其变成电子电路的一部分。然后,可将其他电子组件焊接到电子电路上。
PCT专利公开WO 2014/114707(等离子体创新股份有限公司)(PlasmaInnovations GmbH)中披露了激光加工和等离子体金属化方法的例子。
需要管理和消散热的一个行业是照明行业,特别是与灯丝电灯相对的发光二极管(LED)产生的照明。LED的性能对温度敏感,就如同点亮的LED附近或毗邻的电子器件一样。因此,优选的模塑制品是LED照明组件或其他电子部件。由于能够进行激光成型和等离子体金属化,LED照明组件或其他电子部件自身能够在其表面形成电子电路。
聚合物基体的物理性质决定了配混物是否适合具体的聚合物工程目的;导热添加剂(绝缘或导电)的使用提供了导热性,而聚合物基体原本没有导热性或仅有一点点导热性;可选的非传导性填料能够增强聚合物基体的物理性质。
所述配混物可在各种器件中用于多种类型的电子电路应用,所述器件如个人计算机、笔记本电脑、智能电话、全球定位系统设备、医疗器械、RFID发射器和接收器,以及通常用于医疗、汽车、建筑、航空及其他工业的电子器件。更具体而言,LED照明组件、印刷电路板、天线及其他电子组件或部件可受益于导热聚合物制品的多样性,无论是绝缘型还是导电型,具体取决于用户的选择。
实施例提供了成功的试验结果。
实施例
实施例1-4
表3显示了成分和配方的清单。
利用双螺杆挤出机,在高于聚苯硫醚熔点的温度下操作,通过熔融混合挤出制备了实施例1-4。对挤出物进行造粒,在RF-Plast股份有限公司完成后续注射成型,并在等离子体创新股份有限公司完成激光成型和等离子体金属化。
简而言之,实施例1-3的聚合物配混物注射成型为部件100,其具有尺寸约为3cmx3cm的平坦表面120,如图1所示。相反表面包含柱体阵列140,用于散热。然后在平坦表面上沉积掩模。然后,在具有掩模的平坦表面上,对平坦表面的具体区域150和160进行激光成型,同样如图1所示。然后,将铜等离子体涂层附着到平坦表面的这些具体区域150和160,如图2所示。然后,如图3所示,将LED 180焊接到平坦表面上被铜涂覆的具体区域,并连接到电源(未示出),以验证在平坦表面的这些具体区域150和160上构建起电路。
用与实施例1-3相同的方式测试实施例4,不同之处是在成型步骤和掩蔽步骤之间,通过等离子体沉积氧化铝将陶瓷层附着到整个平坦表面。同样构建电路,并利用LED验证。
等离子体创新股份有限公司在塑料结构金属化领域为人所熟知,它能够提供约5-50微米之间的层的金属化工艺,因成本和导热/导电性的原因,通常是铜层。等离子体涂覆工艺采用在10000℃下操作的高能电弧放电,它将离子化等离子体导向要金属化的表面。等离子体金属化工艺中可以使用粒度为1-40微米的粉末。
上文所述的聚合物配混物的优点之一在于,由这种配混物形成的聚合物制品不仅能够通过激光成型和等离子体金属化形成具体的精确电子电路,而且这种配混物具有导热性,使对热敏感的电子电路和器件散热。
实施例1-4的热导率是约1-4W/m.K范围内的层间热导率,通过C-Therm TCiTM技术在厚4mm的成型样品上测量。
本发明不限于上述实施方式。以下是权利要求书。
Claims (10)
1.一种进行了激光成型和等离子体金属化的聚合物制品,包含:
导热聚合物配混物,包含:
(a)能够进行激光成型和等离子体金属化的聚合物树脂;以及
(b)选自下组的导热添加剂,该组由以下各项组成:导热绝缘添加剂和导热导电添加剂。
2.如权利要求1所述的聚合物制品,其中,所述聚合物树脂是聚苯硫醚。
3.如权利要求1或2所述的聚合物制品,其中,所述导热绝缘添加剂选自下组,该组由以下各项组成:氮化硼、铝硅酸盐、氧化锌、二氧化钛或其组合,其中所述导热导电添加剂是石墨。
4.如权利要求1或2或3所述的聚合物制品,还包含选自下组的添加剂,该组由以下各项组成:粘合促进剂;杀生物剂;抗雾化剂;抗静电剂;粘结、发泡和起泡剂;分散剂;填料和增容剂;阻燃剂;玻璃纤维;烟雾抑制剂;抗冲击改性剂;引发剂;润滑剂;云母;颜料、着色剂和染料;增塑剂;加工助剂;脱模剂;硅烷、钛酸盐和/或酯和锆酸盐和/或酯;滑爽和抗粘连剂;稳定剂;硬脂酸盐和/或酯;紫外光吸收剂;粘度改性剂;石蜡;催化剂失活剂;及其组合。
5.如前述权利要求中任一项所述的聚合物制品,其中,所述配混物是绝缘的,并具有含量用重量百分数表示的以下成分:
6.如前述权利要求中任一项所述的聚合物制品,其中,所述配混物是导电的,并具有含量用重量百分数表示的以下成分:
7.如前述权利要求1-6中任一项所述的聚合物制品,其中,所述制品是挤出、模塑、压延、热成型或3D打印的。
8.如前述权利要求1-6中任一项所述的聚合物制品,其中,所述制品是印刷电路板或LED照明组件。
9.一种制备权利要求1所述聚合物制品的方法,其中将配混物模塑成成形体,该成形体设计成接触受热物体,将热从该物体传导走;或者接触受热物体,将热传导到也需要加热的第二物体,其中所述制品已经进行了激光成型和等离子体金属化,从而为所述制品提供集成电路。
10.如权利要求9所述的方法,其中,所述聚合物制品还通过无铅回流焊实施了表面装配技术。
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US201462060707P | 2014-10-07 | 2014-10-07 | |
US62/060,707 | 2014-10-07 | ||
PCT/US2015/054066 WO2016057418A1 (en) | 2014-10-07 | 2015-10-05 | Thermally conductive polymer articles for electronic circuitry |
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CN108587219A (zh) * | 2018-05-09 | 2018-09-28 | 南通强生石墨烯科技有限公司 | 石墨烯树脂复合材料及其在led灯杯中的用途 |
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US10870749B2 (en) | 2017-07-05 | 2020-12-22 | The University Of Akron | Thermally conductive polymers and methods for making |
WO2021126736A1 (en) * | 2019-12-17 | 2021-06-24 | Ticona Llc | Three-dimensional printing system employing a thermally conductive polymer composition |
CN115151403A (zh) | 2019-12-17 | 2022-10-04 | 提克纳有限责任公司 | 采用热致液晶聚合物的三维打印系统 |
WO2021126739A1 (en) * | 2019-12-17 | 2021-06-24 | Ticona Llc | Three-dimensional printing system employing a toughened polyarylene sulfide composition |
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EP3204446B1 (en) | 2020-06-17 |
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US20170218245A1 (en) | 2017-08-03 |
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WO2016057418A1 (en) | 2016-04-14 |
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