CN102906867A - 包括底部填充用围堰的印刷电路板及其制造方法 - Google Patents
包括底部填充用围堰的印刷电路板及其制造方法 Download PDFInfo
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- CN102906867A CN102906867A CN2011800250374A CN201180025037A CN102906867A CN 102906867 A CN102906867 A CN 102906867A CN 2011800250374 A CN2011800250374 A CN 2011800250374A CN 201180025037 A CN201180025037 A CN 201180025037A CN 102906867 A CN102906867 A CN 102906867A
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
- H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/2612—Auxiliary members for layer connectors, e.g. spacers
- H01L2224/26152—Auxiliary members for layer connectors, e.g. spacers being formed on an item to be connected not being a semiconductor or solid-state body
- H01L2224/26175—Flow barriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/27—Manufacturing methods
- H01L2224/27011—Involving a permanent auxiliary member, i.e. a member which is left at least partly in the finished device, e.g. coating, dummy feature
- H01L2224/27013—Involving a permanent auxiliary member, i.e. a member which is left at least partly in the finished device, e.g. coating, dummy feature for holding or confining the layer connector, e.g. solder flow barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
- H01L2224/8119—Arrangement of the bump connectors prior to mounting
- H01L2224/81191—Arrangement of the bump connectors prior to mounting wherein the bump connectors are disposed only on the semiconductor or solid-state body
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
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Abstract
本发明涉及一种具有优良检测能力的底部填充用围堰。本发明提供一种在晶片元件周围以围墙的形状形成,并且用于防止填充在基板和晶片元件之间的底部填充材料流出的围堰,其特征在于围堰由干膜型阻焊剂形成。
Description
技术领域
本发明涉及一种包括底部填充用围堰的印刷电路板及其制造方法,尤其涉及一种包括使用干膜型(dry film type)阻焊剂(Solder Resist)的底部填充用围堰的印刷电路板及其制造方法。
背景技术
为了保护以集成电路(IC)为中心的元件,使用主要为环氧树脂的各种树脂进行包装,近年来随着小型化和轻量化,IC的贴装方法主要采用被称为表面安装的直接将IC等元件载置于基板并使用液体树脂进行包装的方法(底部填充(Under-Fill)工序)。
这种底部填充工序是用于解决热机械疲劳问题的方法,具体是指向环氧树脂等粘合力优良的高分子材料中填充无机颗粒使其获得接近焊剂的热膨胀系数的值,然后将其填充于晶片和印刷电路板之间的缝隙的工序,此时所使用的填充有无机颗粒的高分子复合材料称为底部填充材料(Under-fill)。
一般所知的底部填充材料是液体形态,存在如下问题:具有高流动性的底部填充材料流出至不需要其的区域,从而导致不利的污染或产品不良又或者难以实现高密度的安装。为了防止这些问题,采用在元件周围形成称为围堰(Dam)的围墙的方法。
现有围堰主要以使用通过冲压形成的薄片形状的材料或液体阻焊剂(例如,日本专利公开第1996-325476号等)的方法来形成,由现有液体阻焊剂形成围堰的方法在IC的高密度安装中厚度的偏差大,由此导致粘合剂(液体密封剂)流出的问题等,而且当围堰的厚度单位微细化到μm时,不能形成均匀的围堰。
为了解决使用这种液体阻焊剂的围堰形成方法中存在的问题,提出了使用干膜(dry film)形状阻焊剂的方法。举例来说,JP1996-097841或者US2010-0116534等文献公开了制造如下围堰的方法:该围堰通过使用干膜阻焊剂(dry film resist)而来防止底部填充材料的流动。但即使通过现有方法也存在如下问题:在微细化围堰的厚度方面有一定局限性,从而难以适用于高密度集成电路,当实现薄的厚度时,不能形成具有一定标准以上的高度的围堰或形成非常不均匀的围堰。
发明内容
发明所要解决的问题
本发明的目的在于提供一种包括具有优良的机械性能并具有微细、均匀厚度的底部填充用围堰的印刷电路板。另外,本发明的目的还在于提供一种上述印刷电路板的制造方法。
解决问题的手段
本发明提供一种包括沿着基板外缘形成的底部填充用围堰的印刷电路板,其中所述底部填充用围堰包含干膜阻焊剂,所述干膜阻焊剂包含感光性树脂组合物的干燥物或固化物,所述感光性树脂组合物包含:具有羧基(-COOH)和可光固化的官能团的酸改性低聚物(acid modifiedoligomer);光聚合性单体;热固性粘合剂树脂;以及颜料。
另外,本发明提供一种印刷电路板的制造方法,包含如下步骤:在基板上层叠包含有感光性树脂组合物的干燥物或固化物的干膜的步骤,其中所述感光性树脂组合物包含具有羧基(-COOH)和可光固化的官能团的酸改性低聚物、光聚合性单体、光敏引发剂、热固性粘合剂树脂、以及包含有机溶剂和颜料;对所述基板外缘部位的干膜进行曝光的步骤;以及清洗所述已曝光的干膜的步骤。
下面,对根据本发明的具体实施方案的印刷电路板及其制造方法进行具体说明。
根据本发明的一实施方案,能提供一种包括沿着基板外缘形成的底部填充用围堰的印刷电路板,其中所述底部填充用围堰包含干膜阻焊剂,所述干膜阻焊剂包含感光性树脂组合物干燥物或固化物,所述感光性树脂组合物包含:具有羧基(-COOH)和可光固化的官能团的酸改性低聚物;光聚合性单体;热固性粘合剂树脂;以及颜料。
若使用由包含具有所述特定官能团的酸改性低聚物、光聚合性单体、热固性粘合剂树脂等组分的感光性树脂组合物制备的干膜阻焊剂,则能形成很薄且具有均匀厚度的底部填充用围堰。尤其是,这种底部填充用围堰表现出优良的机械性能,因此以薄的厚度也能实现一定标准以上的高度和强度,由此能防止对印刷电路板注入或填充的底部填充材料的流出,并能最大限度地减少在所述底部填充工序或半导体制备工序中可能发生的底部填充用围堰的损伤或物理性能的下降现象。所述“底部填充用围堰”是指在印刷电路板的外缘形成并在底部填充工序中防止注入于基板和半导体晶片之间的材料流出的结构或基板上的一定部位。
另一方面,所述印刷电路板可以是包括基板并沿着所述基板的外缘形成有上述底部填充用围堰的形态。这种印刷电路板可以包括:在所述基板上形成的电极极板(electrode pad);在所述电极极板上形成的焊料隆起焊盘(solder bump);以及以所述焊料隆起焊盘为介质通过倒装晶片(flip chip)结合的半导体晶片。对有关所述电极极板、焊料隆起焊盘以及半导体晶片的具体内容并无大的限制,只要适用于印刷电路板的通常公知的结构都可以采用。
如上所述,所述底部填充用围堰用于防止填充于基板和半导体晶片之间的填充材料的流出,具体地,位于所述基板的外缘和半导体晶片的外缘之间起到防止注入的底部填充材料向基板外部流出的作用。
因此,所述底部填充用围堰可以具有基板和半导体晶片之间的间隔大小以上的高度,例如,在所述基板上形成的底部填充用围堰可以以具有与所述半导体晶片的最外侧一面(即离基板最远的面)相同的高度的方式形成。
另一方面,所述底部填充用围堰根据所使用的颜料或其他材料的颜色可呈现多种颜色,例如白色、黄色、绿色、黑色又或者红色。尤其是,当所述底部填充用围堰的颜色是白色(White)时,由于其具有反射光的性质,因此在光学设备AOI(Automated Optical Inspection:自动光学检测仪)设备中的检测能力与其他颜色相比更优良。
还有,所述底部填充用围堰可以具有不同于所述基板、可在所述基板上选择性形成的阻焊剂或印刷电路板内的其他结构的颜色。相同地,通过所述底部填充用围堰具有不同于基板或其他阻焊剂的颜色,能够容易检测、判断出是否存在外观不良的现象。
所述底部填充用围堰是使用由含有特定组分的感光性树脂组合物制备的干膜阻焊剂而形成的,所以其能具有通过现有方法难以实现的厚度和均匀度。具体来讲,所述底部填充用围堰的厚度可以为10-20μm,优选为10-15μm,其厚度的误差(平均值和最大/最小值之差)可以在3μm以内。
当使用上述特定组分的感光性树脂组合物时,所制备的干膜阻焊剂呈现优良的显影性,尤其是碱性显影性,因此能容易形成微细图案或具有薄厚度的围堰。
具体而言,所述感光性树脂组合物的固化物可以包含:所述酸改性低聚物和光聚合性单体的光固化物;所述酸改性低聚物和热固性粘合剂树脂的热固化物;以及颜料。在所述感光性树脂组合物中,由于照射的光使光聚合性单体与酸改性低聚物的感光性部分(例如,'-C=C-'等双键等)进行反应而形成交联结构,在后续工序中用碱性显影液对非曝光部进行显影且对其余部分进行热固化时,热固性粘合剂树脂和酸改性低聚物的一定部分(例如,羧基(-COOH)等)进行反应能形成交联结构。因此,在使用所述感光性树脂组合物而获得的干膜阻焊剂中,各组分在热固化或光固化过程中能形成基于交联结合的网状结构,故能呈现更高的交联度。因此,使用所述干膜阻焊剂而形成的底部填充用围堰能具有优良的尺寸稳定性、耐热性、强度或其他机械性能。
所述感光性树脂组合物可包含具有羧基(-COOH)和可光固化的官能团的酸改性低聚物、光聚合性单体、热固性粘合剂树脂、以及颜料,还可以再包含光敏引发剂和有机溶剂。另外,所述感光性树脂组合物还可以任选地再包含热固性粘合剂树脂固化剂、热固性粘合剂催化剂、填料(filler)、均化剂(levelling agent)等添加剂。下面,对所述感光性树脂组合物的各组分进行具体说明。
酸改性低聚物
所述感光性树脂组合物包含具有羧基(-COOH)和可光固化的官能团的酸改性低聚物。这种酸改性低聚物能通过光固化与树脂组合物的其他成分(即光聚合性单体和/或热固性粘合剂树脂)形成交联结合,并且因为包含羧基所以使树脂组合物具有碱性显影性。
这种酸改性低聚物是在分子内具有羧基和可光固化的官能团的低聚物,该可光固化的官能团例如为丙烯酸酯基(acrylate group)或具有不饱和双键,可为已知的可用于光固化性树脂组合物的所有成分而并无特别限制。例如,这种酸改性低聚物的主链可以由酚醛环氧树脂(novolacepoxy resin)或聚氨酯(polyurethane)构成,可以使用在这种主链中导入羧基和丙烯酸酯基等的酸改性低聚物。所述可光固化的官能团优选由丙烯酸酯基构成,所述酸改性低聚物可通过使具有羧基的可聚合的单体和包括丙烯酸酯类化合物等的单体进行共聚,以低聚物的形式得到。更具体为,可用于所述树脂组合物的酸改性低聚物具体可以列举如下的组分。
(1)将(甲基)丙烯酸等不饱和羧酸(a)和苯乙烯、α-甲基苯乙烯(α-methylstyrene)、低级(甲基)丙烯酸烷基酯(alkyl(meth)acrylate)、异丁烯(isobutylene)等具有不饱和双键的化合物(b)进行共聚而得到的含羧基的树脂;
(2)通过将不饱和羧酸(a)和具有不饱和双键的化合物(b)的共聚物的一部分与具有乙烯基、烯丙基、(甲基)丙烯酰基等烯键式不饱和基和环氧基、酰基氯(acid chloride)等反应性基团的化合物(例如,(甲基)丙烯酸缩水甘油酯(glycidyl(meth)acrylate))反应,并将烯键式不饱和基作为侧链(pendant)而添加,从而得到的含羧基的感光性树脂;
(3)将(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸α-甲基缩水甘油酯(α-methylglycidyl(meth)acrylate)等具有环氧基和不饱和双键的化合物(c)、和具有不饱和双键的化合物(b)的共聚物与不饱和羧酸(a)反应,将生成的仲羟基与邻苯二甲酸酐(phthalic anhydride)、四氢邻苯二甲酸酐(tetrahydrophthalic anhydride)、六氢邻苯二甲酸酐(hexahydrophthalic anhydride)等饱和或不饱和多元酸酐(d)反应而得到的含羧基的感光性树脂;
(4)将顺丁烯二酸酐(maleic anhydride)、衣康酸酐(itaconicanhydride)等具有不饱和双键的酸酐(e)和具有不饱和双键的化合物(b)的共聚物与(甲基)丙烯酸羟烷基酯(hydroxyalkyl(meth)acrylate)等具有一个羟基和一个以上的烯键式不饱和双键的化合物(f)反应而得到的含羧基的感光性树脂;
(5)使在一分子中具有两个以上环氧基的下述的多官能环氧化合物(g)或进一步将多官能环氧化合物的羟基用环氧氯丙烷(epichlorohydrin)环氧化的多官能环氧树脂的环氧基与(甲基)丙烯酸等不饱和一元羧酸(monocarboxylic acid)(h)的羧基进行酯化反应(全部酯化或部分酯化,优选全部酯化),并将羟基进一步与饱和或不饱和多元酸酐(d)反应而得到的含羧基的感光性化合物;
(6)将具有不饱和双键的化合物(b)和(甲基)丙烯酸缩水甘油酯的共聚物的环氧基与碳原子数为2-17的烷基羧酸、含芳香基的烷基羧酸等一个分子中具有一个羧基且不具有烯键式不饱和双键的有机酸(i)反应,并将生成的仲羟基与饱和或不饱和多元酸酐(d)反应而得到的含羧基的树脂;
(7)通过脂肪族二异氰酸酯(diisocyanate)、支化的脂肪族二异氰酸酯、脂环族二异氰酸酯、芳香族二异氰酸酯等二异氰酸酯(j)、和二羟甲基丙酸(dimethylolpropionic acid)、二羟甲基丁酸(dimethylolbutanoic acid)等含羧基的二醇(dialcohol)化合物(k),以及聚碳酸酯类多元醇(polycarbonate based polyol)、聚醚类多元醇(polyther based polyol)、聚酯类多元醇(polyster based polyol)、聚烯烃类多元醇(polyolefine based polyol)、丙烯酸类多元醇(acrylic basedpolyol)、双酚A环氧烷烃加成物类二醇(bisphenol A alkyleneoxideadduct diol)、具有酚羟基(phenolic hydroxyl)和醇羟基(alcoholichydroxyl)的化合物等二醇化合物(m)的加聚反应(polyaddition)而得到的含羧基的聚氨酯树脂(urethane resin);
(8)通过二异氰酸酯(j)和双酚A环氧树脂、氢化双酚A环氧树脂、溴化双酚(Brominated bisphenol)A环氧树脂、双酚F环氧树脂、双酚S环氧树脂、联二甲苯酚(bixylenol)环氧树脂、联苯酚(biphenol)环氧树脂等二官能环氧树脂的(甲基)丙烯酸酯或其部分改性酸酐(n)和含羧基的二醇化合物(k)以及二醇化合物(m)的加聚反应而得到的含羧基的感光性聚氨酯树脂;
(9)在所述(7)或(8)树脂的合成中加入(甲基)丙烯酸羟烷基酯(hydroxyalkyl(meth)acrylate)等具有一个羟基和一个以上的烯键式不饱和双键的化合物(f),以在末端导入不饱和双键的含羧基的聚氨酯树脂;
(10)在所述(7)或(8)树脂的合成中加入异佛尔酮二异氰酸酯(isophorone diisocyanate)和季戊四醇三丙烯酸酯(pentaerythritoltriacrylate)的等摩尔反应物等在一分子内具有一个异氰酸酯基(isocyanate group)和一个以上的(甲基)丙烯酰基((meth)acryloylgroup)的化合物,以将末端(甲基)丙烯酸化((meth)acrylated)的含羧基的聚氨酯树脂;
(11)将在一分子中具有两个以上的氧杂环丁烷环(oxetane ring)的下述的多官能氧杂环丁烷化合物与不饱和一元羧酸(h)进行反应,并将得到的改性氧杂环丁烷化合物中的伯羟基与饱和或不饱和多元酸酐(d)进行反应而得到的含羧基的感光性树脂;
(12)在二环氧化合物(bisepoxy compound)和双酚类的反应生成物中导入不饱和双键,继而使其与饱和或不饱和多元酸酐(d)进行反应而得到的含羧基的感光性树脂;
(13)在将酚醛型酚醛树脂(novolac type phenolic resin)和环氧乙烷(ethylene oxide)、环氧丙烷(propylene oxide)、环氧丁烷(butyleneoxide)、氧杂环丁烷(trimethylene oxide)、四氢吡喃(tetrahydropyran)和/或碳酸亚乙酯(ethylene carbonate)、碳酸亚丙酯、碳酸亚丁酯(butylene carbonate)、2,3-碳酸甲基丙烯酸亚丙酯(2,3-carbonatepropyl meth acrylate)等环状碳酸酯(cyclic carbonate)的反应生成物与不饱和一元羧酸(h)进行反应,并将得到的反应生成物与饱和或不饱和多元酸酐(d)进行反应而得到的含羧基的感光性树脂;
在上述成分中,在所述(7)-(10)中用于树脂合成的含异氰酸酯基的化合物为不含苯环(benzene ring)的二异氰酸酯的情况下,和在所述(5)和(8)中用于树脂合成的多官能以及二官能环氧树脂为具有双酚A骨架、双酚F骨架、联苯骨架或联二甲苯酚骨架的线型结构化合物或其氢化产物的情况下,能获得在干膜阻焊剂(DFSR)的可挠性等方面的酸改性低聚物的可优选使用的成分。另外,在另一方面上,所述(7)-(10)的树脂的改性物在其主链上包含氨基甲酸酯键,因此有利于弯曲。
然后,作为上述酸改性低聚物可使用在市场上可得到的组分,这种组分具体可列举日本化学药品公司(Nippon Kayaku Co.Ltd.)的ZAR-2000等。
所述感光性树脂组合物可包含10-80重量%的酸改性低聚物,优选为15-75重量%,更优选为25-65重量%。若所述酸改性低聚物的含量过少,则导致显影性变差并使薄膜强度下降,若过多,则不仅会导致组合物过度显影,还会导致涂布时的均匀性降低。
另外,所述酸改性低聚物的酸值可为40-120mgKOH/g。若所述酸改性低聚物的酸值不满40mgKOH/g,则会导致碱性显影变得困难,若所述酸值超过120mgKOH/g,则会导致曝光部被显影液溶解,因此线会变得过薄或根据情况曝光部和未曝光部均被显影液溶解、剥离,由此导致难以形成正常的阻焊剂图案,因此不优选。
光聚合性单体
所述感光性树脂组合物可包含光聚合性单体。由于其包含这种光聚合性单体,因此在照射光时能形成一定的固化物或交联结构。这种光聚合性单体不仅对组合物赋予光固化性,还能起到调整为适合各种涂布方法的粘度或对碱性水溶液赋予适当的溶解性的作用。
这种光聚合性单体的具体可以列举以下:2-丙烯酸羟乙酯(hydroxyethyl acrylate)、2-丙烯酸羟丙酯(hydroxypropyl acrylate)、季戊四醇三丙烯酸酯(pentaerythritol triacrylate)或双季戊四醇五丙烯酸酯(dipentaerythritol pentaacrylete)等含羟基的丙烯酸酯类化合物;聚乙二醇二丙烯酸酯(polyethylene glycol diacrylate)或聚丙二醇二丙烯酸酯(polypropylene glycol diacrylate)等水溶性丙烯酸酯类化合物;三羟甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate)、季戊四醇四丙烯酸酯(pentaerythritol tetraacrylate)或双季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate)等多元醇的多官能聚酯丙烯酸酯(polyester acrylate)类化合物;三羟甲基丙烷(trimethylolpropane)、氢化双酚Α等多元醇或双酚A、联苯酚(biphenol)等多元酚的环氧乙烷加成物和/或环氧丙烷加成物的丙烯酸酯类化合物;所述含羟基的丙烯酸酯类化合物的异氰酸酯(isocyanate)改性物即多官能或单官能聚氨酯丙烯酸酯;双酚A二缩水甘油醚(bisphenol A diglycidyl ether)、氢化双酚A二缩水甘油醚或酚醛清漆环氧树脂(phenol novolac epoxy resin)的(甲基)丙烯酸加成物即环氧丙烯酸酯类化合物;己内酯(caprolactone)改性双三羟甲基丙烷四丙烯酸酯(ditrimethylolpropane tetraacrylate)、ε-己内酯改性双季戊四醇丙烯酸酯、己内酯改性羟基特戊酸新戊二醇酯二丙烯酸酯(hydroxy pivalic acid neopentyl glycol ester diacrylate)等己内酯改性的丙烯酸酯类化合物;或者对应于所述丙烯酸酯类的甲基丙烯酸酯类(metacrylic acid ester)等感光性(甲基)丙烯酸酯化合物,可以单独使用这些或组合两种以上而使用。
在这些化合物中,优选使用在一个分子中具有两个以上的(甲基)丙烯酰基的多官能(甲基)丙烯酸酯类化合物,更优选为季戊四醇三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、双季戊四醇六丙烯酸酯、己内酯改性双三羟甲基丙烷四丙烯酸酯等。另外,可使用市场上销售的日本化学药品公司的DPEA-12等。
所述感光性树脂组合物可以包含1-30重量%的上述光聚合性单体。如果所述光聚合性单体的含量低于1重量%,则可使光固化不能充分进行,如果所述含量超过30重量%,则可降低薄膜的干燥性或薄膜的物理性质。
光敏引发剂
所述感光性树脂组合物可包含光敏引发剂。这种光敏引发剂例如能起到在树脂组合物曝光部引发自由基光固化的作用。
这种光敏引发剂可使用已知的光敏引发剂,可使用以下物质:苯偶姻(benzoin)、苯偶姻甲醚(benzoin ethyl ether)、苯偶姻乙醚(benzoinmethyl ether)等苯偶姻和其烷基醚类;苯乙酮(acetophenone)、2,2-二甲氧基-2-苯基苯乙酮(2,2-dimethoxy-2-phenyl acetophenone)、1,1-二氯苯乙酮(1,1-dichloro acetophenone)、4-(1-叔丁基二氧基-1-甲基乙基)苯乙酮(4-(l-t-butyldioxy-1-methylethyl)acetophenone)等苯乙酮类;2-甲基蒽醌(2-methylanthraquinone)、2-戊基蒽醌(2-amylanthraquinone)、2-叔丁基蒽醌(2-t-butylanthraquinone)、1-氯蒽醌(1-chloroanthraquinone)等蒽醌类;2,4-二甲基噻吨酮(2,4-dimethylthioxanthone)、2,4-二异丙基噻吨酮(2,4-diisopropylthioxanthone)、2-氯噻吨酮(2-chlorothioxanthone)等噻吨酮类;苯乙酮二甲基缩酮(acetophenonedimethylketal)、苄基二甲基缩酮等缩酮类(benzyldimethylketal);二苯甲酮(benzophenone)、4-(l-叔丁基二氧基-1-甲基乙基)二苯甲酮(4-(l-t-butyldioxy-1-methylethyl)benzophenone)、3,3',4,4'-四(叔丁基二氧基羰基)二苯甲酮(3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone)等二苯甲酮类。
另外,作为优选的光敏引发剂可使用如下物质:2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基丙酮-1,2-苄基-2-二甲基氨基-1-(4-吗啉基苯基)-丁-1-酮(2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propanone-1,2-benzyl-2-dimethyl amino-1-(4-morpholino phenyl)-butane-1-one)、2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-1-[4-(4-吗啉基)苯基]-1-丁酮(2-(dimethylamino)-2-[(4-methyl phenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone)、Ν,Ν-二甲基氨基苯乙酮(Ν,Ν-dimethyl acetophenone)(作为千叶特殊化学品公司(Chiba SpecialtyChemicals Co.Ltd.)(现千叶日本公司,Chiba Japan Co.Ltd.)的Irgacure(注册商标)907、Irgacure369、Irgacur379等产品出售)等α-氨基苯乙酮类(α-amino acetophenone)、2,4,6-三甲基苯甲酰基二苯基氧化膦(2,4,6-trimethyl benzoyl diphenyl phosphine oxide)、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦(bis(2,4,6-trimethyl benzoyl)-phenylphosphine oxide)、双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基-戊基氧化膦(bis(2,6-dimethoxy benzoyl)-2,4,4-trimethyl-pentyl phosphine oxide)(作为BASF公司的Lucilin(注册商标)TPO、千叶特殊化学品公司的Irgacure(注册商标)819等出售)等酰基氧化膦(acyl phosphine oxide)类。
另外,优选的光敏引发剂可以列举肟酯(oxime ester)类。肟酯类的具体可列举如下:2-(乙酰氧基亚胺基甲基)噻吨-9-酮(2-(acetyl oxyimino methyl)thioxanthene-9-one)、(1,2-辛二酮,1-[4-苯硫基苯基]-,2-(O-苯甲酰肟))(1,2-octanedione,1-[4-phenylthio phenyl]-,-2-(O-benzoyl oxime))、(乙酮,1-[9-乙基-6-(2-甲基苯甲酰基)-9H-咔唑-3-基]-,1-(O-乙酰肟))(ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl],1-(O-acetyl oxime)等。市场商品有千叶特殊化学品公司GGI-325、Irgacure OXE01、Irgacure OXE02、ADEKA公司的N-1919、千叶特殊化学品公司的Darocur TPO等产品。
所述感光性树脂组合物可包含0.1-10重量%、优选为1-5重量%的所述光敏引发剂。若所述光敏引发剂的含量过少,则不能充分地进行光聚合反应,若所述含量过多,则可导致树脂组合物的析像能力的降低或所制备的干膜可靠性不充分。
热固性粘合剂树脂
所述感光性树脂组合物还可包含具有可热固化的官能团(例如选自环氧基、氧杂环丁烷基(oxetanyl group)、环状醚基和环状硫醚(thioether)基中的一种以上官能团)的热固性粘合剂树脂。这种热固性粘合剂通过热固化与酸改性低聚物和/或光聚合性单体形成交联,从而能确保干膜阻焊剂或底部填充用围堰的耐热性或机械性能。
所述热固性粘合剂树脂的软化点可以约为70-100°C,由此能在层压(lamination)时减少凹凸。当软化点低时,DFSR的粘着性(Tackiness)增加,当软化点高时,可导致流动性的恶化。
所述热固性粘合剂树脂可使用在一分子中具有两个以上的环状醚基和/或环状硫醚基(以下称为环状(硫)醚基)的树脂,也可使用二官能环氧树脂。还可以包括其他二异氰酸酯(diisocyanate)或其二官能封端异氰酸酯(blocked isocyanate)。
在所述一分子中具有两个以上的环状(硫)醚基的热固性粘合剂可以为在一分子中具有两个以上的三、四或五元环的环状醚基或环状硫醚基中的任意一种或两种以上基团的化合物。还有,所述热固性粘合剂可以是在一分子中至少具有两个以上环氧基的多官能环氧化合物,也可以为在一分子中至少具有两个以上氧杂环丁烷基的多官能氧杂环丁烷化合物或在一分子中具有两个以上硫醚基的环硫化物树脂(episulfide resin)等。
所述多官能环氧化合物具体可例举如下:双酚A环氧树脂、氢化双酚A环氧树脂、溴化双酚A环氧树脂、双酚F环氧树脂、双酚S环氧树脂、酚醛型环氧树脂、苯酚酚醛型环氧树脂(phenol novolac type epoxyresin)、甲酚酚醛型环氧树脂(cresol novolac type epoxy resin)、N-缩水甘油基环氧树脂(N-glycidyl type epoxy resin)、双酚A酚醛型环氧树脂、联二甲苯酚环氧树脂(bixylenol type epoxy resin)、联苯酚型环氧树脂、螯合型环氧树脂、乙二醛环氧树脂(glyoxal type epoxy resin)、含氨基环氧树脂、橡胶改性环氧树脂、双环戊二烯酚型环氧树脂(dicyclopentadiene phenolic type epoxy resin)、邻苯二甲酸二缩水甘油酯树脂(diglycidyl phthalate resin)、杂环环氧树脂(heterocyclic epoxyresin)、四缩水甘油基二甲苯酚乙烷树脂(tetra glycidyl xylenol ethaneresin)、硅氧烷改性环氧树脂、ε-己内酯改性环氧树脂等。另外,为了赋予耐燃性,可使用在其结构中导入磷等原子的物质。这些环氧树脂通过热固化来提高固化覆膜的粘合性、焊接(solder)耐热性、非电解镀覆抗性等特性。
所述多官能氧杂环丁烷化合物可列举双[(3-甲基-3-氧杂环丁烷基甲氧基)甲基]醚(bis[(3-methyl-3-oxetanyl methoxy)methyl]ether)、双[(3-乙基-3-氧杂环丁烷基甲氧基)甲基]醚(bis[(3-ethyl-3-oxetanylmethoxy)methyl ether])、1,4-双[(3-甲基-3-氧杂环丁烷基甲氧基)甲基]苯(1,4-bis[(3-methyl-3-oxetanyl methoxy)methyl]benzen)、1,4-双[(3-乙基-3-氧杂环丁烷基甲氧基)甲基]苯、丙烯酸(3-甲基-3-氧杂环丁烷基)甲酯((3-methyl-3-oxetanyl)methyl acrylate)、丙烯酸(3-乙基-3-氧杂环丁烷基)甲酯((3-ethyl-oxetanyl)methyl acrylate、甲基丙烯酸(3-甲基-3-氧杂环丁烷基)甲酯((3-methyl-3-oxetanyl)methylmethacrylate)、甲基丙烯酸(3-乙基-3-氧杂环丁烷基)甲酯((3-ethyl-3-oxetanyl)methyl methacrylate)或其低聚物或共聚物等多官能氧杂环丁烷类,此外还有氧杂环丁烷醇(oxetane alcohol)和酚醛树脂(novolac resin)、聚(对羟基苯乙烯)(poly(p-hydroxy styrene))、卡尔多型双酚(cardotype bisphenol)类、杯芳烃(calixarene)类、杯间苯二酚芳烃(calyx resorcin arene)类、或者倍半硅氧烷(silsesquioxane)等具有羟基的树脂和醚等。此外,还可以列举具有氧杂环丁烷环(oxetanering)的不饱和单体和(甲基)丙烯酸烷基酯的共聚物等。
在所述分子中具有两个以上的环状硫醚基的化合物可以列举日本环氧树脂公司制造的双酚A环硫化物树脂YL7000等。另外,也可以使用用硫原子取代酚醛型环氧树脂的环氧基的氧原子的环硫化物树脂等。
另外,可使用市场上销售的KUKDO CHEMICAL公司的YDCN-500-80P等。
所述感光性树脂组合物可包含1-30重量%的所述热固性粘合剂树脂。当所述热固性粘合剂树脂的含量不满1重量%时,会降低干膜的机械性能;当所述热固性粘合剂树脂的含量超过30重量%时,会降低树脂组合物的显影性。
有机溶剂
为了溶解各组分或赋予适当的粘度,所述感光性树脂组合物可与一种以上的有机溶剂混合使用。
这种有机溶剂具体可列举如下:甲乙酮(methyl ethyl ketone)、环己酮(cyclohexanone)等酮(ketone)类;甲苯(toluene)、二甲苯(xylene)、四甲基苯(tetra methyl benzene)等芳香烃类;乙二醇单乙醚(ethyleneglycol monoethyl ether)、乙二醇单甲醚(ethylene glycol monomethylether)、乙二醇单丁醚(ethylene glycol monobutyl ether)、二甘醇一乙醚(diethylene glycol monoethyl ether)、二甘醇单甲醚(diethyleneglycol monomethyl ether)、二甘醇单丁醚(diethylene glycol monobutylether)、丙二醇单甲醚(propylene glycol monomethyl ether)、丙二醇单乙醚(propylene glycol monoethyl ether)、双丙甘醇二乙醚(dipropyleneglycol diethyl ether)、三甘醇单乙醚(triethylene glycol monoethyl ether)等二醇醚(glycol ether)类(溶纤剂(cellosolve));乙酸乙酯(ethylacetate)、乙酸丁酯(butyl acetate)、乙二醇单乙醚乙酸酯(ethylene glycolmonoethyl ether acetate)、乙二醇单丁醚乙酸酯(ethylene glycolmonobutyl ether acetate)、二甘醇单乙醚乙酸酯(diethylene glycolmonoethyl ether acetate)、二甘醇单丁醚乙酸酯(diethylene glycolmonobutyl ether acetate)、丙二醇单甲醚乙酸酯(propylene glycolmonomethyl ether acetate)、双丙甘醇单甲醚乙酸酯(dipropylene glycolmonomethyl ether acetate)等乙酸酯(acetic acid ester)类;乙醇(ethanol)、丙醇(propanol)、乙二醇(ethyleneglycol)、丙二醇(propyleneglycol)、卡必醇(carbitol)等醇类;辛烷(octane)、癸烷(decane)等脂族烃;石油醚、石脑油(naphtha)、氢化石脑油、溶剂石脑油等石油类溶剂;二甲基乙酰胺(dimethyl acetamide)、二甲基甲酰胺(DMF,dimethyl formamide)等酰胺(amide)类等。这些溶剂可单独使用,也可使用两种以上的混合物。
所述感光性树脂组合物可包含约5-50重量%的所述有机溶剂。当所述有机溶剂的含量过少时,导致组合物的粘度过大,从而能降低涂布性,当所述含量过多时,会不易干燥而导致干膜阻焊剂特性的降低或者粘着性的增加。
颜料
欲将所述底部填充用围堰的颜色呈现为白色(White)时,作为颜料可使用颜料白6氧化钛(titanium oxide)。用作白色颜料的氧化钛有金红石(rutile)型和锐钛矿(anatase)型。锐钛矿型与金红石型相比,虽然白色度优良,但因具有光学活性而可能会导致由光所引起的黄变,因此优选使用白色度虽差但不具有光学活性的金红石型。
欲将所述底部填充用围堰的颜色呈现为黄色(Yellow)时,可以使用蒽醌类、异吲哚啉酮(isoindolinone)类、缩合偶氮(condensation azo)类、苯并咪唑酮(benzimidazolone)类等颜料,例如可使用颜料黄108、颜料黄147、颜料黄151、颜料黄166、颜料黄181、颜料黄193等。
欲将所述底部填充用围堰的颜色呈现为绿色(Green)时,颜料可使用颜料绿7、颜料绿36、溶剂绿3、溶剂绿5、溶剂绿20、溶剂绿28等。但是,使用绿色颜料时,卤素会造成问题,因此有时也会为了实现绿色而适当地组合黄色和蓝色颜料而使用。
欲将所述底部填充用围堰的颜色呈现为黑色(Black)时,颜料可使用炭黑、钛黑、氧化铬(chrome oxide)、氧化铁、苯胺(aniline)黑、苝(perylene)类颜料等。
欲将所述底部填充用围堰的颜色呈现为红色(Red)时,可使用颜料红13、颜料红32、颜料红122、颜料红177、颜料红185、颜料红226、颜料红246等。
所述感光性树脂组合物可包含0.01-10重量%的、优选为1-5重量%的所述颜料。若所述颜料的含量过少,则会导致可见性(visibility)、遮盖力(hiding power)的降低,若所述含量过多,则会导致耐热性等机械性能的降低。
但使用白色颜料时,因白色颜料其自身也起到填料的作用,因此可排除其他无机填料,相应地白色颜料含量相对于感光性树脂组合物的整体重量可使用50重量%以内。另一方面,所述感光性树脂组合物除上述成分之外还可选择性地包含下述成分。
热固性粘合剂树脂固化剂
所述感光性树脂组合物还可任选地包含可提高热固性粘合剂树脂的固化度的热固性粘合剂树脂固化剂。
这种热固性粘合剂脂固化剂可列举胺(amine)类化合物、酸酐(acidanhydride)类化合物、酰胺(amide)类化合物、苯酚类化合物等。所述胺类化合物可使用二氨基二苯甲烷(diaminodiphenyl methane)、二亚乙基三胺(diethylenetriamine)、三亚乙基四胺(triethylenetetramine)、二氨基二苯砜(diamino-diphenyl-sulfone)、异佛尔酮二胺(isophoronediamine)等。所述酸酐类化合物可使用邻苯二甲酸酐(phthalicanhydride)、偏苯三酸酐(trimellitic anhydride)、均苯四甲酸酐(pyromellitic anhydride)、顺丁烯二酸酐(maleic anhydride)、四氢邻苯二甲酸酐(tetrahydro phthalic anhydride)、甲基四氢邻苯二甲酸酐(methyl tetrahydro phthalic anhydride)、甲基4-降冰片烯-1,2-二羧酸酐(methyl nadic anhydride)、六氢邻苯二甲酸酐(hexahydrophthalicanhydride)、甲基六氢邻苯二甲酸酐(methyl hexahydrophthalicanhydride)等。所述酰胺类化合物可使用双氰胺(dicyandiamide)、由亚油酸(linoleic acid)的二聚体(dimer)和乙二胺(ethylenediamine)合成的聚酰胺树脂(polyamide resin)等。所述苯酚类化合物可使用双酚A、双酚F、双酚S、双酚芴(fluorene bisphenol)、萜二酚(terpenediphenol)等多元酚类;苯酚类和醛(aldehyde)类、酮类或二烯(diene)类等通过缩合得到的酚树脂(phenol resin);通过苯酚类和取代联苯(Substituted Phenyl)类的缩聚而得到的酚树脂;苯酚类和/或酚树脂的改性物;四溴双酚A(tetrabromobis phenol A)、溴化酚树脂等卤化苯酚类;咪唑(imidazole)类、BF3-胺络合物(BF3-amine complex)、胍(guanidine)衍生物等其他物质。
所述感光性树脂组合物还可包含0.01-15重量%的所述热固性粘合剂树脂固化剂。若所述热固性粘合剂树脂固化剂的含量过少,则会导致提高环氧树脂的固化度的效果微乎其微,若所述含量过多,则会导致干膜的物理性质的降低。
热固性粘合剂树脂催化剂
热固性粘合剂树脂催化剂可提高热固性粘合剂树脂的固化速度。
这种热固性粘合剂催化剂可列举如下:咪唑(imidazole)、2-甲基咪唑(2-methyl imidazole)、2-乙基咪唑(2-ethyl imidazole)、2-乙基-4-甲基咪唑(2-ethyl-4-methyl imidazole)、2-苯基咪唑(2-phenylimidazole)、4-苯基咪唑(4-phenyl imidazole)、1-氰乙基-2-苯基咪唑(1-cyanoethyl-2-phenyl imidazole)、1-(2-氰乙基)-2-乙基-4-甲基咪唑(1-(2-cyanoethyl)-2-ethyl-4-methyl imidazole)等咪唑衍生物;双氰胺(dicyandiamide)、苄基甲胺(benzyl methyl amine)、4-(二甲基氨基)-N,N-二甲基苄胺(4-(dimethylamino)-N,N-dimethylbenzyl amine)、4-甲氧基-Ν,Ν-二甲基苄基胺(4-methoxy-N,N-dimethylbenzyl amine)、4-甲基-Ν,Ν-二甲基苄基胺(4-methyl-Ν,Ν-dimethylbenzyl amine)等胺化合物;己二酸二酰肼(adipic acid dihydrazide)、癸二酸二酰肼(sebacic acid dihydrazide)等肼(hydrazine)化合物;三苯基膦(triphenylphospine)等磷化合物等。另外,在市场销售的有例如:四国化成工业公司(Shikoku Kasei Kogyo Co.Ltd.)制备的2MZ-A、2MZ-OK、2PHZ、2P4BHZ、2P4MHZ(均为咪唑类化合物的商品名);San-Apro公司制造的U-CAT3503N、UCAT3502T(均为二甲基胺的封端异氰酸酯化合物的商品名);San-Apro公司制造的DBU、DBN、U-CATSA102、U-CAT5002(均为二环脒(amidine)化合物及其盐)等。尤其是但并不局限于上述物质,还可以是环氧树脂或氧杂环丁烷化合物的热固化催化剂,又或者是能促进环氧基和/或氧杂环丁烷基和羧基的反应的物质,可以单独使用或混合两种以上而使用。另外,可使用胍胺(guanamine)、乙酰胍胺(acetoguanamine)、苯并胍胺(benzoguanamine)、三聚氰胺(melamine)、2,4-二氨基-6-甲基丙烯酰氧基乙基-S-三嗪(2,4-diamino-6-methacryloyloxyethyl-S-triazine)、2-乙烯基-4,6-二氨基-S-三嗪(2-vinyl-4,6-diamino-S-triazine)、2-乙烯基-4,6-二氨基-S-三嗪(2-vinyl-4,6-diamino-S-triazine)和异氰脲酸的加合物、2,4-二氨基-6-甲基丙烯酰氧基乙基-S-三嗪(2,4-diamino-6-methacryloyloxyethyl-S-triazine)和异氰脲酸的加合物等S-三嗪衍生物,优选将这些赋予粘合性功能的化合物与所述热固性粘合剂催化剂一并使用。
从适当的热固化性的方面来讲,基于所述感光性树脂组合物整体重量计,热固性粘合剂催化剂的含量可约为0.3-15重量%。
填料
填料起到提高热稳定性、热尺寸稳定性、树脂粘合力的作用。另外,能增强颜色,因此还起到体质颜料(extender pigment)的作用。填料可使用无机或有机填充剂,例如可使用硫酸钡(barium sulfate)、钛酸钡(barium titanate)、无定形二氧化硅、晶体二氧化硅、熔融二氧化硅、球形二氧化硅、滑石(talc)、粘土(clay)、碳酸镁、碳酸钙、氧化铝(矾土)、氢氧化铝、云母(mica)等。
基于所述感光性树脂组合物整体重量计,填料的含量优选为约5-50重量%。当超过50重量%时,因组合物的粘度变高,从而降低涂布性或固化度,因此不优选。
均化剂
当进行涂膜时,均化剂能起到去除表面的爆裂(Popping)或凹陷(Crater)的作用。
均化剂可使用硅化合物、氟化合物、高分子类等,例如BYK-ChemieGmbH的BYK-380N、BYK-307、BYK-378、BYK-350等。
基于所述感光性树脂组合物整体重量计,均化剂的含量优选为0.05-10重量%。当所述均化剂的使用量不满0.05重量%时,不足以去除爆裂或凹陷,当其使用量超过10重量%时,存在产生很多起泡的问题。
分散剂
分散剂起到提高填料、颜料等的分散稳定性的作用。分散剂例如可使用BYK-Chemie GmbH的Disperbyk-110、Disperbyk-162、Disperbyk-168等。
基于感光性树脂组合物整体重量计,分散剂的含量优选为0.01-10重量%。当所述分散剂不满0.01重量%时,会导致分散不充分,当其超过10重量%时,会对耐热性和可靠性产生不利影响。
另一方面,根据发明的其他实施方案,可提供一种包含如下步骤的印刷电路板的制造方法:在基板上层叠包含感光性树脂组合物的干燥物或固化物的干膜的步骤,其中所述感光性树脂组合物包含具有羧基(-COOH)和可光固化的官能团的酸改性低聚物、光聚合性单体、光敏引发剂、热固性粘合剂树脂、以及包含有机溶剂和颜料;对所述基板外缘部位的干膜进行曝光的步骤;以及清洗所述已曝光的干膜的步骤。
如上所述,若使用由包含所述特定组分的感光性树脂组合物所得到的干膜,则能形成具有很薄且均匀厚度的底部填充用围堰。尤其是,这种底部填充用围堰表现出优良的机械性能,所以即使是以薄的厚度也能实现一定标准以上的高度和强度,并由此能防止注入或填充于印刷电路板的底部填充材料的流出,能最大限度地减少在所述底部填充工序或半导体制造工序中可能发生的底部填充用围堰的损伤或物理性质降低的现象。
图1为示出常规底部填充工序的示意图,已知的底部填充工序依次进行对位和助焊剂分配(Alignment and Flux Dispensing)步骤、铅锡球焊(Solder Bump Reflow)步骤、助焊剂清洗(Flux Cleaning)步骤、以及底部填充(Underfilling)步骤。
具体来讲,底部填充工序可按照以下方法进行:对形成有焊料隆起焊盘2的晶片元件1和形成有电极极板3的基板4进行对位后分配助焊剂,之后对焊料隆起焊盘2进行回焊,洗净助焊剂,然后将底部填充材料5填充在晶片元件1和基板4之间。
图2为示出使用底部填充用围堰的底部填充工序的示意图,其中所述底部填充用围堰是通过使用包含上述感光性树脂组合物的干燥物或固化物的干膜而形成的。所述底部填充用围堰形成于晶片元件1的外缘部位,因此可防止所注入的底部填充材料5的流出。
所述底部填充用围堰在将由含有上述特定组分的感光性树脂组合物所得到的干膜层叠于基板后,经过曝光、显影、清洗步骤而形成。
具体来讲,所述底部填充用围堰可通过以下步骤来形成:使用感光性树脂组合物制造干膜的步骤;在基板和晶片元件之间层叠干膜的步骤;将与所希望的围堰图案相对应的光掩模(photo mask)放置于干膜上,并在之后对其进行曝光的步骤;对曝光后的干膜进行显影而去除不需要的部分,从而形成所希望的围堰图案的步骤;以及在显影后进行加热固化,从而制成由干膜型阻焊剂构成的围堰的步骤。
包含于所述感光性树脂组合物中的各组分的具体内容如上所述。
通过以下步骤可以制备从下到上由承载膜、感光性膜、离型膜所构成的干膜,该步骤包括:将上述感光性树脂组合物涂于承载膜上的步骤;通过烘箱对所述承载膜进行干燥的步骤;以及在所述干燥物上层叠离型膜的步骤。此时,承载膜可使用聚对苯二甲酸乙二醇酯(PET,polyethylene terephthalate)等,离型膜可使用聚乙烯(PE,Poly Ethylene)等。
对所述感光性树脂组合物的涂布或涂层可使用缺角轮涂布机(comma coater)、刮刀涂布机(blade coater)、浸渍提拉涂布机(dipcoater)、棒式涂布机(rod coater)、挤压涂布机(squeeze coater)、反向涂布机(reverse coater)、门辊涂布机(transfer roll coater)、凹槽辊涂布机(gravure coater)或喷雾涂布机(spray coater)等已知的涂布方法。所述烘箱的干燥温度优选为70-110°C左右,感光性树脂组合物形成的感光性膜的厚度优选为10-35μm左右。
在所述印刷电路板的制造方法中,在基板上层叠以上述方式得到的干膜(已去除离型膜的状态),使用一定图案的光掩模进行曝光,以在所述基板的外缘部位能形成底部填充用围堰。
在层叠已去除所述离型膜的干膜的步骤中,可使用真空层压机、贴膜机(hot roll laminator)、真空压膜机(vacuum press)等。在所述曝光步骤中可使用的光源有紫外线(UV)、电子束、X射线等,用具有一定波长的辐射(UV等)对所述基板进行曝光(Exposure)。
所述曝光可以用光掩模选择性地进行曝光,或用激光直接曝光机(laser direct exposer)直接进行图案曝光。在曝光之后剥离承载膜。曝光量根据涂膜厚度而不同,但优选为0-1,000mJ/cm2。若进行所述曝光,例如,在曝光部发生光固化,从而能形成酸改性低聚物和光聚合性单体等的交联结合,其结果是能形成不会被之后的显影去除的状态。与此相比,非曝光部的羧基保持原状态,因此能形成为可碱性显影的状态。
在进行所述曝光步骤之后,对所述干膜进行显影而去除不需要的部分,从而形成所希望的围堰图案。在进行曝光后的显影时,一般使用浸渍法或喷射法而浸泡于显影液中,其中显影液使用氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、磷酸钠、硅酸钠、氨、胺类等碱性水溶液,用碱性水溶液进行显影之后用水清洗。通过这种显影,能够只残留曝光部的膜。
在清洗所述已曝光的干膜之后,可进一步进行后固化(Post Cure)残留物的步骤。此时,后固化温度在100°C以上是适当的。
可通过上述制造步骤(例如,干膜的制备步骤、对干膜进行曝光的步骤或对已清洗的干膜进行的后固化(Post Cure)步骤等),形成包含所述感光性树脂组合物的干燥物或固化物的底部填充用围堰。这种感光性树脂组合物的固化物可包含:所述酸改性低聚物和光聚合性单体的光固化物;所述酸改性低聚物和热固性粘合剂树脂的热固化物;以及颜料。
通过所述制备方法得到的印刷电路板可包含具有10-20μm、优选为10-15μm厚度的所述底部填充用围堰。这种底部填充用围堰的厚度误差(平均值和最大/最小值之差)可以在3μm以内。
另一方面,所述印刷电路板的制备方法还可包含以下步骤:在所述基板上形成电极极板的步骤;将焊料隆起焊盘放置于所述电极极板上的步骤;以及以所述焊料隆起焊盘为介质对半导体晶片通过倒装晶片进行结合的步骤。所述焊料隆起焊盘可以以在半导体晶片上方结合的状态位于所述电极极板上,也可以事先设置于所述电极极板上之后再与所述半导体晶片相结合。
因此,所述印刷电路板可包括:在所述基板上形成的电极极板;在所述电极极板上形成的焊料隆起焊盘;以及以所述焊料隆起焊盘为介质通过倒装晶片结合的半导体晶片。
另外,所述印刷电路板的制备方法还包含在所述基板和所述半导体晶片之间注入底部填充材料的步骤,由此能够提供填充有底部填充材料的印刷电路板。
发明效果
根据本发明,能提供一种包括具有优良机械性能的、具有微细且均匀厚度的底部填充用围堰的印刷电路板及其制造方法。
附图说明
图1是表示常规底部填充工序的示意图。
图2是表示在基板上形成底部填充用围堰时的底部填充工序的示意图。
实施发明的方式
在下述实施例中对本发明进行更详细的说明。但下述实施例只是例示了本发明,本发明的内容并不限于下述实施例。
<实施例:印刷电路板的制造>
实施例1
(1)感光性树脂组合物的制备
作为酸改性低聚物使用35重量%的日本化学药品公司的CCR-1235,作为光聚合性单体使用13重量%的KAYARAD的DPEA-12,作为光敏引发剂使用3重量%的TPO(thermoplastic polyolefin,热塑性聚烯烃),作为环氧树脂使用13重量%的日本化学药品公司的EOCN-1020,作为环氧固化剂使用0.5重量%的双氰胺,作为环氧催化剂使用0.5重量%的2MI,作为白色颜料使用19重量%的金红石型氧化钛(杜邦(DuPont)公司,Tie pure R-931),作为均化剂使用0.5重量%的BYK-380N,作为分散剂使用0.5重量%的Disperbyk-110,作为溶剂使用15重量%的DMF(Dimethyl Formamide,二甲基甲酰胺),由此制备了白色感光性树脂组合物。
(2)干膜的制备
在PET承载膜上涂布所述制备的感光性树脂组合物,然后通过75°C的烘箱对其进行干燥,之后层叠PE离型膜,从而制备了从下到上构成为承载膜、感光性膜(厚度为15μm)、离型膜的干膜。
(3)印刷电路板的制造
在剥离所制备的干膜的保护膜(cover film)之后,在形成有电路的基板上真空层压感光性膜层。然后,将与所希望的底部填充用围堰图案相对应的光掩模放置于干膜上并用UV对其进行曝光,之后用碱性显影液进行显影并去除不需要的部分,从而形成所希望的底部填充用围堰图案。随后,对得到的底部填充用围堰进行后固化,从而制成了形成有由干膜型阻焊剂构成的围堰的印刷电路板。
实施例2
(1)感光性树脂组合物的制备
作为酸改性低聚物使用35重量%的日本化学药品公司的CCR-1235,作为光聚合性单体使用13重量%的KAYARAD的DPEA-12,作为光敏引发剂使用3重量%的TPO,作为环氧树脂使用13重量%的日本化学药品公司的EOCN-1020,作为环氧固化剂使用0.5重量%的双氰胺,作为环氧催化剂使用0.5重量%的2MI,作为填料使用18重量%的BaSO4,作为颜料分别使用0.5重量%的颜料蓝15:3和0.5重量%颜料黄151,作为均化剂使用0.5重量%的BYK-380N,作为分散剂使用0.5重量%的Disperbyk-110,作为溶剂使用15重量%的DMF,由此制备了绿色感光性树脂组合物。
(2)干膜的制备以及印刷电路板的制造
除使用所述制备的感光性树脂组合物之外,通过与实施例1相同的方法制备了干膜和印刷电路板。
实施例3
(1)感光性树脂组合物的制备
作为酸改性低聚物使用35重量%的日本化学药品公司的CCR-1235,作为光聚合性单体使用13重量%的KAYARAD的DPEA-12,作为光敏引发剂使用3重量%的TPO,作为环氧树脂使用13重量%的日本化学药品公司的EOCN-1020,作为环氧固化剂使用0.5重量%的双氰胺,作为环氧催化剂使用0.5重量%的2MI,作为填料使用18重量%的BaSO4,作为颜料使用1.0重量%的颜料黄151,作为均化剂使用0.5重量%的BYK-380N,作为分散剂使用0.5重量%的Disperbyk-110,作为溶剂使用15重量%的DMF,由此制备了黄色感光性树脂组合物。
(2)干膜的制备以及印刷电路板的制造
除使用所述制造的感光性树脂组合物之外,通过与实施例1相同的方法制备了干膜和印刷电路板。
<比较例:印刷电路板的制造>
除使用日本专利公开第1996-325476号公开的液态阻焊剂形成底部填充用围堰之外,通过与实施例1相同的方法制备了干膜和印刷电路板。
<实验例:底部填充用围堰的物理性质测定>
对实施例和比较例制备的围堰进行了颜色、厚度和均匀度、倒装晶片适用与否、以及在AOI设备上的检测能力的比较,其结果如表1所示。
表1
从表1中可以看出,比较例的颜色为绿色,相反地实施例可以具有白色等多种颜色。另外,在比较例中不仅以1mm左右的厚度较厚地形成,且厚度偏差严重而不均匀,相反地在实施例中能形成具有均匀厚度的围堰,且能以10-15μm厚度形成很薄且厚度均匀的围堰。
另外,在比较例中因厚度不均匀而难以使用倒装晶片,相反地在实施例中因厚度薄且均匀而可以使用倒装晶片。另外,在比较例中因颜色有限而导致检测能力降低,相反地在实施例中在AOI设备中的检测能力优良。
符号说明
1:晶片元件
2:焊料隆起焊盘
3:电极极板
4:基板
5:底部填充材料
6:围堰
Claims (19)
1.一种印刷电路板,其包括沿着具有半导体晶片的基板外缘形成的底部填充用围堰,其中
所述底部填充用围堰包含干膜阻焊剂,所述干膜阻焊剂包含感光性树脂组合物的干燥物或固化物,所述感光性树脂组合物包含:具有羧基(-COOH)和可光固化的官能团的酸改性低聚物;光聚合性单体;热固性粘合剂树脂;以及颜料。
2.权利要求1所述的印刷电路板,其中
所述感光性树脂组合物的固化物包含:所述酸改性低聚物和光聚合性单体的光固化物;所述酸改性低聚物和热固性粘合剂树脂的热固化物;以及颜料。
3.权利要求1所述的印刷电路板,
其包括:在所述基板上形成的电极极板;在所述电极极板上形成的焊料隆起焊盘;以及以所述焊料隆起焊盘为介质通过倒装晶片结合的半导体晶片。
4.权利要求1所述的印刷电路板,其中
所述底部填充用围堰用于防止填充于基板和半导体晶片之间的填充材料的流出。
5.权利要求3所述的印刷电路板,其中
所述底部填充用围堰形成在所述基板的外缘和半导体晶片的外缘之间,
并且其具有基板和半导体晶片之间间隔的大小以上的高度。
6.权利要求1所述的印刷电路板,其中
所述底部填充用围堰具有选自由白色、黄色、绿色、黑色以及红色组成的组群中的一种颜色。
7.权利要求6所述的印刷电路板,其中
所述底部填充用围堰具有不同于所述基板或所述基板上的阻焊剂的颜色。
8.权利要求1所述的印刷电路板,其中
所述底部填充用围堰具有10-20μm的厚度。
9.权利要求1所述的印刷电路板,其中
所述酸改性低聚物的可光固化的官能团为丙烯酸酯基。
10.权利要求1所述的印刷电路板,其中
所述酸改性低聚物为具有羧基的可聚合的单体和包括丙烯酸酯类化合物的单体的共聚物。
11.权利要求1所述的印刷电路板,其中
所述酸改性低聚物的酸值为40-120mgKOH/g。
12.权利要求1所述的印刷电路板,其中
所述光聚合性单体包括选自由含羟基的丙烯酸酯类化合物、水性丙烯酸酯类化合物、多元醇的多官能聚酯丙烯酸酯类化合物、多元醇或多元酚的环氧乙烷加成物的丙烯酸酯类化合物、多元醇或多元酚的环氧丙烷加成物的丙烯酸酯类化合物、多官能或单官能聚氨酯丙烯酸酯、环氧基丙烯酸酯类化合物、己内酯改性的丙烯酸酯类化合物以及感光性(甲基)丙烯酸酯类化合物组成的组群中的一种以上的化合物。
13.权利要求1所述的印刷电路板,其中
所述光敏引发剂为选自由苯偶姻和其烷基醚类、苯乙酮类、蒽醌类、噻吨酮类、缩酮类、二苯甲酮类、α-氨基苯乙酮类、酰基氧化膦类以及肟酯类组成的组群中的一种以上。
14.权利要求1所述的印刷电路板,其中
所述热固性粘合剂树脂包含被选自由环氧基、氧杂环丁烷基、环状醚基以及环状硫醚基组成的组群中的一种以上官能团取代的化合物。
15.权利要求1所述的印刷电路板,其中
所述感光性树脂组合物还包含光敏引发剂和有机溶剂。
16.权利要求15所述的印刷电路板,其中
所述感光性树脂组合物包含:
10-80重量%的具有羧基(-COOH)和可光固化的官能团的酸改性低聚物;
1-30重量%的光聚合性单体;
0.1-10重量%的光敏引发剂;
1-30重量%的热固性粘合剂树脂;
0.01-10重量%的颜料;以及
5-50重量%的溶剂。
17.一种印刷电路板的制造方法,其包括:
在基板上层叠包含感光性树脂组合物的干燥物或固化物的干膜的步骤,其中所述感光性树脂组合物包含具有羧基(-COOH)和可光固化的官能团的酸改性低聚物、光聚合性单体、光敏引发剂、热固性粘合剂树脂、有机溶剂以及颜料;
对所述基板的外缘部位的干膜进行曝光的步骤;以及
清洗所述已曝光的干膜的步骤。
18.权利要求17所述的印刷电路板的制造方法,其中
所述制造方法还包括:
在所述基板上形成电极极板的步骤;
将焊料隆起焊盘放置于所述电极极板上的步骤;以及
以所述焊料隆起焊盘为介质对半导体晶片进行倒装晶片结合的步骤。
19.权利要求18所述的印刷电路板的制造方法,
其还包括在所述基板和所述半导体晶片之间注入底部填充材料的步骤。
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Also Published As
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JP2013534714A (ja) | 2013-09-05 |
KR101450727B1 (ko) | 2014-10-16 |
US20130063917A1 (en) | 2013-03-14 |
TW201220972A (en) | 2012-05-16 |
US9865480B2 (en) | 2018-01-09 |
CN102906867B (zh) | 2016-04-27 |
KR20110128135A (ko) | 2011-11-28 |
TWI503055B (zh) | 2015-10-01 |
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