CN107614564B - 热膨胀性调整剂、作为热膨胀性调整剂的用途、热固性树脂组成物 - Google Patents
热膨胀性调整剂、作为热膨胀性调整剂的用途、热固性树脂组成物 Download PDFInfo
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- CN107614564B CN107614564B CN201680010463.3A CN201680010463A CN107614564B CN 107614564 B CN107614564 B CN 107614564B CN 201680010463 A CN201680010463 A CN 201680010463A CN 107614564 B CN107614564 B CN 107614564B
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Classifications
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- C08G59/20—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 characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
- C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
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- C—CHEMISTRY; METALLURGY
- 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
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- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- 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
- C08G59/20—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 characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明提供一种热膨胀性调整剂,对抑制加热所致电路基板的变形有效,可降低绝缘树脂层等所用的热固性树脂组成物的硬化物的线热膨胀系数。通过调配含有下述式(1)的乙炔脲衍生物化合物的热膨胀性调整剂,可降低热固性树脂组成物硬化而成的硬化物的线热膨胀系数,因此可提供热所致变形较小的构材。
Description
技术领域
本发明涉及一种热膨胀性调整剂、作为热膨胀性调整剂的用途、热固性树脂组成物、含有该热固性树脂组成物的绝缘材、密封材、导电膏、使该热固性树脂组成物硬化而成的硬化物、具有该热固性树脂组成物的基板材料、该热固性树脂组成物含浸于基材而成的预浸体、该预浸体的热固性树脂组成物硬化而成的构材、热膨胀率的调整方法、以及使用该调整方法所制造的构材。
背景技术
于以电气电子产业为中心的各种领域中,随着追求电子机器的小型化、多功能化、通信速度的高速化等,要求电子机器中所用的电路基板进一步高密度化。为了响应此种高密度化的要求,谋求电路基板的多层化。
多层化的电路基板例如以如下方式制作:在包含电气绝缘层与形成于其表面的导体层的内层基板上,积层电气绝缘层,在所述电气绝缘层上形成导体,进一步重复于电气绝缘层上形成导体。为了响应电路基板的多层化的要求,提出有各种热固性树脂组成物(专利文献1~3)。
专利文献1中记载有为了解决将无机填充材高填充而产生的问题,而使用含有特定环氧树脂、酚树脂、顺丁烯二酰亚胺化合物及无机填充材的树脂组成物。
专利文献2中,作为可适宜用于电路基板的绝缘层形成的树脂组成物,记载有含有特定环氧树脂、硬化剂、无机填充剂而成者。
专利文献3中记载有为了提供低热膨胀性、翘曲特性优异的预浸体等,将预浸体中所含的热固性树脂组成物层以含有特定顺丁烯二酰亚胺化合物、特定硅氧烷二胺、及特定具有酸性取代基的胺化合物的热固性树脂组成物而构成。
[现有技术文献]
[专利文献]
专利文献1:日本特开2014-185221号公报。
专利文献2:日本特开2011-89038号公报。
专利文献3:日本特开2014-24927号公报。
发明内容
[发明所要解决的问题]
专利文献1~3所揭示的热固性树脂组成物为了使线热膨胀系数下降而使用无机填充剂。然而,调配无机填充剂会成为使热固性树脂组成物的成形容易度(以下称为「成形性」)下降的原因。
专利文献3记载有使用特定的热固性树脂组成物使线热膨胀率系数下降。然而,该文献中所记载的热固性树脂组成物含浸于基材而使用,并非使仅由热固性树脂组成物形成的硬化物的线热膨胀系数下降。
本发明的目的在于提供一种可降低使热固性树脂组成物硬化而成的硬化物的线热膨胀系数的热膨胀性调整剂、作为热膨胀性调整剂的用途、热固性树脂组成物、含有该热固性树脂组成物的密封材及导电膏、使该热固性树脂组成物硬化而成的硬化物、具有该热固性树脂组成物的基板材料、使该热固性树脂组成物含浸于基材而成的预浸体、使该预浸体的热固性树脂组成物硬化而成的构材、热膨胀率的调整方法、以及使用该调整方法所制造的构材。
[解决问题的技术手段]
为了解决上述课题而提供的本发明如下所述。
(1)一种热膨胀性调整剂,含有下述式(1)的乙炔脲衍生物化合物。
(2)一种作为热膨胀性调整剂的用途,上述式(1)的乙炔脲衍生物化合物作为热膨胀性调整剂的用途。
(3)一种热固性树脂组成物,含有根据(1)所述的热膨胀性调整剂。
(4)一种绝缘材,含有根据(3)所述的热固性树脂组成物。
(5)一种密封材,含有根据(3)所述的热固性树脂组成物。
(6)一种导电膏,含有根据(3)所述的热固性树脂组成物。
(7)一种硬化物,使根据(3)所述的热固性树脂组成物硬化而成。
(8)根据(7)所述的硬化物,其中线热膨胀系数为40ppm/℃以下。
(9)根据(7)所述的硬化物,其中玻璃转移温度为180℃以上。
(10)一种基板材料,具有根据(3)所述的热固性树脂组成物。
(11)一种预浸体,根据(3)所述的热固性树脂组成物含浸于基材而成。
(12)一种构材,根据(5)所述的密封材、根据(6)所述的导电膏、根据(10)所述的基板材料的所述热固性树脂组成物、或根据(11)所述的预浸体的所述热固性树脂组成物硬化而成。
(13)一种线热膨胀系数的调整方法,具备:测定工序,测定根据(3)所述的热固性树脂组成物硬化而成的构材的线热膨胀系数;以及调整工序,基于所述测定的线热膨胀系数,调整所述热固性树脂组成物的使用量及所述热固性树脂组成物中的热膨胀率调整剂的含量的至少一个。
(14)根据(12)所述的构材,其中所述热固性树脂组成物的使用量或所述热膨胀率调整剂的含量使用根据(13)所述的线热膨胀系数的调整方法而设定。
[发明的效果]
根据本发明可降低硬化性树脂硬化而形成的硬化物的线热膨胀系数。因此可抑制构成电路基板等的硬化物所构成的构材与其他构材的间的线热膨胀系数差,藉此抑制热应力所致电路基板等的变形。
具体实施方式
以下说明本发明的实施方式。
本发明的热膨胀性调整剂含有下述式(1)的乙炔脲衍生物化合物。
发明者们发现:有关于热固性树脂组成物中以式(1)所示的乙炔脲衍生物化合物(以下适当称为「乙炔脲衍生物化合物」),通过使其自身硬化,而可获得线热膨胀系数较低的硬化物,且若调配于热固性树脂组成物中,则使热固性树脂组成物硬化而成的硬化物的线热膨胀系数变小。即,发明者们通过发现上述乙炔脲衍生物化合物的新性质,而想到含有乙炔脲衍生物化合物的热膨胀性调整剂的本发明。
本实施方式的热固性树脂组成物由于含有乙炔脲衍生物化合物,故通过热固性树脂组成物硬化而成的硬化物而可形成线热膨胀率较低的构材。
本实施方式的含有乙炔脲衍生物化合物的热膨胀性调整剂,包括含有乙炔脲衍生物化合物作为其成分的一部分者、及仅由乙炔脲衍生物化合物所构成。而且,含有热膨胀性调整剂的热固性树脂组成物也同样地,包括含有热膨胀性调整剂作为其成分的一部分、及仅由热膨胀性调整剂所构成。
本实施方式的热固性树脂组成物含有热固性树脂。作为热固性树脂的例子,可列举环氧树脂。环氧树脂的种类并无特别限定,例如6可列举:双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛清漆型环氧树脂、苯酚酚醛清漆型环氧树脂、联苯型环氧树脂、苯酚联苯基芳烷基型环氧树脂、通过苯酚、萘酚等与伸苯二甲基键结的芳烷基树脂的环氧化物、二环戊二烯型环氧树脂、二羟基萘型环氧树脂、三酚基甲烷型环氧树脂等缩水甘油醚型环氧树脂、缩水甘油酯型环氧树脂、缩水甘油胺型环氧树脂等于一分子中具有2个以上环氧基的环氧化合物。这些环氧树脂可单独使用,也可并用2种以上。
于环氧树脂硬化时,优选为并用硬化促进剂。作为硬化促进剂,可使用以酚系硬化剂使环氧树脂硬化的公知硬化促进剂,例如可列举:三级胺化合物、四级铵盐、咪唑类、脲化合物、膦化合物、鏻盐等。更具体而言可列举:三乙胺、三乙二胺、苄基二甲基胺、2,4,6-三(二甲基胺基甲基)苯酚、1,8-二氮双环(5,4,0)十一烯-7等三级胺化合物;2-甲基咪唑、2,4-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等咪唑类;3-苯基-1,1-二甲基脲、3-(邻甲基苯基)-1,1-二甲基脲、3-(对甲基苯基)-1,1-二甲基脲、1,1'-伸苯基双(3,3-二甲基脲)、1,1'-(4-甲基-间伸苯基)-双(3,3-二甲基脲)等脲化合物;三苯基膦、三丁基膦、三(对甲基苯基)膦、三(壬基苯基)膦等膦化合物;三苯基鏻酚盐、四苯基鏻四苯基硼酸盐、四苯基鏻四萘甲酸硼酸盐等鏻盐。
乙炔脲衍生物化合物为热固性树脂组成物的硬化物的热膨胀调整剂且也为环氧树脂。热固性树脂组成物可含有乙炔脲衍生物化合物及其他环氧树脂等作为热固性树脂,也可仅含有乙炔脲衍生物化合物作为热固性树脂。
通过使含有乙炔脲衍生物化合物的热固性树脂组成物硬化,而可形成各种形状的硬化物。因此,若使用本发明的热固性树脂组成物,则可容易地形成具备特定线热膨胀性系数的构材。
通过在热固性树脂组成物中调配乙炔脲衍生物化合物,可获得线热膨胀系数较小的硬化物。通过将上述乙炔脲衍生物化合物调配于热固性树脂组成物中,可获得线热膨胀系数为40ppm/℃以下、进一步为25ppm/℃以下的硬化物。
为了减小热固性树脂组成物硬化而成的硬化物的线热膨胀系数,以往使用有无机填充剂。本实施方式的热固性树脂组成物含有包含乙炔脲衍生物化合物的热膨胀性调整剂。因此,可减少为了减小硬化物的线热膨胀系数所需的无机填充剂的量。进一步于不调配无机填充剂的情况下也可形成线热膨胀系数较小的硬化物。
硬化物的玻璃转移温度优选为180℃以上,更优选为200℃以上,进一步优选为250℃以上。
通过将玻璃转移温度设为上述范围内,可使包含硬化物的构材的刚性、耐热性变得良好。玻璃转移温度是指使用示差热分析法(TMA(热机械分析法,ThermomechanicalAnalysis))自40℃以每分钟10℃升温至300℃进行测定所得的值。
热固性树脂组成物中的乙炔脲衍生物化合物的调配量根据硬化物所要求的线热膨胀系数而调整即可,为了获得作为热膨胀性调整剂的效果,于热固性树脂组成物100质量%中优选为调配5质量%以上,更优选为调配20质量%以上。
本实施方式的热固性树脂组成物优选为作为绝缘材的用途。例如可作为密封材(底部填充材)、导电膏、成形材、各种粘合剂、嵌装(mounting)材、涂布材、积层材等而使用。
所谓密封材是指通过封堵间隙而防止构成电路基板的零件接触外部空气。以防止焊料附着于多余部分为目的而使用的阻焊剂也包含于密封材。
所谓导电膏是指代替焊料而使用的具有导电性的膏状材料,通常使用将低温熔融金属粒子分散于热固性树脂组成物中而成的树脂组成物。
本实施方式的热固性树脂组成物可作为具有热固性树脂组成物的基板材料、或作为热固性树脂组成物含浸于基材而成的预浸体而使用。通过使这些基板材料及预浸体的热固性树脂组成物硬化,可制作线热膨胀系数较低的构材。所得的构材用作构成可挠性基板或刚性基板的构材。
具有热固性树脂组成物的基板材料是指使用热固性树脂组成物作为其原料或构成要素者。作为此种基板材料,例如可列举将热固性树脂组成物制成膜状的绝缘树脂片等膜状基板材料、具备含有热固性树脂组成物的树脂的附有树脂的铜箔(Resin CoatedCopper,RCC)等。
所谓预浸体是指将本实施方式的热固性树脂组成物制成清漆,含浸于基材并将其加热或干燥而成为半硬化状态者。作为基材,例如可使用玻璃布、碳纤维等无机纤维;聚酰胺、聚酰亚胺、聚酯等有机纤维。这些可单独使用或组合多种而使用。
就成为高耐热、阻燃性优异者的观点而言,本实施方式的热固性树脂组成物也可含有聚顺丁烯二酰亚胺化合物及酚化合物。作为聚顺丁烯二酰亚胺化合物,优选为于1分子中具有2个以上顺丁烯二酰亚胺基者。另外,作为酚化合物,优选为于分子中至少具有2个OH基者。作为上述聚顺丁烯二酰亚胺化合物及酚化合物具体而言可使用国际公开编号WO2012/057171中所记载者。
本实施方式的热固性树脂组成物中,可视需要添加硬化剂、无机填充剂、偶合剂、脱模剂、着色剂、阻燃剂、低应力剂等,而且,也可将这些预先反应而使用。
作为无机填充剂的例子,可列举非晶性二氧化硅、结晶性二氧化硅、氧化铝、玻璃、硅酸钙、菱镁矿、粘土、滑石、云母、氧化镁、硫酸钡等,尤佳为非晶性二氧化硅、结晶性二氧化硅、硫酸钡。而且,于欲维持优异的成形性并提高无机填充剂的调配量时,优选为使用可细密填充的粒度分布较广的球形无机填充剂。
作为偶合剂的例子,可例示巯基硅烷系、乙烯基硅烷系、胺基硅烷系、环氧硅烷系等硅烷偶合剂或钛偶合剂,作为脱模剂的例子,可例示巴西棕榈蜡(carnauba wax)、石蜡等,另外,作为着色剂,可例示碳黑等。作为阻燃剂的例子,可列举磷化合物、金属氢氧化物等,作为低应力剂的例子,可列举硅橡胶、改质腈橡胶、改质丁二烯橡胶、改质硅油等。
使本实施方式的热固性树脂组成物硬化而成的硬化物,使用乙炔脲衍生物化合物作为热膨胀性调整剂,故可形成无机填充剂含量较少的构材。例如,相对于包含硬化物的构材的100质量%而可将无机填充剂的含量设为80质量%以下,进一步可设为50质量%以下。通过减少热固性树脂组成物中的无机填充剂的含量,可抑制无机填充剂所引起的成形性下降。
本发明也可作为线热膨胀系数(热膨胀率)的调整方法而实施。本实施方式的调整方法具备:测定工序,测定上述本实施方式的热固性树脂组成物硬化而成的构材的线热膨胀系数;以及调整工序,基于所述测定的线热膨胀系数,调整所述热固性树脂组成物的使用量及所述热固性树脂组成物中的热膨胀率调整剂的含量的至少一个。
在调整工序中,基于测定工序中测定的线热膨胀系数的测定值,调整热固性树脂组成物的使用量及热固性树脂组成物中的热膨胀率调整剂的含量的至少一个。通过该调整工序,可使构材的线热膨胀系数接近特定值。因此,视需要重复测定工序与调整工序,藉此可调整线热膨胀系数而获得具备特定线热膨胀系数的构材。
根据上述构材的线热膨胀系数的调整方法,可通过调整工序调整热固性树脂组成物的使用量或热固性树脂组成物中的热膨胀率调整剂的含量,而容易地获得包含特定线热膨胀系数的硬化物的构材。
作为包含热固性树脂组成物硬化而成的硬化物的构材,可列举:将本实施方式的热固性树脂组成物制成清漆并加热使其硬化而成的树脂膜、将预浸体加热使其硬化而成者。清漆中可使用丙酮、甲基乙基酮、二甲基乙酰胺、N-甲基-2-吡咯啶酮等通用者作为树脂成分的溶剂,溶剂的调配量并无特别限定。
实施例
以下以实施例更具体地说明本发明,但本发明并不限定于这些。
(评价方法)
以下实施例及比较例的性能评价中所使用的试验方法如下述。
(1)玻璃转移温度
于实施例所得预浸体一片的上下部分配置Sepanium(铝箔表面经耐热脱模皮膜处理的脱模剂),于4MPa、180℃~230℃加热120分钟使其热硬化。测定所得试样(样品)的玻璃转移温度。测定装置、测定条件等如下所述。
测定机器:Rigaku公司制造的「TMA8310evo」。
环境:氮气中。
测定温度:30℃~300℃。
升温速度:10℃/min。
负荷:47mN。
(2)线热膨胀系数
树脂膜于该状态下、预浸体于一片的上下部分配置Sepanium,且在4MPa、180℃~230℃加热120分钟使其热硬化。测定所得成形品的线热膨胀系数。测定装置、测定条件等如下所述。
测定机器:Rigaku公司制造的「TMA8310evo」。
环境:氮气中。
测定温度:50℃~100℃。
升温速度:10℃/min。
负荷:47mN。
实施例及比较例中所使用原料的详情如下述。
(1)乙炔脲衍生物:1,3,4,6-四缩水甘油基乙炔脲,TG-G(商品名,四国化成股份有限公司制造)。
(2)环氧树脂A:双酚环氧树脂,JER828EL(商品名,三菱化学股份有限公司制造)。
环氧树脂B:联苯芳烷基环氧树脂,NC3000(商品名,日本化药股份有限公司制造)。
(3)双顺丁烯二酰亚胺化合物A:苯甲烷顺丁烯二酰亚胺,BMI-2000(商品名,大和化成工业股份有限公司制造)。
(4)双顺丁烯二酰亚胺化合物B:4,4'-二苯甲烷双顺丁烯二酰亚胺,BMI-1000(商品名,大和化成工业股份有限公司制造)。
(5)酚树脂:萘酚芳烷基树脂,SN-485(商品名,新日铁住金化学股份有限公司制造)。
(6)硬化促进剂:U-CAT 3513N(商品名,三洋化成工业股份有限公司制造)。
(7)反应稀释剂:NEOALLYL G(商品名,Daiso股份有限公司制造)。
(合成例1)
(清漆(I)的合成)
于设置有搅拌机、温度计、冷却管的圆底烧瓶加入4,4'-二苯甲烷双顺丁烯二酰亚胺(BMI-1000)270质量分、萘酚芳烷基树脂(SN-485)82质量分、联苯芳烷基环氧树脂(NC-3000)221质量分、甲基乙基酮(MEK)120质量分,于内温达到80℃后混合搅拌2小时。其后,添加反应性稀释剂(烯丙基缩水甘油醚)27质量分、N-甲基-2-吡咯啶酮(NMP)12质量分,于80℃保持4小时。
其次,添加28质量分的NMP,进一步于80℃保持18小时。添加200质量分的MEK、40质量分的NMP并搅拌2小时,而获得均匀溶解状态的改质聚酰亚胺树脂组成物的清漆(I)。
(实施例1)
将30质量分的TG-G与70质量分的清漆(I)混合,且添加0.2质量分作为硬化促进剂的U-CAT3513N,于150℃至230℃硬化6小时而获得薄膜状的树脂膜。TG-G用溶剂使用20质量分的甲基乙基酮。
(实施例2)
将实施例1的TG-G设为20质量分,将70质量分的清漆(I)设为78.4质量分的清漆(I)与1.6质量分的JER828EL混合而成者,且将TG-G用溶剂的甲基乙基酮设为15质量分,除此以外,利用与实施例1相同的方法获得薄膜状的树脂膜。
(比较例1)
代替30质量分的TG-G及70质量分的清漆(I),而使用100质量分的清漆(I),且不使用TG-G用溶剂的甲基乙基酮,除此以外,利用与实施例1相同的方法获得薄膜状的树脂膜。
(比较例2)
代替30质量分的TG-G及70质量分的清漆(I),而使用100质量分的JER828EL及115.0质量分的SN-485,除此以外,利用与实施例1相同的方法获得薄膜状的树脂膜。
将实施例1、2及比较例1、2的结果示于以下的表。
[表1]
相较于未调配有TG-G的比较例1及2,于热固性树脂组成物调配有TG-G的实施例1及2作为硬化物的薄膜状的膜的线热膨胀系数较小。根据这些结果可知TG-G具有减小硬化物的线热膨胀系数的性质,且作为热固性树脂组成物的热膨胀调整剂有用的。
(实施例3)
于100质量分的TG-G添加0.2质量分作为硬化促进剂的U-CAT3513N,于150℃至230℃硬化6小时而获得薄膜状的树脂膜。
(实施例4)
将100质量分的TG-G设为30质量分的TG-G及70质量分的BMI-2000,添加64质量分的SN485,且TG-G用溶剂使用110质量分的二甲基乙酰胺,除此以外,利用与实施例3相同的方法获得树脂膜。
(实施例5)
将SN485设为47质量分,除此以外,利用与实施例4相同的方法获得树脂膜。
(实施例6)
将70质量分的BMI-2000设为70质量分的BMI-1000,除此以外,利用与实施例4相同的方法获得树脂膜。
(实施例7)
将70质量分的BMI-2000设为70质量分的BMI-1000,除此以外,利用与实施例5相同的方法获得树脂膜。
[表2]
可知通过仅使用TG-G作为热固性树脂组成物中的热固性树脂,且使用TG-G作为环氧树脂的主成分,而可获得线热膨胀系数较小的薄膜状树脂膜作为热固性树脂组成物的硬化物。
(实施例8)
于10质量分的TG-G添加88.2质量分的清漆(I)、1.8质量分的JER828EL、7质量分的甲基乙基酮、0.5质量分作为硬化促进剂的U-CAT3513N、0.01质量分的添加剂(调平剂)、65质量分的无机填充剂(球状二氧化硅)并均匀搅拌,而调制树脂清漆。
使其含浸于玻璃布(旭化成电子材料股份有限公司制造的2319),于230℃干燥2小时,而获得预浸体。将两片该预浸体重迭,进一步于其上下的最外层配置18μm的铜箔,于2MPa~4MPa的压力且180℃~230℃、120分钟的加热条件下使其成形而获得覆铜积层板。
(实施例9)
将10质量分的TG-G、88.2质量分的清漆(I)、1.8质量分的JER828EL及7质量分的甲基乙基酮设为20质量分的TG-G、78.4质量分的清漆(I)、1.6质量分的JER828EL、13质量分的甲基乙基酮,除此以外,利用与实施例8相同的方法获得覆铜积层板。
(实施例10)
将10质量分的TG-G、88.2质量分的清漆(I)、1.8质量分的JER828EL及7质量分的甲基乙基酮设为30质量分的TG-G、68.6质量分的清漆(I)、1.4质量分的JER828EL及20质量分的甲基乙基酮,除此以外,利用与实施例8相同的方法获得覆铜积层板。
将以上述方式制成的实施例8~10的预浸体,利用实施例说明最初的评价方法所记载的方法测定玻璃转移温度及线热膨胀系数。将结果示于下表。
[表3]
根据上述结果可知,通过增加TG-G的调配量,而使预浸体的热固性树脂组成物硬化所得的硬化物的线热膨胀系数变小。
(产业上的可利用性)
本发明提供的热膨胀性调整剂可用于调整例如用作电路基板的材料等的热固性树脂组成物的硬化物的热膨胀性,而获得所希望的线热膨胀系数的构材。
本发明提供的热固性树脂组成物可提供线热膨胀系数较低的优异硬化物的组成物,具体一例为包含环氧树脂的热固性树脂组成物。
Claims (11)
2.一种绝缘材,其特征在于,含有根据权利要求1所述的热固性树脂组成物。
3.一种密封材,其特征在于,含有根据权利要求1所述的热固性树脂组成物。
4.一种导电膏,其特征在于,含有根据权利要求1所述的热固性树脂组成物。
5.一种硬化物,其特征在于,使根据权利要求1所述的热固性树脂组成物硬化而成。
6.根据权利要求5所述的硬化物,其特征在于,线热膨胀系数为40ppm/℃以下。
7.根据权利要求5所述的硬化物,其特征在于,玻璃转移温度为180℃以上。
8.一种基板材料,其特征在于,具有根据权利要求1所述的热固性树脂组成物。
9.一种预浸体,其特征在于,使根据权利要求1所述的热固性树脂组成物含浸于基材而成。
10.一种构材,其特征在于,使根据权利要求3所述的密封材、根据权利要求4所述的导电膏、根据权利要求8所述的基板材料的所述热固性树脂组成物、或根据权利要求9所述的预浸体的所述热固性树脂组成物硬化而成。
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CN107614564A (zh) | 2018-01-19 |
WO2016139989A1 (ja) | 2016-09-09 |
JP6670293B2 (ja) | 2020-03-18 |
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