CN112341581B - 含烯丙基树脂及其应用 - Google Patents

含烯丙基树脂及其应用 Download PDF

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CN112341581B
CN112341581B CN202010770657.1A CN202010770657A CN112341581B CN 112341581 B CN112341581 B CN 112341581B CN 202010770657 A CN202010770657 A CN 202010770657A CN 112341581 B CN112341581 B CN 112341581B
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allyl
containing resin
resin
spectral intensity
group
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CN112341581A (zh
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杜安邦
杨士德
王炳杰
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Chang Chun Plastics Co Ltd
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Chang Chun Plastics Co Ltd
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Abstract

本发明提供一种含烯丙基树脂，其具有一重复单元，该重复单元包含如下式(I)所示的第一结构单元：[式(I)]
Figure DDA0002616493740000011
其中，式(I)的R1至R3如说明书中所定义；该含烯丙基树脂的傅立叶转换红外光谱于1650cm‑1至1630cm‑1处具有光谱强度a，于1620cm‑1至1560cm‑1处具有光谱强度b，且0<a/b≤1.20；以及该含烯丙基树脂的定量1H‑NMR光谱于3.2ppm至6.2ppm处具有光谱强度c，于6.6ppm至7.4ppm具有光谱强度d，且0<c/d≤1.20。

Description

含烯丙基树脂及其应用
技术领域
本发明关于一种含烯丙基树脂，特别是关于一种低介电损耗的含烯丙基树脂及该树脂于印刷电路板的应用。
背景技术
随着电子产品的应用逐渐朝高频化、高速化、电子元件小型化及基板线路高密度化等趋势发展，对电子材料的物化性质要求也随之提升，尤其在高频传输应用中，低介电损耗材料已是必然的趋势。传统以环氧树脂作为主要成分的介电材料已难以满足需求。
氟类树脂，例如聚四氟乙烯(polytetrafluoroethene)的介电损耗因子(dissipation factor，Df)可低至0.0004，但其加工不易且成本高昂，因而用途受到限制。聚苯醚树脂(polyphenylenether)的Df可达0.0007水准，但加工不易及玻璃转移温度(Tg)低为其缺点。双马来酰亚胺树脂(bismaleimide)树脂具有优异的介电性质、耐热性及反应活性，且具有自聚合后无副产物的优势，并可进一步通过例如二烯丙基双酚A(diallylbisphenol A，DABPA)进行改质，以改良其溶解性及韧性。
发明内容
本发明旨在提供一种含烯丙基树脂，其具有优异介电性质，特别适合用于双马来酰亚胺树脂的改质，除能扩大双马来酰亚胺树脂的可操作区间，且仍保有双马来酰亚胺树脂的高耐热性优点外，尤其可降低双马来酰亚胺树脂的介电耗损因子(Df)与介电常数(Dk)，从而使得所致电子材料特别适合高频传输应用。因此，本发明涉及以下发明目的。
本发明的一目的在于提供一种含烯丙基树脂，其具一重复单元，该重复单元包含如下式(I)所示的第一结构单元：
[式(I)]
Figure GDA0004110609920000021
于式(I)中，R1及R2各自独立为H或烯丙基，且R1及R2的至少一个为烯丙基，R3为H、C1至C21烃基、或C1至C21的含羟基基团；
该含烯丙基树脂以傅立叶转换红外光谱术(fourier transform infraredspectroscopy，FT-IR)测定时，于1650cm-1至1630cm-1处具有光谱强度a，于1620cm-1至1560cm-1处具有光谱强度b，且0<a/b≤1.20；以及
该含烯丙基树脂以定量核磁共振(qNMR)测定1H-NMR光谱时，于3.2ppm至6.2ppm处具有光谱强度c，于6.6ppm至7.4ppm具有光谱强度d，且0<c/d≤1.20。
于本发明的部分实施方案中，该傅立叶转换红外光谱术测定是以如下方式利用傅立叶转换红外光谱仪测量而得到：将含烯丙基树脂以薄膜法涂抹于KBr锭上，测量经涂抹的KBr锭于4000cm-1至400cm-1范围的吸收光谱，并利用衰减全反射法(attenuated totalreflection，ATR)测定光谱强度a及b，其中傅立叶转换红外光谱仪的解析度为1cm-1，光谱的累积扫描次数为16次，光谱强度为各波长下的吸光度(任意单位)。
于本发明的部分实施方案中，该1H-NMR光谱是在以下条件下利用核磁共振仪测量而得到：以氘代氯仿(chloroform-d)作为溶剂并以四甲基硅烷(tetramethylsilane)作为基准物质，共振频率为500兆赫(MHz)，脉冲宽度为10微秒，脉冲延时时间为2秒，累积次数为32次，以及基准物质的化学位移设为0ppm。
于本发明的部分实施方案中，0.10≤a/b≤1.20，且0.50≤c/d≤1.20。
于本发明的部分实施方案中，该重复单元还包含一个或多个选自以下群组的第二结构单元：-CH2-、-C2H4-、-C2H2-、-C2-、-C3H6-、-C3H4-、-C3H2-、-C4H8-、-C4H6-、-C4H4-、-C5H10-、-C5H8-、-C5H6-、-C6H12-、-C6H10-、-C6H8-、-C7H14-、-C7H12-、-C7H10-、-C8H16-、-C8H14-、-C8H12-、-C9H18-、-C9H16-、-C9H14-、-C10H20-、-C10H18-、-C10H16-、
Figure GDA0004110609920000031
羰基(carbonyl)、硫酰基(sulfuryl)及-O-。
本发明的另一目的在于提供一种双马来酰亚胺树脂，其是经如上所述的含烯丙基树脂改质。
本发明的又一目的在于提供一种树脂组合物，其包含如上所述的双马来酰亚胺树脂。
本发明的又一目的在于提供一种半固化片，其是通过将一基材含浸或涂布如上所述的树脂组合物，并干燥经含浸或涂布的基材而制得。
本发明的又一目的在于提供一种金属箔积层板，其是通过将如上所述的半固化片与金属箔加以层合而制得。
本发明的又一目的在于提供印刷电路板，其是由如上所述的积层板所制得。
为使本发明的上述目的、技术特征及优点能更明显易懂，下文以部分具体实施方案进行详细说明。
具体实施方式
以下将具体地描述根据本发明的部分具体实施方案；但是，在不背离本发明的精神下，本发明还可以多种不同形式的方案来实践，不应将本发明保护范围限于所述具体实施方案。
除非另有说明，于本说明书及权利要求书中所使用的“一”、“该”及类似用语应理解为包含单数及复数形式。
除非另有说明，于本文中(尤其是在权利要求书中)，所使用的“第一”、“第二”及类似用语仅是用于区隔所描述的元件或成分，本身并无特殊涵义，且非意欲指代先后顺序。
于本文中，“可操作区间”是指树脂的软化点至热交联温度的温度区间。
于本文中，用语“末端羟基”是指连接于聚合物主链上的末端的羟基(-OH)。
1.含烯丙基树脂
本发明提供一种含烯丙基树脂，其具有低黏度、低软化点及优异介电性质，可用于改质双马来酰亚胺树脂，使其具有宽广的操作温度(即可操作区间)，并维持优异的介电性质与高耐热性。
1.1.含烯丙基树脂的性质
本发明的含烯丙基树脂以傅立叶转换红外光谱术(FT-IR)测定时，于1650cm-1至1630cm-1处具有光谱强度a，于1620cm-1至1560cm-1处具有光谱强度b，且光谱强度a与光谱强度b的比值(a/b)为大于0至1.20，即0<a/b≤1.20。例如，a/b可为0.125、0.15、0.175、0.20、0.225、0.25、0.275、0.30、0.325、0.35、0.375、0.40、0.425、0.45、0.475、0.50、0.525、0.55、0.575、0.60、0.625、0.65、0.675、0.70、0.725、0.75、0.775、0.80、0.825、0.85、0.875、0.90、0.925、0.95、0.975、1.00、1.025、1.05、1.075、1.10、1.125、1.15、或1.175，或介于由上述任意两个数值所构成的范围。于本发明的部分实施方案中，光谱强度a与光谱强度b的比值(a/b)为0.10至1.20，即0.10≤a/b≤1.20，较佳为0.19至1.18，即0.19≤a/b≤1.18。当含烯丙基树脂的a/b值在本发明指定范围内时，含烯丙基树脂可具有优异的介电性质(低Dk及低Df)。
本发明的含烯丙基树脂的FT-IR测定可以如下方式利用傅立叶转换红外光谱仪测量而得到：将1毫克的含烯丙基树脂以薄膜法涂抹厚度为0.02微米的薄膜在直径13毫米、厚度为0.5毫米的KBr锭上，将经涂抹的KBr锭放入锭剂架中，置于傅立叶转换红外光谱仪中并测量经涂抹的KBr锭于4000cm-1至400cm-1范围的吸收光谱，并利用衰减全反射法(ATR)测定光谱强度a及b，其中傅立叶转换红外光谱仪的解析度为1cm-1，光谱的累积扫描次数为16次，光谱强度为各波长下的吸光度，计算方式为指定范围内的峰的起点与终点连线的积分面积。
本发明的含烯丙基树脂以定量核磁共振(qNMR)测定1H-NMR光谱时，于3.2ppm至6.2ppm处具有光谱强度c，于6.6ppm至7.4ppm具有光谱强度d，且光谱强度c与光谱强度d的比值(c/d)为大于0至1.20，即0<c/d≤1.20。于本发明的部分实施方案中，光谱强度c与光谱强度d的比值(c/d)为0.50至1.20，即0.50≤c/d≤1.20，较佳为0.93至1.15，即0.93≤c/d≤1.15。例如，c/d可为0.10、0.125、0.15、0.175、0.20、0.225、0.25、0.275、0.30、0.325、0.35、0.375、0.40、0.425、0.45、0.475、0.50、0.525、0.55、0.575、0.60、0.625、0.65、0.675、0.70、0.725、0.75、0.775、0.80、0.825、0.85、0.875、0.90、0.925、0.95、0.975、1.00、1.025、1.05、1.075、1.10、1.125、1.15、或1.175，或介于由上述任意两个数值所构成的范围。当含烯丙基树脂的c/d值在本发明指定范围内时，可提供优异的介电性质(低Dk及低Df)。
本发明的含烯丙基树脂的1H-NMR光谱可在以下条件下利用核磁共振仪测量而得到：将15毫克含烯丙基树脂溶于750微升的氘代氯仿，将所得溶液置于核磁共振仪(例如Bruker AVANCE 500NMR)的样品加料器中，经匀场(shimming)步骤后，使用5毫米的探针(例如BBFO Smart探针)进行分析，其中以四甲基硅作为基准物质，共振频率为500兆赫(MHz)，脉冲宽度为10微秒，脉冲延时时间为2秒，累积次数为32次，且基准物质的化学位移设为0ppm。
1.2.含烯丙基树脂的结构
本发明含烯丙基树脂具有一重复单元，该重复单元包含如下式(I)所示的第一结构单元，且本发明含烯丙基树脂可具有选自羟基与烯丙基的末端基团，且各末端基团可相同或不同。
[式(I)]
Figure GDA0004110609920000061
于式(I)中，R1及R2各自独立为H或烯丙基，且R1及R2的至少一个为烯丙基，R3为H、C1至C21烃基、或C1至C21的含羟基基团。C1至C21烃基包括但不限于C1至C21烷基、C2至C21烯基、及C2至C21炔基，且C1至C21烃基可具有直链、支链或环状结构。C1至C21的含羟基基团包括但不限于C1至C21羟烷基(hydroxyalkyl)。
C1至C21烷基的实例包括但不限于甲基、乙基、正丙基、异丙基、正丁基、异丁基、三级丁基、正戊基、异戊基、三级戊基、新戊基、正己基、异己基、正庚基、异庚基、正辛基、异辛基、正壬基、异壬基、正癸基、异癸基、十一烷基、十二烷基、十五烷基、及二十烷基。C2至C21烯基的实例包括但不限于乙烯基、丙烯基、烯丙基、正丁烯基、异丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、及癸烯基。C2至C21炔基的实例包括但不限于乙炔基、丙炔基、丁炔基、戊炔基、己炔基、庚炔基、辛炔基、壬炔基、及癸炔基。C1至C21羟烷基的实例包括但不限于羟甲基、羟乙基、羟丙基、羟丁基、羟戊基、及羟己基。
于本发明的一实施方案中，式(I)中的R1为烯丙基，R2为H。于本发明的另一实施方案中，式(I)中的R1为H，R2为烯丙基。
于本发明的一实施方案中，式(I)中的R3选自以下群组：-CH3、-CH2OH、-C2H5、-C2H3、-C2H4OH-、-C2H、-C3H7、-C3H5、-C3H3、-C4H9、-C4H7、-C4H5、-C4H8OH、-C5H11、-C5H9、-C5H7、-C6H13、-C6H11、-C6H9、-C7H15、-C7H13、-C7H11、-C8H17、-C8H15、-C8H13、-C8H14OH、-C9H19、-C9H17、-C9H15、-C10H21、-C10H19、-C10H17、-C11H23、-C11H21-、-C11H19、-C12H25、-C12H23、-C12H21、-C13H27、-C13H25、-C13H23、-C14H29、-C14H27、-C14H25、-C15H31、-C15H29、-C15H27、-C16H33、-C16H31、-C16H29、-C17H35、-C17H33、-C17H31、-C18H37、-C18H35、-C12H18OH、-C17H33、-C19H39、-C19H37、-C19H35、-C20H41、-C20C39、-C20H37、-C21H43、-C21H41、-C21H34OH、-C21H32OH、-C21H30OH、及-C21H28OH。
于本发明的一实施方案中，式(I)中的R3具有如下式(i)所示结构，其中R4是-C15H25、-C15H27、-C15H29、或-C15H31。
[式(i)]
Figure GDA0004110609920000071
于本发明的一实施方案中，本发明含烯丙基树脂的该重复单元还包含直链或支链伸烷基、直链或支链伸烯基、二价稠环基团、二价桥联双环基团(bridged bicyclic group)结构单元的一个或多个。更特定言之，本发明含烯丙基树脂的该重复单元还包含一个或多个选自以下群组的第二结构单元：-CH2-、-C2H4-、-C2H2-、-C2-、-C3H6-、-C3H4-、-C3H2-、-C4H8-、-C4H6-、-C4H4-、-C5H10-、-C5H8-、-C5H6-、-C6H12-、-C6H10-、-C6H8-、-C7H14-、-C7H12-、-C7H10-、-C8H16-、-C8H14-、-C8H12-、-C9H18-、-C9H16-、-C9H14-、-C10H20-、-C10H18-、-C10H16-、
Figure GDA0004110609920000072
羰基(carbonyl)、硫酰基(sulfuryl)及-O-。
于本发明的一实施方案中，本发明含烯丙基树脂的该重复单元包含第一结构单元与第二结构单元，且第一结构单元与第二结构单元相邻。于本发明的另一实施方案中，本发明含烯丙基树脂的重复单元是由第一结构单元与第二结构单元所构成。
2.经改质双马来酰亚胺树脂
本发明含烯丙基树脂可用于改质双马来酰亚胺树脂，使双马来酰亚胺树脂在保有高耐热性的优势下，进一步具有优异介电性质，特别是低介电损耗特性，并具有宽广的温度操作空间(即可操作区间广)。因此，本发明也提供一种双马来酰亚胺树脂，其经如前所述的含烯丙基树脂改质。
于本发明的一实施方案中，双马来酰亚胺树脂具有下式(II)所示结构：
[式(II)]
Figure GDA0004110609920000081
其中R5及R6各自独立为H、-CH3、或-C2H5，R7为-CH2-、-O-、-C3H6-、-SO2-
Figure GDA0004110609920000082
具有式(II)所示结构的双马来酰亚胺树脂的实例包括但不限于4,4'-二苯甲烷双马来酰亚胺、4,4'-二苯醚双马来酰亚胺、4,4'-二苯异丙基双马来酰亚胺、及4,4'-二苯砜双马来酰亚胺。
双马来酰亚胺树脂的改质通过与含烯丙基树脂的加成聚合反应来进行，聚合反应的条件并无特殊限制，只要可使双马来酰亚胺树脂的双键与含烯丙基树脂的双键进行反应即可。一般而言，聚合反应的温度可为110℃至250℃，例如115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃、180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃、220℃、225℃、230℃、235℃、240℃、或245℃，或介于由上述任意两个数值所构成的范围。聚合反应的反应时间可为10分钟至10小时。
含烯丙基树脂与双马来酰亚胺树脂的聚合反应可视需要于催化剂存在下进行，所述催化剂包括但不限于三级膦、三芳基膦、三烷基膦、三苯基膦、三甲基膦、三正丁基膦、及三环己基膦，且各催化剂可单独使用或任意组合使用。催化剂的用量并无特殊限制，一般而言，以含烯丙基树脂与双马来酰亚胺树脂的总重量计，可为0重量％至5重量％。
含烯丙基树脂与双马来酰亚胺树脂的反应比例以双键当量数计，可为1：2至2：1，较佳为1：1.5至1.5：1，更佳为1：0.9至1：1.3。当含烯丙基树脂与双马来酰亚胺树脂的反应比例在上述范围内，经改质的双马来酰亚胺树脂可具有宽广的温度操作空间(即可操作区间)，并维持优异耐热性(高Tg)与介电性质(低Dk及低Df)。
3.树脂组合物
本发明的经改质双马来酰亚胺树脂具有宽广的操作温度(即可操作区间)，并维持优异的介电性质与高耐热性。因此，本发明另提供一种树脂组合物，其包含如前所述的经改质双马来酰亚胺树脂，其受热固化后所得的固化物可作为印刷电路板中的介电材料。
本发明的树脂组合物可视需要进一步包含其他选用成分，例如其他热固性树脂成分、交联剂、阻燃剂、填料及本领域现有的添加剂，以适应性改良树脂组合物在制造过程中的可加工性，或改良树脂组合物所制材料的物化性质。其他热固性树脂成分的实例包括但不限于聚苯醚树脂及环氧树脂。本领域所现有的添加剂包括但不限于聚合起始剂，例如有机过氧化合物及偶氮类。
交联剂指具有不饱和基团而能够与热固性树脂，如聚苯醚树脂及双马来酰亚胺树脂发生交联反应以形成立体网状结构的成分。交联剂包括但不限于多官能型烯丙基系化合物、多官能型丙烯酸酯、多官能型丙烯酰胺、及多官能型苯乙烯系化合物。多官能型烯丙基系化合物的实例包括三烯丙基异氰尿酸酯(triallyl isocyanurate，TAIC)及三烯丙基氰尿酸酯(triallyl cyanurate，TAC)。多官能型丙烯酸酯的实例包括三羟甲基丙烷三(甲基)丙烯酸酯(trimethylolpropane tri(meth)acrylate)。多官能型苯乙烯系化合物的实例包括1,3-二乙烯基苯(1,3-divinylbenzene)及1,4-二乙烯基苯(1,4-divinylbenzene)。各该交联剂可单独使用或任意组合使用。
阻燃剂可增益树脂组合物所制得的电子材料的耐热性及阻燃性。阻燃剂包括但不限于含磷阻燃剂、含溴阻燃剂、及含氮化合物，且各类型阻燃剂可单独使用或任意组合使用。含磷阻燃剂的实例包括但不限于磷酸酯类(phosphate ester)及磷腈类(phosphazene)。含溴阻燃剂的实例包括但不限于四溴双酚A(tetrabromobisphenol A)、十溴二苯基氧化物(decabromodiphenyl oxide)、及十溴化二苯基乙烷(decabrominateddiphenyl ethane)。含氮化合物的实例包括但不限于三聚氰胺及其衍生物。
填料可改善树脂组合物所制得电子材料的机械强度、导热性及尺寸安定性。合适的填料的实例包括但不限于选自以下群组的填料：二氧化硅、氧化镁、氢氧化镁、碳酸钙、滑石、黏土、氮化铝、氧化铝、氢氧化铝、氮化硼、氮化硅、碳化铝硅、碳化硅、碳酸钠、碳酸镁、二氧化钛、氧化锌、氧化锆、石英、钻石粉、类钻石粉、石墨、煅烧高岭土、白岭土、云母、水滑石、PTFE粉体、玻璃珠、陶瓷晶须、奈米碳管、奈米级无机粉体、及前述的组合。
关于本发明树脂组合物的制备，可通过将树脂组合物各成分，包括双马来酰亚胺树脂及其他选用成分，以搅拌器均匀混合并溶解或分散于溶剂中而制成清漆状的形式，供后续加工利用。所述溶剂可为任何可溶解或分散树脂组合物各成分、但不与这些成分反应的惰性溶剂。举例言之，可用以溶解或分散树脂组合物各成分的溶剂包含但不限于：甲苯、γ-丁内酯、甲乙酮、环己酮、丁酮、丙酮、二甲苯、甲基异丁基酮、N,N-二甲基甲酰胺(N,N-dimethyl formamide，DMF)、N,N-二甲基乙酰胺(N,N-dimethyl acetamide，DMAc)、及N-甲基吡咯烷酮(N-methyl-pyrolidone，NMP)。各溶剂可单独使用或混合使用。溶剂的用量并无特殊限制，原则上只要能使树脂组合物各组分均匀溶解或分散于其中即可。于后附实施例中，使用甲乙酮作为溶剂。
4.半固化片
本发明也提供一种由上述树脂组合物所制得的半固化片，其中是通过将一基材含浸或涂布如上述的树脂组合物，并干燥该经含浸或涂布的基材而制得。含浸或涂布树脂组合物的方法包括但不限于浸渍、辊式涂布、模具涂布、棒式涂布、凹版涂布、旋转涂布、狭缝涂布、及喷雾。经含浸或涂布的基材可在80℃至180℃的温度下干燥1至30分钟，从而获得呈半固化状态(B-阶段)的半固化片。于后附实施例中，干燥是在90℃下进行30分钟。
常用的基材包括但不限于由选自下列群组的材料所制得的纸、布或毡：纸纤维、玻璃纤维、石英纤维、有机高分子纤维、碳纤维、及前述的组合。有机高分子纤维的实例包括但不限于高模量聚丙烯(high-modulus polypropylene，HMPP)纤维、聚酰胺纤维、超高分子量聚乙烯(ultra-high molecular weight polyethylene，UHMWPE)纤维、及液晶聚合物(liquid crystal polymer，LCP)。于本发明的部分实施方案中，使用玻璃纤维布作为基材。
5.金属箔积层板及印刷电路板
本发明也提供一种由上述半固化片制得的金属箔积层板，其包含一合成层及一金属层，其中该合成层由前文所述的半固化片提供。具体而言，本发明的金属箔积层板可通过以下方式制备：使用一层的半固化或多层经层叠的半固化片作为合成层，接着于合成层的至少一外侧表面层叠一金属箔(如铜箔)以提供一包含合成层及金属层的层叠物，对该层叠物进行热压操作而得到金属箔积层板。热压操作的条件可如下所述：在180℃至220℃的温度下及5公斤/平方厘米至30公斤/平方厘米的压力下，进行60至200分钟的热压。
上述金属箔积层板可通过进一步图案化其外侧的金属箔，而形成印刷电路板。
6.实施例
6.1.测量方式说明
现以下列具体实施方案进一步例示说明本发明，其中，所采用的测量仪器及方法分别如下：
[FT-IR光谱测量]
将所制得的含烯丙基树脂以有机溶剂及水萃取，取得有机层后以减压浓缩方式完全移除有机溶剂，获得待分析的含烯丙基树脂样品。
将1毫克的含烯丙基树脂样品以薄膜法涂抹厚度为0.02微米的薄膜在直径13毫米、厚度0.5毫米的KBr锭上，将经涂抹的KBr锭放入锭剂架中，置于傅立叶转换红外光谱仪(型号：Spotlight 200i；仪器商：PerkinElmer)中并测量经涂抹的KBr锭于4000cm-1至400cm-1范围的吸收光谱，并利用衰减全反射法(ATR)测定光谱强度a及b，其中傅立叶转换红外光谱仪的解析度为1cm-1，光谱的累积扫描次数为16次，光谱强度为各波长下的吸光度(任意单位)，计算方式为指定范围内的峰的起点与终点连线的积分面积。
[1H-NMR图谱测量]
将所制得的含烯丙基树脂以有机溶剂及水萃取，取得有机层后以减压浓缩方式完全移除有机溶剂，获得待分析的含烯丙基树脂样品。
将15毫克的含烯丙基树脂样品溶解于750微升的氘化氯仿(CDCl3)中，将所得溶液置于核磁共振仪(型号：Bruker AVANCE 500NMR)的样品加料器中，经匀场步骤后，使用5毫米的探针(探针类型：BBFO Smart探针)进行分析，其中，以四甲基硅烷作为基准物质，共振频率为500兆赫，脉冲宽度为10微秒，脉冲延时时间为2秒，累积次数为32次，以及基准物质的化学位移设为0ppm。
[玻璃转移温度(Tg)测试]
利用差示扫描热分析仪(differential scanning calorimeter，DSC)来测量样品的玻璃转移温度(Tg)。Tg的测试规范为电子电路互联与封装学会(the Institute forInterconnecting and Packaging Electronic Circuits，IPC)的IPC-TM-650.2.4.25号检测方法。
[介电常数(Dk)与介电耗损因子(Df)测试]
根据IPC-TM-650 2.5.5.13规范，利用微波诱电分析仪(购自日本AET公司)，在25℃及工作频率10GHz下，测量待测样品的介电常数(Dk)与介电耗损因子(Df)。
6.2.含烯丙基树脂的制备
[实施例1]
取一个带有4颈磨砂口的1升玻璃反应釜，包含温控设备、搅拌叶片及加热设备，在釜中加入230克的苯酚架桥树脂(型号：PF9110；购自中国台湾长春人造树脂厂股份有限公司)、300克醋酸烯丙酯。接者，搅拌所得混合物并将混合物升温至80℃，再加入0.06克的醋酸钯(Palladium(II)acetate，(Pd)OAc2)及0.3克三苯基膦(Triphenylphosphine，TPP)并搅拌0.5小时，以玻璃滴管滴入180毫升的50％碳酸钾溶液，反应3小时，得到284克的含烯丙基树脂A，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为烯丙基，R2为H，且R3为H。
依照前文所载方法测定含烯丙基树脂A的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[实施例2]
取一个1升玻璃反应釜，倒入280克实施例1所制得的烯丙基树脂A，通入流量为50毫升/分钟的氮气，搅拌并升温至190℃，反应8小时后，得到272克的含烯丙基树脂B，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为H，R2为烯丙基，且R3为H。
依照前文所载方法测定含烯丙基树脂B的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[实施例3]
取一个3升高压反应釜，在釜中加入225克对-第三丁基苯酚(para-tert-butylphenol)、130克双环戊二稀、2克路易士酸催化剂(AlCl3)，搅拌所得混合物并将混合物升温至150℃，并维持该温度3小时，接着再升温至180℃并减压移除未反应物。之后再加入1350克乙醇、350克烯丙基氯及140克碳酸钾，搅拌所得混合物并将混合物升温至100℃，反应10小时后，得到144克的含烯丙基树脂C，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为烯丙基，R2为H，且R3为第三丁基。
依照前文所载方法测定含烯丙基树脂C的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[实施例4]
取一个1升玻璃反应釜，倒入130克实施例3所制得的烯丙基树脂C，通入流量为130毫升/分钟的氮气，搅拌并升温至195℃，持续反应5小时后，得到128克含烯丙基树脂D，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为H，R2为烯丙基，且R3为第三丁基。
依照前文所载方法测定含烯丙基树脂D的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[实施例5]
取一个3升高压反应釜，在釜中加入300克腰果酚(Cardanol)、130克双环戊二稀、2克路易士酸催化剂(AlCl3)，搅拌所得混合物并将混合物升温至135℃，并维持该温度4小时，之后再加入1500克乙醇、339克烯丙基氯、及163克碳酸钾，搅拌所得混合物并将混合物升温至80℃，反应6小时后，得到137克的含烯丙基树脂E，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为烯丙基，R2为H，且R3为-C15H27。
依照前文所载方法测定含烯丙基树脂E的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[实施例6]
取一个1升玻璃反应釜，倒入120克实施例5所制得的烯丙基树脂E，在10托(torr)压力下搅拌并升温至194℃，反应4.5小时后，得到106克的含烯丙基树脂F，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为H，R2为烯丙基，且R3为-C15H27。
依照前文所载方法测定含烯丙基树脂F的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[比较例1]
取一个带有4颈磨砂口的2升玻璃反应釜，包含温控设备、搅拌叶片及加热设备。在釜中加入115克双酚A(BPA；购自中国台湾长春人造树脂厂股份有限公司)及200克的醋酸烯丙酯后，搅拌所得混合物并将混合物升温至82℃，加入0.048克醋酸钯((Pd)OAc2)及0.3克三苯基膦(TPP)，再以玻璃滴管滴入165毫升的50％碳酸钾溶液，持续反应4小时，得到150克比较含烯丙基树脂G，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为烯丙基，R2为H，且R3为H。
依照前文所载方法测定比较含烯丙基树脂G的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[比较例2]
取一个1升玻璃反应釜，倒入114克二烯丙基醚双酚A(Homide 126A；购自奥地利Hos-Technik公司)，通入流量为65毫升/分钟的氮气，搅拌并升温至195℃，反应12小时，得到107克比较含烯丙基树脂H，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为H，R2为烯丙基，且R3为H。
依照前文所载方法测定比较含烯丙基树脂H的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[比较例3]
取一个3升高压反应釜，在釜中加入120克OCN88(购自中国台湾长春人造树脂厂股份有限公司)、1350克乙醇、350克烯丙基氯、及140克碳酸钾，搅拌并升温至100℃，反应12小时后，得到172克比较含烯丙基树脂I，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为烯丙基，R2为H，且R3为H。
依照前文所载方法测定比较含烯丙基树脂I的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[比较例4]
取一个1升玻璃反应釜，倒入134克比较例3制得的比较烯丙基树脂I，通入流量为100毫升/分钟的氮气，搅拌并升温至200℃，持续反应5小时后，得到126克比较含烯丙基树脂J，其具有末端羟基且重复单元包含式(I)所示的第一结构单元，其中R1为H，R2为烯丙基，且R3为H。
依照前文所载方法测定比较含烯丙基树脂J的FT-IR光谱及1H-NMR图谱，并计算光谱强度a与光谱强度b的比值(a/b)以及光谱强度c与光谱强度d的比值(c/d)，将结果纪录于表1中。
[表1]
实施例/比较例 含烯丙基树脂 a/b c/d
实施例1 含烯丙基树脂A 0.78 0.93
实施例2 含烯丙基树脂B 0.19 0.93
实施例3 含烯丙基树脂C 0.75 1.15
实施例4 含烯丙基树脂D 0.95 1.07
实施例5 含烯丙基树脂E 1.18 0.94
实施例6 含烯丙基树脂F 1.06 1.02
比较例1 比较含烯丙基树脂G 0.16 1.24
比较例2 比较含烯丙基树脂H 1.98 2.08
比较例3 比较含烯丙基树脂I 1.1 2.49
比较例4 比较含烯丙基树脂J 1.26 2.22
如表1所示，本发明的含烯丙基树脂A至F均具有0<a/b≤1.20且0<c/d≤1.20的特征；相比之下，比较例的比较含烯丙基树脂G至J则不具有0<a/b≤1.20且0<c/d≤1.20的特征。
6.3.改质双马来酰亚胺树脂的耐热性质分析
分别以实施例1至2及比较例1至2的含烯丙基树脂进行改质双马来酰亚胺树脂(BMI-70；购自KI化学)的耐热性质分析。首先，将含烯丙基树脂与双马来酰亚胺树脂依表2所示比例混合并将温度保持于50℃，接着以每分钟10℃的速率将温度升高至160℃，并维持1小时，再以每分钟10℃的速率将温度升高至180℃，并维持3小时，再以每分钟10℃的速率将温度升高至300℃，并维持5小时，最后以每分钟10℃的速率将所得产物降温至50℃，制得以含烯丙基树脂改质的双马来酰亚胺树脂的热交联固化物。
依照前文所载测量方法测量所得固化物的玻璃转移温度(Tg)，并将结果纪录于下表2。
[表2]
分析 含烯丙基树脂(克) BMI树脂(克) <![CDATA[T<sub>g</sub>(℃)]]>
1 含烯丙基树脂A(5.88) BMI-70(7.51) 252
2 含烯丙基树脂B(7.61) BMI-70(9.72) 256
3 比较含烯丙基树脂G(4.62) BMI-70(6.63) 247
4 比较含烯丙基树脂H(5.94) BMI-70(7.96) 252
如表2所示，使用本发明含烯丙基树脂改质的双马来酰亚胺树脂仍可保有优异的耐热性(高Tg)。
6.4.改质双马来酰亚胺树脂的介电性质分析
分别以实施例1与比较例1及3的含烯丙基树脂进行改质双马来酰亚胺树脂(BMI-70；购自KI化学)的介电性质分析。首先，将烯丙基树脂与双马来酰亚胺树脂以下表3所示比例混合，并于160℃下反应1小时，获得一改质双马来酰亚胺预聚物。将所得的改质双马来酰亚胺预聚物与聚酰亚胺黏着剂(PIAD-200；购自荒川化学公司)以7：3的重量比例混合提供一树脂混合物。
将所得的树脂混合物涂覆于液晶高分子膜(型号：CTZ-25；购自Kuraray公司)表面，并以热压机(型号：VLP-60；购自活泉机械股份有限公司)于200℃下真空热压1小时，接着将所得树脂固化物自液晶高分子膜剥下，并依照前文所载测量方法测量所得树脂固化物的介电性质(Dk及Df)，并将结果纪录于下表3。
[表3]
Figure GDA0004110609920000191
如表3所示，使用本发明含烯丙基树脂改质的双马来酰亚胺树脂还可具有更优异的介电性质，特别是更低的Df值，尤其适合高频应用。
6.4.改质聚苯醚树脂组合物的性质分析
分别以实施例1至6与比较例1至4的含烯丙基树脂进行改质聚苯醚树脂组合物的介电性质分析。首先，将含烯丙基树脂与双马来酰亚胺树脂以下表4所示比例混合，并于250℃下反应3小时，以提供一改质双马来酰亚胺预聚物。
将所得的改质双马来酰亚胺预聚物配制成固形分占70重量％的甲乙酮溶液，并以表4所示比例加入聚苯醚树脂(SA9000；购自沙特基础工业)及聚合起始剂(双异苯丙基过氧化物(Dicumyl peroxide))，以提供聚苯醚树脂组合物。
使用所制得的聚苯醚树脂组合物制备金属箔积层板。首先，通过辊式涂布机，将玻璃纤维布(型号：2116；购自中国台湾玻璃工业股份有限公司)以滚轮涂布聚苯醚树脂组合物，将涂布后的玻璃纤维布置于90℃的干燥机中加热干燥30分钟，借此制得半固化状态(B-stage)的半固化片。之后，将四片半固化片层合，并在其两侧的最外层各层合一张PLS型电解铜箔(购自中国台湾长春石油化学股份有限公司)，随后置于热压机中进行高温热压固化，以制得金属箔积层板。热压条件为：以2.5℃/分钟的升温速度升温至180℃，并在该温度下，以全压20至30公斤/平方厘米的压力热压60分钟。
依照前文所载测量方法测量所得金属箔积层板的耐热性及介电性质(Dk及Df)，并将结果纪录于下表4。
[表4]
Figure GDA0004110609920000201
Figure GDA0004110609920000211
如表4所示，使用本发明含烯丙基树脂改质的聚苯醚树脂的固化产物不仅具有良好耐热性，更具有优异介电性质，特别是更低的Df值(≦0.0035)，尤其适合作为高频用印刷电路板的介电材料。
上述实施例仅为例示性说明本发明的原理及其功效，并阐述本发明的技术特征，而非用于限制本发明的保护范畴。任何本领域技术人员在不违背本发明的技术原理及精神下，可轻易完成的改变或安排，均属本发明所主张的范围。因此，本发明的权利保护范围如权利要求书所列。

Claims (8)

1.一种含烯丙基树脂，其特征在于，其具一重复单元，该重复单元包含如下式(I)所示的第一结构单元：
[式(I)]
Figure FDA0004110609910000011
于式(I)中，R1及R2各自独立为H或烯丙基，且R1及R2的至少一个为烯丙基，R3为H、C1至C21烃基、或C1至C21的含羟基基团；
该含烯丙基树脂以傅立叶转换红外光谱术测定时，于1650cm-1至1630cm-1处具有光谱强度a，于1620cm-1至1560cm-1处具有光谱强度b，且0<a/b≤1.20；以及
该含烯丙基树脂以定量核磁共振测定1H-NMR光谱时，于3.2ppm至6.2ppm处具有光谱强度c，于6.6ppm至7.4ppm具有光谱强度d，且0<c/d≤1.20；
其中该傅立叶转换红外光谱术测定是以如下方式利用傅立叶转换红外光谱仪测量而得到：将含烯丙基树脂以薄膜法涂抹于KBr锭上，测量经涂抹的KBr锭于4000cm-1至400cm-1范围的吸收光谱，并利用衰减全反射法测定光谱强度a及b，其中傅立叶转换红外光谱仪的解析度为1cm-1，光谱的累积扫描次数为16次，光谱强度为各波长下的吸光度；
其中该1H-NMR光谱在以下条件下利用核磁共振仪测量而得到：以氘代氯仿作为溶剂并以四甲基硅烷作为基准物质，共振频率为500兆赫，脉冲宽度为10微秒，脉冲延时时间为2秒，累积次数为32次，以及基准物质的化学位移设为0ppm。
2.如权利要求1所述的含烯丙基树脂，其特征在于，其中0.10≤a/b≤1.20，且0.50≤c/d≤1.20。
3.如权利要求1所述的含烯丙基树脂，其特征在于，其中该重复单元还包含一个或多个选自以下群组的第二结构单元：-CH2-、-C2H4-、-C2H2-、-C2-、-C3H6-、-C3H4-、-C3H2-、-C4H8-、-C4H6-、-C4H4-、-C5H10-、-C5H8-、-C5H6-、-C6H12-、-C6H10-、-C6H8-、-C7H14-、-C7H12-、-C7H10-、-C8H16-、-C8H14-、-C8H12-、-C9H18-、-C9H16-、-C9H14-、-C10H20-、-C10H18-、-C10H16-、
Figure FDA0004110609910000021
Figure FDA0004110609910000022
羰基、硫酰基及-O-。
4.一种双马来酰亚胺树脂，其特征在于，其是经如权利要求1至3中任一项所述的含烯丙基树脂改质。
5.一种树脂组合物，其特征在于，其是包含如权利要求4所述的双马来酰亚胺树脂。
6.一种半固化片，其特征在于，其是通过将一基材含浸或涂布如权利要求5所述的树脂组合物，并干燥经含浸或涂布的基材而制得。
7.一种金属箔积层板，其特征在于，其是通过将如权利要求6所述的半固化片与金属箔加以层合而制得。
8.一种印刷电路板，其特征在于，其是由如权利要求7所述的金属箔积层板所制得。
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