CN116554425A - 一种含磷苯并恶嗪树脂、树脂组合物及应用 - Google Patents
一种含磷苯并恶嗪树脂、树脂组合物及应用 Download PDFInfo
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- CN116554425A CN116554425A CN202310588369.8A CN202310588369A CN116554425A CN 116554425 A CN116554425 A CN 116554425A CN 202310588369 A CN202310588369 A CN 202310588369A CN 116554425 A CN116554425 A CN 116554425A
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- 239000011347 resin Substances 0.000 title claims abstract description 81
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 43
- 239000011574 phosphorus Substances 0.000 title claims abstract description 43
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
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- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
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Classifications
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明公开了一种含磷苯并恶嗪树脂、树脂组合物及应用,包括结构式(1):其中,Y为环氧树脂残基;T基为C1~C4的直链或支链烷烃、取代或未取代的芳基、取代或未取代的芳氧基中的一种;Z基为直接连接、C1‑C5亚烷基、取代或未取代亚芳基、亚砜基、亚硫基或C3‑20亚脂环族基;R为苯基或取代苯基、萘基或取代萘基、C1‑C5烷基或含不饱和双键基团。本发明采用含酚氧基的含磷苯并恶嗪树脂,增加了反应交联点,将反应交联点更加均匀分布,使整体交联密度进一步提高,并配合苯氧基键和含磷基团,改善固化物的脆性的同时达到无卤阻燃要求,当配合马来酰亚胺树脂时获得优异的无卤阻燃性的同时不降低耐热性、吸水率、耐湿性,并进一步提高韧性、降低CTE和翘曲。
Description
技术领域
本发明涉及电子材料技术领域,尤其涉及一种含磷苯并恶嗪树脂、树脂组合物及应用。
背景技术
随着通讯技术的发展,印制线路板(PCB)上需要承载更多的芯片和模组,要求覆铜板具备较高的模、较高的耐热性和较低的热膨胀系数。随着电子产品体积越来越小,线路设计越来越密集,越来越多的设计厂商采用HDI工艺,要求基板材料在尺寸安定性,多次冷热冲击,长时间热氧老化等方面的性能要有所提升,传统的树脂配方体系的各项性能已无法满足现有的要求。另一方面,受欧盟颁发的“绿色”法规的影响,溴元素作为阻燃元素是否应该用在高分子领域又被推到了争议的风口浪尖上。虽然四溴双酚A作为阻燃剂还未发现其对环境有什么较大的负面影响,但是对于将其列为禁用物质的呼声越来越高。因此未来阻燃对于溴元素的依赖程度势必会逐渐降低。
苯并恶嗪树脂在高温下聚合反应过程中固化收缩率小,并固化物的耐热性高、残碳率高、热稳定性优异,因此在覆铜板领域中被广泛地应用,但是存在韧性差、刚性差、介电性能差等缺点,并单依靠苯并恶嗪树脂的氮原子难以满足无卤阻燃要求。
现有技术JP2020158705中公开马来酰亚胺树脂、烯丙基苯并恶嗪树脂和高分子树脂组合的技术方案,该方案在一定程度上改善固化物的韧性,并保持较好的耐热性,但是高分子树脂与其他树脂之间的相容性方面较差,在固化过程中容易析出至表面,影响了绝缘树脂和铜箔之间的粘结性、吸水率等。现有技术CN109082118中公开马来酰亚胺树脂、苯并恶嗪树脂和阻燃剂组合的技术方案,其中所述阻燃剂为热分解温度大于380℃的阻燃剂、次磷酸金属盐阻燃剂和十溴二苯乙烷,均属于添加性阻燃剂,在方案中添加适量的阻燃剂时固化后阻燃性可达到UL94 V-0级别,但添加型阻燃剂不同程度上影响了固化物的耐热性和湿热性。
因此,本发明制备了一种含磷苯并恶嗪树脂、树脂组合物及应用,提供一种同时满足优异的耐热性、低CTE、高韧性、低吸水率及阻燃性能优的树脂材料和树脂组合物,显然具有积极的现实意义。
发明内容
本发明的发明目的是一种含磷苯并恶嗪树脂、树脂组合物及应用,满足优异的无卤阻燃性的同时不降低耐热性、吸水率、耐湿性,并进一步提高韧性、降低CTE和翘曲。
为达到上述发明目的,本发明采用的技术方案是:一种含磷苯并恶嗪树脂,包括结构式(1):
其中,Y为环氧树脂残基,n为1-10的整数;
X为
T基为C1~C4的直链或支链烷烃、取代或未取代的芳基、取代或未取代的芳氧基中的一种;
Z基为直接连接、C1-C5亚烷基、取代或未取代亚芳基、亚砜基、亚硫基或C3-20亚脂环族基;
R为苯基或取代苯基、萘基或取代萘基、C1-C5烷基或含不饱和双键基团。上述技术方案中,所述Y基为环氧树脂开环后残基,如以下基团:
其中R1和R2为相同或不同,分别选自氢、C1-C5烷基或不饱和基团。
优选地,所述结构式(1)中R基为取代或未取代的C2-C10烯基、取代或未取代的苯乙烯基、取代或未取代的萘基、取代或未取代的丙烯酸酯基团中的一种。
优选地,所述结构式(1)中R基为烯丙基、丙烯基、乙烯基、苯乙烯基或苯烯丙基。
优选地,通过将结构式(2)所示的含磷双酚化合物和环氧树脂反应,然后再与单胺化合物反应获得;
其中,Z为直接连接、C1-C5亚烷基、取代或未取代亚芳基、亚砜基、亚硫基或C3-20亚脂环族基;
T基为C1~C4的直链或支链烷烃、取代或未取代的芳基、取代或未取代的芳氧基中的一种。
优选地,所述含磷双酚树脂和环氧树脂的反应摩尔比为2:1。
优选地,所述含磷双酚树脂和环氧树脂的反应温度为120-180℃,反应时间为2h-10h。
优选地,上述反应过程中,根据需要添加催化剂,所述催化剂选用碱金属氢氧化物、叔胺化合物、季铵化合物、第三膦化合物和第四鏻化合物或咪唑化合物中至少一种。
本申请还要求保护一种树脂组合物,包括上文所述的含磷苯并恶嗪树脂。
优选地,以重量计,包括:
(A)含磷苯并恶嗪树脂:5-50重量份;
(B)马来酰亚胺树脂:30-100重量份。
优选地,以重量计,包括:
(A)含磷苯并恶嗪树脂:5-50重量份;
(B)马来酰亚胺树脂:30-100重量份;
(C)环氧树脂:10-100重量份。
上述技术方案中,所述马来酰亚胺树脂为分子结构至少含2个马来酰亚胺基化合物,具体选自以下结构所示的马来酰亚胺树脂。
其中,R2为氢、甲基或乙基,R1为亚甲基、亚乙基或n为0或1~10的整数;
其中,n为1-10的整数;
其中,n为1-10的整数;
其中,n为1-10的整数;
其中,n为1-10的整数;
其中,n为1-10的整数;
其中,n为1-10的整数,m为1-10的整数;
其中,n为1-10的整数,m为1-10的整数;
其中,n为1-10的整数;
更进一步,所述马来酰亚胺树脂选自大和化成制BMI-2300,BMI-1000、BMI-1000H、BMI-1100、BMI-1100H、BMI-4000、BMI-5100、日本KI化成制BMI-70、BMI-80、日本化药制MIR-3000,MIR-5000。
上述技术方案中,所述的环氧树脂选自双环戊二烯环氧树脂、含磷环氧树脂、异氰酸酯改性环氧树脂、联苯环氧树脂、双酚A型环氧树脂、苯酚型酚醛环氧树脂、邻甲酚醛型环氧树脂、环氧化聚丁二烯树脂、含萘环的环氧树脂、双酚F型环氧树脂,三官能环氧树脂、氢化的双酚A环氧树脂或氢化的双酚F型环氧中的任意一种或至少两种的组合,其中典型但非限制性的组合为:双环戊二烯环氧树脂和含磷环氧树脂、联苯环氧树脂和双酚A型环氧树脂、邻甲酚醛型环氧树脂和环氧化聚丁二烯树脂,邻甲酚醛型环氧树脂和双环戊二烯型环氧树脂。
进一步优选,所述环氧树脂选自以下结构中的至少一种:
上述结构(16)~结构(21)中重复单元数(p、n、m)为1~10的整数。
进一步优选,所述环氧树脂选自DIC制HP4032、HP4032H、HP4032D、HP4032SS、HP4700、HP4710、N-690、N-695、HP7200、HP7200H、HP7200HH、EXA7311、HP6000,日本化药制NC3000、NC7000、NC3100,日铁化学制ESN475V、ESN485。
上述技术方案中,所述树脂组合物中还含有填料。以树脂组合物100重量份计,填料含量为20~200重量份。
所述填料包括无机填料、有机填料、复合填料。优选地,填料为球形二氧化硅、勃姆石、氧化铝或氢氧化铝,更优选为球形二氧化硅。
进一步的,填料用含反应基的硅烷偶联剂进行表面处理,所述硅烷偶联剂为氨基硅烷偶联剂、含碳碳双键硅烷偶联剂或环氧硅烷偶联剂中至少一种。优选的,硅烷偶联剂选自以下结构:
上述技术方案中,所述树脂组合物中的苯并恶嗪树脂和马来酰亚胺树脂可预先进行预聚反应,其预聚温度为100-150℃,预聚时间为30-120min。
上述技术方案中,所述树脂组合物中还含有阻燃剂,以树脂组合物合计100重量份计,含1-50重量份。
所述阻燃剂选自溴系阻燃剂、磷系阻燃剂、氮系阻燃剂、有机硅阻燃剂、有机金属阻燃剂、无机系阻燃剂中的至少一种。
其中,溴系阻燃剂可以是十溴二苯醚、十溴二苯乙烷、溴化苯乙烯或者四溴邻苯二甲酰胺。磷系阻燃剂可以是无机磷、缩合磷酸酯化合物、膦酸化合物、次膦酸化合物、氧化膦化合物、以及9,10-二氢-9氧杂-10-膦杂菲-10-氧化物、10-(2,5二羟基苯基)-9,10-二氢-9氧杂-10-膦杂菲-10-氧化物、10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、三(2,6二甲基苯基)膦、(m为1~5的整数)、/>膦腈等有机含磷化合物。氮系阻燃剂可以是三嗪化合物、氰尿酸化合物、异氰酸化合物、吩噻嗪。有机硅阻燃剂可以是有机硅油、有机硅橡胶、有机硅树脂。有机金属盐阻燃剂可以是二茂铁、乙酰丙酮金属络合物、有机金属羰基化合物。无机阻燃剂可以是氢氧化铝、氢氧化镁、氧化铝、氧化钡。
当然,所述阻燃剂地种类并不以此为限,可以理解的是,所添加的阻燃剂可以根据层压板的具体应用领域而选择,如,对卤素有要求的应用领域,优选非卤阻燃剂,如含磷或者含氮的阻燃剂,更优选为磷腈或双DOPO。
优选地,在选择含磷阻燃剂时,可以与固化剂中的活性酯化合物的氮元素形成氮磷协同阻燃,提高阻燃效率。
进一步的,前述树脂组合物中还含有0.01~5重量份的催化剂,催化剂为咪唑类催化剂、吡啶类催化剂、有机金属盐类催化剂中至少一种。
优选的,催化剂为4-二甲氨基吡啶、2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、改性咪唑以及辛酸锌中的至少一种。
优选的,改性咪唑为如下结构所示:
其中,R3、R4、R5和R6相同或不同,分别为甲基、乙基或叔丁基,B为亚甲基、亚乙基、/>可使用JER株式会社制备的牌号为P200F50的改性咪唑。
其中,R3、R4、R5和R6相同或不同,分别为甲基、乙基或叔丁基,A为亚甲基、亚乙基、/>或芳香族碳氢基,可使用第一工业株式会社制备的牌号为G8009L的改性咪唑。
本申请还要求保护一种上文所述的树脂组合物在半固化片、层压板和印制线路板中的应用。
本申请所述的树脂组合物应用于半固化片时,所述半固化片包括增强材料和前述树脂组合物,半固化片的制备方法为:将树脂组合物用溶剂溶解制成胶液,然后将增强材料浸渍在上述胶液中,将浸渍后的增强材料取出在100~180℃环境下烘烤1~15min;干燥后即可得到半固化片。
其中,溶剂选自丙酮、丁酮、甲苯、甲基异丁酮、N、N-二甲基甲酰胺、N、N-二甲基乙酰胺、乙二醇甲醚、丙二醇甲醚、苯、甲苯、二甲苯、环己烷中的至少一种。
增强材料选自天然纤维、有机合成纤维、有机织物、无机织物中的至少一种。优选地,增强材料采用玻璃纤维布;玻璃纤维布中优选使用开纤布或扁平布;玻璃纤维布优选为E玻璃纤维布、S玻璃纤维布、T玻纤布或Q玻璃纤维布。
此外,当增强材料采用玻璃纤维布时,玻璃纤维布使用偶联剂进行化学处理,以改善树脂组合物与玻璃纤维布之间的界面结合。偶联剂优选用环氧硅烷偶联剂或者氨基硅烷偶联剂,以提供良好的耐水性和耐热性。
本申请所述的树脂组合物应用于一种层压板时,所述层压板包括一片前述半固化片以及设置在半固化片至少一侧表面的金属箔;或者包括由多片前述半固化片相互叠合而成的组合片以及设置在组合片至少一侧表面的金属箔。
层压板采用以下方法制备:在一片半固化片的一侧或双侧表面覆上金属箔,或者将至少两片半固化片叠合而成组合片,在组合片的一侧或双侧表面覆上金属箔,热压成形得到金属箔层压板。热压的压制条件为:在0.2~2MPa、150~250℃下压制2~4小时。
优选地,金属箔选自铜箔或铝箔。金属箔的厚度为1μm、1.5微米、3微米、5微米、8微米、12微米、18微米、35微米或70微米。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:
1.本发明采用含酚氧基的含磷苯并恶嗪树脂,增加了反应交联点,将反应交联点更加均匀分布,使整体交联密度进一步提高,并配合苯氧基键和含磷基团,改善固化物的脆性的同时达到无卤阻燃要求,当配合马来酰亚胺树脂时获得优异的无卤阻燃性的同时不降低耐热性、吸水率、耐湿性,并进一步提高韧性、降低CTE和翘曲;
2.本发明设置的树脂组合物具有优良的综合性能,在在半固化片、层压板和印制线路板领域具有广泛的发展和应用前景。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
合成例1:合成苯并恶嗪树脂A
步骤1:在反应容器中添加536g含磷双酚化合物(以下结构式所示)、双环戊二烯型环氧树脂358g和甲苯溶剂700g,升温至100℃后均匀搅拌溶解,再添加咪唑化合物0.05g,继续升温至145℃后保温反应8小时,然后冷却至室温,获得中间反应物A-1。
(T为苯基,Z为/>)
步骤2:在上述中间反应物A-1中继续滴加83g甲醛(36%福尔马林溶液)和93g苯胺化合物,然后升温至95℃进行6小时反应,然后,取出该反应物,在130℃下减压干燥4小时,粉碎得到热固性苯并恶嗪树脂A。
合成例2:合成苯并恶嗪树脂B(相比合成例1,含磷树脂不同)
步骤1:在反应容器中添加505g含磷双酚化合物(以下结构式所示)、双环戊二烯型环氧树脂358g和甲苯溶剂700g,升温至100℃后均匀搅拌溶解,再添加咪唑化合物0.05g,继续升温至145℃后保温反应8小时,然后冷却至室温,获得中间反应物B-1。
(T为甲基,Z为/>)
步骤2:在上述中间反应物A-1中继续滴加83g甲醛(36%福尔马林溶液)和93g苯胺化合物,然后升温至95℃进行6小时反应,然后,取出该反应物,在130℃下减压干燥4小时,粉碎得到热固性苯并恶嗪树脂B。
合成例3:合成苯并恶嗪树脂C(相比对比例1,末端含烯丙基苯)
步骤1:在反应容器中添加536g含磷双酚化合物(以下结构式所示)、双环戊二烯型环氧树脂358g和甲苯溶剂700g,升温至100℃后均匀搅拌溶解,再添加咪唑化合物0.05g,继续升温至145℃后保温反应8小时,然后冷却至室温,获得中间反应物C-1。
(T为苯基,Z为/>)
步骤2:在上述中间反应物A-1中继续滴加83g甲醛(36%福尔马林溶液)和133g烯丙基苯胺化合物,然后升温至90℃进行5小时反应,然后,取出该反应物,在130℃下减压干燥4小时,粉碎得到热固性苯并恶嗪树脂C。
合成例4:苯并恶嗪改性马来酰亚胺树脂预聚物D
在反应瓶中添加40g苯并恶嗪树脂C、100g马来酰亚胺树脂(结构式(6))和甲苯溶剂200g,将反应温度升至120℃,搅拌均匀后开始反应60min获得含磷苯并恶嗪改性马来酰亚胺树脂预聚物D。
合成例5:含磷苯并恶嗪树脂E
在反应容器中添加505g含磷双酚化合物(以下结构式所示)滴加166g甲醛(36%福尔马林溶液)和186g苯胺化合物,然后升温至100℃进行8小时反应,然后取出该反应物,在130℃下减压干燥4小时,粉碎得到热固性苯并恶嗪树脂E。
(T为苯基,Z为/>)
实施例1
本实施例按重量份计,将35份苯并恶嗪树脂A、70份马来酰亚胺树脂A、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片A。
实施例2
本实施例按重量份计,将30份苯并恶嗪树脂B、65份马来酰亚胺树脂A、5份马来酰亚胺树脂B、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片B。
实施例3
本实施例按重量份计,将45份苯并恶嗪树脂C、60份马来酰亚胺树脂B、20份环氧树脂、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片C。
实施例4
本实施例按重量份计,将90份预聚物D、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片D。
实施例5
本实施例按重量份计,将85份预聚物D、20份环氧树脂、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片E。
实施例6
本实施例按重量份计,将20份苯并恶嗪树脂A、20份苯并恶嗪树脂B、60份马来酰亚胺树脂A、20份环氧树脂、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片F。
实施例7
本实施例按重量份计,将50份苯并恶嗪树脂B、30份马来酰亚胺树脂A、50份环氧树脂、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片G。
对比例1
按重量份计,将35份苯并恶嗪树脂E、70份马来酰亚胺树脂A、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片H。
对比例2
按重量份计,将30份苯并恶嗪树脂F、65份马来酰亚胺树脂A、5份马来酰亚胺树脂B、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片I。
对比例3
按重量份计,将40苯并恶嗪树脂G、60份马来酰亚胺树脂A、25份环氧树脂、5份助燃剂、0.1份催化剂和80份填料通过溶剂调节胶液至固含量60%,将胶液涂覆于E玻璃纤维布上,浸润后取出,放置于160℃鼓风干燥箱中,烘烤3~6min,制成半固化片J。
上文中,实施例1-7及对比例1-3所采用的各组分物质及重量份如表1所示,所采用的组分材料牌号如表2所述。
将上述实施例1-7及对比例1-3制备的半固化片裁剪至300×300mm,在半固化片两侧各放置一张电解铜箔,叠配成一定叠构,送入真空压机中压合制得金属箔层压板(或者覆铜层压板),具体性能检测如表3所示。
表1、各组分物质及重量份:
表2、材料牌号:
对上述所有实施例1~7和比较例1~2中制备的覆铜板进行性能测试的方法主要包括:
1)玻璃化转变温度采用DMA(热机械分析),升温速率为10℃/min;
2)PCT 2HR吸水率测定:取3块10cm×10cm、厚度为0.40mm、两面去除金属箔的样品,在100℃干燥2小时,称重,记重量为W1,然后在高压锅蒸煮试验(Pressure Cookertest)机中,在121℃、2个大气压下处理2小时,称重,重量记为W2,测定吸水率为(W2-W1)/W1×100%;
3)X/Y热膨胀系数(CTE)测定:采用TMA(热机械分析),升温速率10℃/min,测试温度范围30~100℃;
4)Dk和Df:按照IPC-TM-650 2.5.5.9使用平板法,测定10GHz下。
5)固化收缩率:通过TMA,温度在室温-260℃-室温循环过程中测试前后固化物收缩率。
6)阻燃性:根据UL94标准测试。
表3、性能测试结果:
从上数测试结果可以看出,实施例1-7制备的覆铜板相对于对比例1-3具有更优异的无卤阻燃性的同时不降低耐热性、吸水率、耐湿性,并进一步提高韧性、降低CTE和翘曲,还具有低热膨胀系数、低介电常数和低介质损耗、高粘结性和低的固化收缩率,综合性能更加优异。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (10)
1.一种含磷苯并恶嗪树脂,其特征在于,包括结构式(1):
其中,Y为环氧树脂残基,n为1-10的整数;
X为
T基为C1~C4的直链或支链烷烃、取代或未取代的芳基、取代或未取代的芳氧基中的一种;
Z基为直接连接、C1-C5亚烷基、取代或未取代亚芳基、亚砜基、亚硫基或C3-20亚脂环族基;
R为苯基或取代苯基、萘基或取代萘基、C1-C5烷基或含不饱和双键基团。
2.根据权利要求1所述的含磷苯并恶嗪树脂,其特征在于,所述结构式(1)中R基为取代或未取代的C2-C10烯基、取代或未取代的苯乙烯基、取代或未取代的萘基、取代或未取代的丙烯酸酯基团中的一种。
3.根据权利要求1所述的含磷苯并恶嗪树脂,其特征在于,通过将结构式(2)所示的含磷双酚化合物和环氧树脂反应,然后再与单胺化合物反应获得;
其中,Z为直接连接、C1-C5亚烷基、取代或未取代亚芳基、亚砜基、亚硫基或C3-20亚脂环族基;
T基为C1~C4的直链或支链烷烃、取代或未取代的芳基、取代或未取代的芳氧基中的一种。
4.根据权利要求3所述的含磷苯并恶嗪树脂,其特征在于,所述含磷双酚树脂和环氧树脂的反应摩尔比为2:1。
5.一种树脂组合物,其特征在于,包括权利要求1-4任一项所述的含磷苯并恶嗪树脂。
6.根据权利要求5所述的树脂组合物,其特征在于,以重量计,包括:
(A)含磷苯并恶嗪树脂:5-50重量份;
(B)马来酰亚胺树脂:30-100重量份。
7.根据权利要求5所述的树脂组合物,其特征在于,以重量计,包括:
(A)含磷苯并恶嗪树脂:5-50重量份;
(B)马来酰亚胺树脂:30-100重量份;
(C)环氧树脂:10-100重量份。
8.根据权利要求5所述的树脂组合物,其特征在于,所述树脂组合物中还含有填料。
9.根据权利要求8所述的树脂组合物,其特征在于,所述填料用含反应基的硅烷偶联剂进行表面处理。
10.一种根据权利要求5所述的树脂组合物的应用,其特征在于,应用于半固化片、层压板和印制线路板中。
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