CN101044204A - 非卤素阻燃剂环氧树脂组合物,和使用其的预浸料坯和包铜的层压制品 - Google Patents
非卤素阻燃剂环氧树脂组合物,和使用其的预浸料坯和包铜的层压制品 Download PDFInfo
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Abstract
本发明提供一种非卤素阻燃剂环氧树脂组合物,包括(A)含硅的磷改性环氧树脂,(B)多官能环氧树脂,(C)胺类固化剂与酚醛固化剂的混合固化剂,与(D)金属水合物无机阻燃剂,与使用其的预浸料坯和包铜的层压制品。根据本发明的环氧树脂组合物显示优异的阻燃性,而不使用卤素阻燃剂,以及有利地提供充分平衡的在包铜层压制品中需要的各种物理性质,例如较高的耐热性与铜剥离强度,和吸湿之后的铅耐热性。
Description
发明领域
本发明涉及用于印刷电路板(PCBs)等的非卤素阻燃剂环氧树脂组合物,和使用该环氧树脂组合物的预浸料坯和包铜层压制品。
发明背景
最近,在全世界大量的注意力关注于环境问题,许多的国家严格强化与废物处理用过的电/电子产品有关的有毒物质的条例。总的来说,环氧树脂组合物使用溴化的双官能环氧树脂和多官能环氧树脂作为主要成分,并使用另外的胺类固化剂和硫化促进剂,及为满足材料燃烧的标准,即Underwriters Laboratory燃烧分类94V-0,该环氧树脂组合物包括15-20wt%的溴。包括溴的卤素化合物提供优异的阻燃性,然而,但当它们燃烧时引起产生毒气,可能产生致癌物质二噁英。正因如此,含磷或氮的化合物或阻燃剂无机材料最近研究作为含溴阻燃剂的代替物。
现有技术中最广泛地使用包括加入磷阻燃剂作为非卤素阻燃剂的方法。例如,日本专利公开2002-88139,2002-161191和和2002-161197公开了一种包含磷化合物和氮化合物作为阻燃剂的组合物。另外,美国专利6353080和日本专利公开10-195178公开了包括使用基于反应性磷酯的阻燃剂的环氧树脂反应技术。然而,当使用该上述提及专利中采用的磷基阻燃剂制备包铜层压制品时,发现未反应的磷化合物很有可能降低耐热性和铜的剥离强度。德国专利DE 438184通过形成双官能的或多官能环氧树脂解决这种问题,所述的环氧树脂预先地与该磷基阻燃剂起反应,但是与常规的产品相比不利地遭受相对差的防潮性能和耐热性。
正因如此,常规的非卤素环氧树脂组合物不能提供充分平衡的在包铜层压制品中需要的各种物理性质。
发明内容
因此,完成本发明解决上述问题,及其他还有待于解决的技术问题。
由于进行了各种各样的大量和深入细致的研究和试验以解决如上所述的问题,本发明的发明人研发了非卤素阻燃剂环氧树脂组合物,包括:(A)含硅的磷改性环氧树脂,(B)多官能环氧树脂,(C)胺类固化剂和酚醛固化剂的混合固化剂,和(D)金属水合物无机阻燃剂,和已经发现,通过不使用卤素阻燃剂,这种组合物当它燃烧时没有导致产生有毒致癌物质比如二噁英,减轻了如下的缺点,比如磷基阻燃剂防潮性能和耐热性的降低,通过利用含硅的磷改性环氧树脂能提供改进的铜剥离强度。另外,本发明发明人发现将金属水合物无机阻燃剂加入到组合物中能保证稳定的阻燃性。本发明已经基于这些发现而得以完成。
特别地,本发明的目的是提供非卤素阻燃剂环氧树脂组合物,显示出优异的阻燃性而且当热分解时不会就产生致癌物质,并能够实现平衡的物理性质,比如优异的玻璃化转变温度(Tg),包铜附着力,耐热性,防潮性能和阻燃性稳定性。
本发明另外的目的是提供使用上述提及的组合物制备的预浸料坯和包铜层压制品。
根据本发明的一个方面,上述及其他的目的通过提供非卤素阻燃剂环氧树脂组合物得以实现,所述的组合物包括(A)含硅的磷改性环氧树脂,B)多官能环氧树脂,(C)胺类固化剂和酚醛的固化剂的混合固化剂,和(D)金属水合物无机阻燃剂。
通常,常规的阻燃剂环氧树脂组合物面临实现其不同的物理性质平衡改进的困难。然而,本发明提供一种能够通过特别组分的组合发挥希望物理性质的非卤素阻燃剂环氧树脂组合物。另外,本发明提供上述提及的组合物制备的预浸料坯和包铜的层压制品。
优选实施方式的详细说明
现在更详细地描述本发明。
本发明涉及环氧树脂组合物,其用于制备由具有浸渍环氧树脂的阻燃剂玻璃纤维层压板组成的包铜层压制品。
本发明的环氧树脂组合物包括同时作为阻燃剂和环氧树脂的含硅的磷改性环氧树脂,而且不使用常规的卤素阻燃剂。
该含硅的磷改性环氧树脂(A)在磷改性环氧树脂中包括大于0.5wt%的硅。
该含硅的磷改性环氧树脂的例子包括(i)非硅的磷改性环氧树脂和含硅的化合物的混合物,和(ii)在其分子结构中包含硅原子的磷改性环氧树脂。
在(i)的化合物中,该非硅的磷改性环氧树脂的优选的例子包括由以下通式I代表的环氧树脂:
其中每一个R独立是双官能或多官能环氧树脂的部分,在环氧开环后通过羟基化作用与环氧树脂主链连接。
双官能或多官能环氧树脂的例子包括如下:
<双酚A环氧树脂:通式Ia>
<双酚A酚醛清漆环氧树脂:通式Ib>
<四苯基乙烷环氧树脂:通式Ic>
含硅化合物的例子包括由通式II代表的含甲氧基的硅中间体:
其中每一个R′是苄基或甲基。
含甲氧基的硅中间体的比重为1.120-1.140,25℃的粘度为50-100cps,甲氧基的含量为14.0-16.0wt%。
在(ii)的化合物中,在其分子结构中包含硅原子的磷改性环氧树脂可以通过通式I的磷改性环氧树脂与含硅化合物缩聚获得。
在其分子结构中包含硅原子的磷改性环氧树脂的例子可以包括由通式III代表的树脂:
其中Y是:
包含于本发明中含硅的磷改性环氧树脂中的磷酸,当树脂燃烧时,形成碳化物,其然后用来阻滞热和氧,因此赋予包铜层压制品阻燃性。
调节含硅的磷改性环氧树脂的混合量,使得在总环氧树脂组合物中磷含量优选为1-8wt%,更优选为2-4wt%。如果在总环氧树脂组合物中的磷含量小于1wt%,则难以得到足够的阻燃性。相反,如果磷含量超过8wt%,这会导致物理性质例如吸湿性,耐热性与玻璃态转化温度明显恶化。
在含硅的磷改性环氧树脂中环氧基的当量比优选为300-1500。在含硅的磷改性环氧树脂中的磷含量优选为2-5wt%。
所述含硅的磷改性环氧树脂可以通过硅实现改善的防潮性能与耐热性。就防潮性能与耐热性而言,优选硅原子化学结合到磷改性环氧树脂分子中。
当环氧基含量较高时,所述含硅的磷改性环氧树脂可以形成为具有更高玻璃化转变温度的树脂。当玻璃化转变温度较低时,在高温制造过程期间,所述环氧树脂组合物膨胀,因此伴随有缺点,例如铜剥落及内层的破裂。
根据本发明,多官能环氧树脂(B)是改进所述环氧树脂组合物的玻璃化转变温度(Tg)与耐热性的主要成分,而且可以包括例如三官能与四官能的酚醛清漆树脂。这种多官能环氧树脂更优选的例子包括苯酚酚醛环氧树脂,甲酚酚醛环氧树脂,双酚A酚醛清漆环氧树脂与聚缩水甘油胺环氧树脂。
基于100重量份的含硅的磷改性环氧树脂,多官能环氧树脂的含量优选为20-100重量份,更优选为50-80重量份。如果多官能环氧树脂的含量小于20重量份,则不能发挥对玻璃化转变温度(Tg)足够的提高影响。相反,如果多官能环氧树脂的含量超过100重量份,则在总的树脂组合物中磷的含量下降,因此导致产生阻燃性降低与脆性的固化产品。
如以上描述的,根据本发明的环氧树脂固化剂(C)由胺类固化剂与酚醛固化剂组合组成。这样的固化剂组合能够控制固化速率,并实现平衡的包铜粘着性,耐热性与防潮性能。更具体地说,所述的胺类固化剂能补偿酚醛固化剂不利的差的包铜粘着性,而酚醛固化剂能用于补偿胺类固化剂低的耐热性与防潮性能的缺点。亦即,两种固化剂的组合弥补彼此的缺点,因此改进得到的固化产物的物理性质。另外,所述胺类固化剂可以通过其自身的氮组分的存在发挥阻燃剂效果。
所述胺类固化剂的例子包括聚胺,聚酰胺,二氨基二苯甲烷与双氰胺。通常,所述胺类固化剂双氰胺广泛地用作包铜层压制品的环氧树脂固化剂。作为可用于本发明的胺类固化剂,优选双氰胺由以下通式IV代表:
为固化环氧树脂组分,双氰胺的加入量应该至少大于30%的环氧当量。加入小于30%的双氰胺导致极低的固化速率。相反,如果双氰胺的加入量超过80%,这会导致防潮性能与耐热性的恶化。因此,相对于环氧当量,双氰胺的加入量优选为30-80%,更优选为40-60%的。
所述酚醛固化剂的优选例子包括线型酚醛清漆树脂树脂与三嗪改性的酚醛清漆树脂。线型酚醛清漆树脂的加入量较高导致总树脂组合物中磷含量的减少,而三嗪改性的酚醛清漆树脂的较高的量导致物理性质例如耐热性与防潮性能的恶化。
根据本发明所述酚醛固化剂的优选例子是由以下通式V代表的双酚酚醛清漆:
所述酚醛固化剂的含量优选为5-40%,更优选为5-20%,相对于环氧当量。如果所述酚醛固化剂的含量低于5%,则固化速率太低,因此不可能一经模制为预浸料坯就得到具有均一厚度的层压制品。相反,所述酚醛固化剂的含量超过40%,则固化速率过高,因此不可能确保所述预浸料坯的储藏稳定性。
在所述固化剂中胺组分:酚醛组分的当量比优选为90∶10-40∶60,更优选为80∶20-60∶40。如果所述胺类固化剂的当量比超过90%,这会导致耐热性与防潮性能恶化的问题。如果所述胺类固化剂的当量比小于40%,这是不希望的,因为固化速率太短,玻璃化转变温度(Tg)下降。
所述金属水合物无机阻燃剂(D)是当其与聚合材料同时使用时能够提供希望阻燃性的组分。没有特别限制金属水合物无机阻燃剂,只要它是能够赋予阻燃性的非卤素无机材料。这种非卤素无机材料的例子可以包括氢氧化铝,氢氧化镁,氢氧化铝/锡酸锌与氢氧化铝/钼酸锌。这些材料可以单独使用或者其任意组合使用。
基于100重量份的总树脂组合物,所述无机阻燃剂的含量优选为20-100重量份,更优选为30-60重量份。如果所述无机阻燃剂的含量小于20重量份,难以得到希望的阻燃性。相反,如果所述无机阻燃剂的含量大于100重量份,它是不希望的,因为包铜粘着性会降低。
根据本发明的环氧树脂组合物可以另外包含其它的组分,只要对本发明不产生下降的影响。
例如,所述组合物可以另外包含固化促进剂以促进固化。咪唑硫化促进剂优选作为这样的环氧树脂硫化促进剂。咪唑基固化加速剂的例子包括咪唑与咪唑衍生物,例如1-甲基咪唑,2-甲基咪唑,2-乙基-4-甲基咪唑,2-苯基咪唑,2-环己基-4-甲基咪唑,4-丁基-5-乙基咪唑,2-甲基-5-乙基咪唑,2-辛基-4-己基咪唑,2,5-氯代-4-乙基咪唑与2-丁氧基-4-烯丙基咪唑。就优良的反应稳定性与廉价而言,特别优选2-苯基咪唑。基于100重量份的所述环氧树脂组分,优选咪唑的含量为0.1-10重量份,更优选为0.2-5重量份。
为控制固化速率并改进玻璃化转变温度(Tg),所述组合物可以另外包含固化阻滞剂,与上述提到的咪唑同时使用。可用于本发明的固化阻滞剂的具体例子包括硼酸,水杨酸,盐酸,硫酸,草酸,对苯二甲酸,间苯二酸,磷酸与乳酸。基于所述咪唑固化促进剂的摩尔当量,固化阻滞剂的用量优选为0.1-10摩尔当量,更优选为0.5-5摩尔当量。
另外,本发明提供一种预浸料坯,包括在30-60重量份的玻璃纤维内的40-70重量份的上述提到的非卤素阻燃剂环氧树脂组合物,并提供一种包铜的层压制品,其中由预浸料坯组成的一种或多种层压制品与由位于层压制品外面的导电片(例如包铜)组成的外层通过加热和受压结合成一整体。
使用树脂组合物与玻璃纤维制备预浸料坯的方法,和使用这样的预浸料坯制备包铜层压制品的方法,是本领域已知的,因此此处省略其详细的描述。在这一点上,这样的方法的具体例子通过以下举例说明的试验性实施例得以证实。
实施例
现在,参考以下实施例更详细地描述本发明。提供这些实施例仅仅用于说明本发明,不应该解释为限制本发明的范围与精神。
[实施例1]
根据以下如表1中描述的组合物配方制备非卤素阻燃剂环氧树脂组合物。
首先,9重量份的双氰胺引入到1000mL的烧杯中,然后加入120重量份的甲基溶纤剂,并完全溶解。将500重量份的含硅的磷改性环氧树脂(见配方III),25重量份的四官能环氧树脂(见配方Ic),30重量份的线型酚醛清漆树脂固化剂(见配方V)与0.6重量份的2-苯基咪唑加入到得到的溶液中并搅动,直到它们完全溶解混合,从而制备环氧树脂组合物。
此后,将100重量份的氢氧化铝加入到如此制备的环氧树脂组合物中,然后加入甲基溶纤剂,以使非挥发性组分的浓度调节到60重量份。然后,使用高速搅拌器充分搅拌得到的溶液。此处,在总树脂组合物中磷与氮组分的含量各自调节到2.7wt%与0.8wt%。
[实施例2]
根据以下如表1中描述的组合物配方制备非卤素环氧树脂组合物。
首先,14重量份的双氰胺引入到1000mL的烧杯中,然后加入200重量份的甲基溶纤剂,并完全溶解。将500重量份的含硅的磷改性环氧树脂(见配方III),25重量份的四官能环氧树脂(见配方Ic),200重量份的双酚A酚醛清漆环氧树脂(见配方Ic),40重量份的线型酚醛清漆树脂固化剂(见配方V)与0.6重量份的2-苯基咪唑加入到得到的溶液中并搅动,直到它们完全溶解混合,因此制备环氧树脂组合物。
此后,将200重量份的氢氧化铝加入到如此制备的环氧树脂组合物中,然后加入甲基溶纤剂,以使非挥发性组分的浓度调节到60重量份。然后,使用高速搅拌器充分搅拌得到的溶液。此处,制备环氧树脂组合物,其中在总树脂组合物(除填充组分以外)中磷与氮组分的含量各自为1.9wt%与0.9wt%。
[实施例3]
用和实施例2一样的方法制备非卤素环氧树脂组合物,不同之处为如以下表1描述的改变双酚A酚醛清漆环氧树脂,氢氧化铝,双氰胺与线型酚醛清漆树脂固化剂的含量。
[实施例4-6]
用和实施例2一样的方法制备非卤素环氧树脂组合物,不同之处为如以下表2描述的改变四官能环氧树脂,双酚A酚醛清漆环氧树脂,双氰胺与线型酚醛清漆树脂固化剂的含量。
[比较例1]
用和实施例1一样的方法制备环氧树脂组合物,不同之处为单独使用双氰胺固化剂,如以下表3描述的改变氢氧化铝的含量。
[比较例2]
用和实施例1一样的方法制备环氧树脂组合物,不同之处为单独使用线型酚醛清漆树脂固化剂,如以下表3描述的改变氢氧化铝的含量。
[比较例3]
用和实施例2一样的方法制备环氧树脂组合物,不同之处如以下表3描述的改变双氰胺与线型酚醛清漆树脂固化剂的含量。
[比较例4]
用和实施例2一样的方法制备非卤素环氧树脂组合物,不同之处为如以下表4描述的改变含硅的磷改性环氧树脂,氢氧化铝,双氰胺与线型酚醛清漆树脂固化剂的含量。
[比较例5]
用和实施例2一样的方法制备环氧树脂组合物,不同之处使用以下表4给出的组合物配方,而不加入氢氧化铝,以单独在含硅的磷改性环氧树脂的情况下实现阻燃性。
[试验性实施例1]
制备包铜的层压制品
在实施例1-6和比较实施例1-5中制备的环氧树脂组合物在玻璃纤维(7628,Nittobo制造)中浸渍,并经热风干燥处理,因此制备树脂含量为43wt%的玻璃纤维预浸料坯。
将8片如此制备的玻璃纤维预浸料坯堆叠,在各个预浸料坯的两面上堆叠35μm厚的铜箔,随后使用压力机在195℃,40kg/cm2压力下加热并受压90分钟,因此制备包铜的厚度为1.6毫米的层压制品。
[试验性实施例2]
包铜层压制品的评价
-玻璃化转变温度(Tg):通过浸蚀除去包铜层压制品的包铜层,通过使用差示扫描量热计(DSC),测量玻璃化转变温度(Tg)。
-铜剥离强度:宽度为1厘米的包铜从所述的包铜层压制品表面剥落,使用质地分析器测量其剥离强度。
-铅耐热性:厚度为1.6毫米的样品切割为5厘米×5厘米的大小,放置在288℃的铅浴上,然后测量其耐受时间,因此决定铅耐热性。
-吸湿之后的铅耐热性:厚度为1.6毫米的样品切割为5厘米×5厘米的大小,在120℃温度,在2atm下经受蒸汽处理2小时,浸渍在288℃的铅浴中10秒。在样品中观察产生白斑现象的存在/消失,根据以下标准评价样品
◎:没有产生白斑
○:部分产生白斑
△:几乎产生白斑
×:完全产生白斑
-阻燃性:使用从其中除去包覆铜的层压制品制备棒状的样品,并经受UL94测试,一种可燃性试验方法,其中物质的可燃性(燃烧阻滞性质)通过立式耐燃性试验分为等级V-0,V-1和V-2。
<表1>
实施例1 | 实施例2 | 实施例3 | ||
树脂组合物(phr) | 含硅的磷改性环氧树脂 | 500 | 500 | 500 |
四官能环氧树脂 | 25 | 25 | 25 | |
双酚A酚醛清漆环氧树脂 | - | 200 | 330 | |
氢氧化铝 | 100 | 200 | 330 | |
双氰胺 | 9 | 14 | 16 | |
线型酚醛清漆树脂固化剂 | 30 | 40 | 60 | |
2-苯基咪唑 | 0.6 | 0.6 | 0.6 | |
含磷量(wt%) | 2.7 | 1.9 | 1.6 | |
含氮量(wt%) | 0.8 | 0.9 | 0.9 | |
物理性质 | 在170℃的清漆胶凝时间(sec) | 240 | 200 | 360 |
DSC Tg(℃) | 130 | 142 | 152 | |
铜剥离强度(kN/m) | 2.0 | 1.7 | 1.6 | |
在288℃的铅耐热性(sec) | 480 | 360 | 420 | |
吸湿之后在288℃下的铅耐热性 | ○○△ | ○○△ | ○△△ | |
可燃性(UL94) | V-0 | V-0 | V-0 |
<表2>
实施例4 | 实施例5 | 实施例6 | ||
树脂组合物(phr) | 含硅的磷改性环氧树脂 | 500 | 500 | 500 |
四官能环氧树脂 | 50 | 100 | 150 | |
双酚A酚醛清漆环氧树脂 | 200 | 150 | 100 | |
氢氧化铝 | 200 | 200 | 200 | |
双氰胺 | 15 | 20 | 20 | |
线型酚醛清漆树脂固化剂 | 15 | 25 | 25 | |
2-苯基咪唑 | 0.6 | 0.6 | 0.6 | |
含磷量(wt%) | 2.7 | 1.8 | 1.8 | |
含氮量(wt%) | 0.8 | 0.9 | 0.9 | |
物理性质 | 在170℃的清漆胶凝时间(sec) | 260 | 300 | 320 |
DSC Tg(℃) | 148 | 155 | 158 | |
铜剥离强度(kN/m) | 1.6 | 1.6 | 1.5 | |
在288℃的铅耐热性(sec) | 540 | 300 | 280 | |
吸湿之后在288℃下的铅耐热性 | ○○○ | ○△△ | △△△ | |
可燃性(UL94) | V-0 | V-0 | V-0 |
如从表1和2可见,根据本发明的实施例1-6显示良好的阻燃性与优异的铜剥离强度和铅耐热性。另外,当多官能环氧树脂(四官能环氧树脂与双酚A酚醛清漆环氧树脂)的含量较高时,特别当四官能环氧树脂的含量增加时,玻璃化转变温度(Tg)显示提高。
<表3>
比较例1 | 比较例2 | 比较例3 | ||
树脂组合物(phr) | 含硅的磷改性环氧树脂 | 500 | 500 | 500 |
四官能环氧树脂 | 25 | 25 | 25 | |
双酚A酚醛消漆环氧树脂 | - | - | - | |
氢氧化铝 | 200 | 200 | 200 | |
双氰胺 | 20 | - | 5 | |
线型酚醛清漆树脂固化剂 | - | 80 | 35 | |
2-苯基咪唑 | 0.6 | 0.6 | 0.6 | |
含磷量(wt%) | 2.8 | 2.5 | 2.6 | |
含氮量(wt%) | 1.8 | - | 0.4 | |
物理性质 | 在170℃的清漆胶凝时间(sec) | 540 | 140 | 175 |
DSC Tg(℃) | 135 | 128 | 131 | |
铜剥离强度(kN/m) | 2.1 | 1.8 | 1.9 | |
在288℃的铅耐热性(sec) | 170 | 960 | 860 | |
吸湿之后在288℃下的铅耐热性 | △×× | ○○○ | ○○○ | |
可燃性(UL94) | V-0 | V-0 | V-0 |
<表4>
比较例4 | 比较例5 | ||
树脂组合物(phr) | 含硅的磷改性环氧树脂 | 200 | 500 |
四官能环氧树脂 | 25 | 25 | |
双酚A酚醛清漆环氧树脂 | 200 | 200 | |
氢氧化铝 | 500 | - | |
双氰胺 | 10 | 14 | |
线型酚醛清漆树脂固化剂 | 25 | 40 | |
2-苯基咪唑 | 0.5 | 0.6 | |
含磷量(wt%) | 2.8 | 1.9 | |
含氮量(wt%) | 1.8 | 0.9 | |
物理性质 | 在170℃的清漆胶凝时间(sec) | 180 | 195 |
DSC Tg(℃) | 158 | 145 | |
铜剥离强度(kN/m) | 1.3 | 2.0 | |
在288℃的铅耐热性(sec) | 150 | 780 | |
吸湿之后在288℃下的铅耐热性 | ××× | ○○○ | |
可燃性(UL94) | V-0 | V-1 |
如从表3和4中可见,其中在非卤素环氧树脂组合物中单独使用双氰胺固化剂,显示优异的铜剥离强度,但是显示恶化的铅耐热性与防潮性能。然而,比较例2,其中单独使用线型酚醛清漆树脂固化剂,与比较例3,其中双氰胺与线型酚醛清漆树脂固化剂以当量比15∶85使用,显示优异的铅耐热性与防潮性能,但是显示很短的清漆固化时间与下降的玻璃化转变温度(Tg)。
另外,可以证实比较例4,其中含硅的磷改性环氧树脂含量明显减少,而氢氧化铝含量显著增加,以弥补阻燃性,显示良好的阻燃性,但是显示出铜剥离强度与铅耐热性的下降。在比较例5的情况下,其中单独使用含硅的磷改性环氧树脂以得到希望的阻燃性而不使用氢氧化铝,显示出组合物的阻燃性降低到V-1等级。
工业实用性
根据本发明的非卤素环氧树脂组合物,由于使用非卤素阻燃剂,所以没有导致一经燃烧就出现有毒致癌物质例如二噁英,由于使用含硅的磷改性环氧树脂,减轻了磷基阻燃剂显示的耐热性与铜剥离强度下降的缺点,由于使用多官能环氧树脂,提高了玻璃化转变温度(Tg),而且由于使用金属水合物无机阻燃剂以弥补由于多官能环氧树脂含量增加引起的阻燃性降低,同时提供了在包铜层压制品中需要的平衡的各种物理性质。
虽然为了说明性的目的公开了本发明的优选实施方式,但本领域普通技术人员理解可以有各种各样的修改,增加与置换,而不背离本发明的如随附的权利要求公开的本发明的范围与精神。
Claims (10)
1.一种非卤素阻燃剂环氧树脂组合物,包括:
(A)平均环氧当量为300-1500,并且磷含量为2-5wt%的含硅的磷改性环氧树脂;
(B)相对于含硅的磷改性环氧树脂,20-100重量份的多官能环氧树脂;
(C)相对于环氧当量,35-120%的胺类固化剂与酚醛固化剂的混合固化剂;与
(D)相对于树脂组合物,20-100重量份的金属水合物无机阻燃剂。
2.根据权利要求1的组合物,其中含硅的磷改性环氧树脂是非硅的磷改性环氧树脂与含硅化合物的混合物,或者在其分子结构中包含硅原子的磷改性环氧树脂。
3.根据权利要求1的组合物,其中所述含硅的磷改性环氧树脂包括具有由通式I所代表结构的磷改性环氧树脂及包含大于0.5wt%的硅:
其中每个R独立地是双官能或者多官能环氧树脂的部分,并在环氧开环后通过羟基化作用与环氧树脂主链连接。
4.根据权利要求1的组合物,其中所述多官能环氧树脂是四官能环氧树脂和双酚A酚醛清漆环氧树脂。
5.根据权利要求1的组合物,其中在混合固化剂中胺组分:酚醛组分的当量比为90∶10-40∶60。
6.根据权利要求1的组合物,其中所述胺类固化剂是双氰胺。
7.根据权利要求1的组合物,其中所述酚醛的固化剂是线型酚醛清漆树脂固化剂。
8.权利要求1的组合物,其中所述金属水合物无机阻燃剂是氢氧化铝。
9.一种预浸料坯,包括在30-60重量份的玻璃纤维内的权利要求1-8任一项的40-70重量份的非卤素阻燃剂环氧树脂组合物。
10.一种包铜的层压制品,其中由权利要求9的预浸料坯组成的一种或多种层压制品与位于层压制品外面的包铜外层通过加热与受压结合成一整体。
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CN102399415A (zh) * | 2010-09-14 | 2012-04-04 | 联茂电子股份有限公司 | 预浸体组合物及应用该预浸体组合物所制成的胶片和基板 |
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CN104448237A (zh) * | 2014-11-05 | 2015-03-25 | 广东一通管业科技有限公司 | 一种适用于钢管的硅氮磷协同阻燃环氧树脂粉末涂料及其制备方法 |
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