CN110431187B - 氰酸酯树脂组合物及预浸料 - Google Patents
氰酸酯树脂组合物及预浸料 Download PDFInfo
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Abstract
在本发明中,为了提供即使不添加用于调整粘度的热塑性树脂,也能够抑制加热固化时的树脂流动,消除树脂缺损、厚度的不均匀,并且具有优异的操作性的氰酸酯树脂组合物,而配合(A)氰酸酯树脂、(B)固化剂或固化促进剂、(C)二氧化硅微粒、和(D)核壳橡胶粒子,相对于上述(A)氰酸酯树脂100质量份,上述(C)二氧化硅微粒为1~5质量份并且上述(D)核壳橡胶粒子为2~10质量份,使上述(C)二氧化硅微粒与上述(D)核壳橡胶粒子的质量比以(C)/(D)计为1/1~1/5。
Description
技术领域
本发明涉及氰酸酯树脂组合物以及预浸料。
背景技术
已知将以环氧树脂为代表的热固性树脂作为基体的纤维强化复合材料。例如在专利文献1中,公开了含有作为基体的环氧树脂、用于调整粘度的热塑性树脂、填料、和固化剂的环氧树脂组合物,此外公开了使该组合物与强化纤维复合而获得的预浸料。这样的预浸料由于轻量性和优异的力学特性而在以航空机、车辆等的结构材料、混凝土结构物的增强、高尔夫球杆、网球拍、钓竿等体育领域等为代表的广泛领域中使用。
作为这样的用途所使用的预浸料所要求的特性之一,可举出耐热性。因此,研究了各种以比环氧树脂耐热性高的树脂作为基体的纤维强化复合材料。
现有技术文献
专利文献
专利文献1:日本特开2011-99094号公报
发明内容
发明所要解决的课题
作为能够成为环氧树脂的替代的树脂,可举出氰酸酯树脂。氰酸酯树脂与环氧树脂相比耐热性优异,能够耐受例如直到300℃附近的热。
然而,氰酸酯树脂具有用于调整粘度的热塑性树脂不易溶解,树脂组合物的粘度调整困难,虽然在室温下具有高粘度但是在固化加热时低粘度化这样的问题。因为该问题,在将预浸料加热固化时树脂组合物从强化纤维流出,所得的纤维强化复合材料发生树脂缺损,厚度变得不均匀。为了抑制固化时的树脂流动,需要使树脂组合物的粘度更高,但在该情况下,由于室温时的树脂组合物的粘度变得过高,因此预浸料成型时的操作性恶化。
因此本发明的目的是提供即使不添加用于调整粘度的热塑性树脂,也能够抑制加热固化时的树脂流动,消除树脂缺损、厚度的不均匀,并且具有优异的操作性的氰酸酯树脂组合物以及使用了该氰酸酯树脂组合物的预浸料。
用于解决课题的方法
本发明人反复进行了深入研究,结果发现,通过在氰酸酯树脂中添加固化剂或固化促进剂、二氧化硅微粒和核壳橡胶粒子,将二氧化硅微粒相对于氰酸酯树脂的配合比例和核壳橡胶粒子相对于氰酸酯树脂的配合比例特定化,能够解决上述课题,从而完成了本发明。
即,本发明如下所述。
1.一种氰酸酯树脂组合物,其特征在于,含有:(A)氰酸酯树脂;(B)固化剂或固化促进剂;(C)二氧化硅微粒;以及(D)核壳橡胶粒子,相对于上述(A)氰酸酯树脂100质量份,包含上述(C)二氧化硅微粒1~5质量份和上述(D)核壳橡胶粒子2~10质量份,上述(C)二氧化硅微粒与上述(D)核壳橡胶粒子的质量比以(C)/(D)计为1/1~1/5。
2.根据上述1所述的氰酸酯树脂组合物,其特征在于,利用平行板在温度70℃、频率1Hz的条件下进行了粘弹性测定时,应变1%的tanδ小于1,并且应变100%的tanδ为1以上。
3.根据上述1所述的氰酸酯树脂组合物,上述(A)氰酸酯树脂为酚醛清漆型的氰酸酯树脂。
4.根据上述1所述的氰酸酯树脂组合物,相对于上述(A)氰酸酯树脂100质量份,上述(C)二氧化硅微粒的配合量为2~4质量份。
5.根据上述1所述的氰酸酯树脂组合物,相对于上述(A)氰酸酯树脂100质量份,上述(D)核壳橡胶粒子的配合量为4~8质量份。
6.根据上述1所述的氰酸酯树脂组合物,上述(C)二氧化硅微粒与上述(D)核壳橡胶粒子的质量比以(C)/(D)计为1/1.5~1/4。
7.一种预浸料,其包含上述1~6中任一项所述的氰酸酯树脂组合物和强化纤维。
8.根据上述7所述的预浸料,上述预浸料中的上述氰酸酯树脂组合物的含量为30~60质量%。
发明的效果
根据本发明,由于在(A)氰酸酯树脂中添加(B)固化剂或固化促进剂、(C)二氧化硅微粒和(D)核壳橡胶粒子,将相对于(A)氰酸酯树脂的(C)二氧化硅微粒和(D)核壳橡胶粒子的配合比例特定化,因此能够提供即使不添加用于调整粘度的热塑性树脂,也能够抑制加热固化时的树脂流动,消除树脂缺损、厚度的不均匀,并且具有优异的操作性的氰酸酯树脂组合物。
此外,利用平行板在温度70℃、频率1Hz的条件下进行了粘弹性测定时,应变1%的tanδ小于1,并且应变100%的tanδ为1以上的本发明的上述氰酸酯树脂组合物在加热固化时的树脂流动的抑制性、树脂缺损、厚度的不均匀的消除、以及操作性方面特别优异。
此外,包含上述氰酸酯树脂组合物和强化纤维的预浸料的耐热性优异,此外,树脂缺损、厚度的不均匀也被抑制,因此机械强度也优异。
具体实施方式
以下,进一步详细对本发明的实施方式进行说明。
(A)氰酸酯树脂
本发明中使用的(A)氰酸酯树脂没有特别限制。一般而言,氰酸酯树脂由下述式表示。
R-(O-C≡N)n
(式中,R表示具有芳香环的2价以上的有机基,n表示2以上的整数。)
作为这样的氰酸酯树脂,可举出酚醛清漆型、双酚A型、双酚E型、双酚F型的氰酸酯树脂等。它们之中,优选为酚醛清漆型的氰酸酯树脂。
作为酚醛清漆型氰酸酯树脂,可以利用市售品,可举出例如ロンザジャパン株式会社制、プリマセットPT-30、プリマセットPT-60等。
(B)固化剂或固化促进剂
作为本发明中使用的(B)固化剂或固化促进剂,只要能够促进氰酸酯树脂的热固化,就没有特别限制,可举出例如,钴、铜等的金属配位化合物、醇类、酸、胺、碱等。
(C)二氧化硅微粒
作为本发明中使用的(C)二氧化硅微粒,优选为亲水性的二氧化硅微粒,可举出沉淀法二氧化硅、凝胶法二氧化硅、热分解法二氧化硅、熔融二氧化硅那样的非晶质合成二氧化硅;结晶合成二氧化硅;天然二氧化硅等。
(C)二氧化硅微粒的平均一次粒径优选为5nm~100nm。
(D)核壳橡胶粒子
本发明中使用的(D)核壳橡胶粒子是公知的,可以为例如将与核成分不同种类的壳成分聚合物接枝聚合于以交联了的橡胶状聚合物作为主成分的粒子状核成分的表面而得的粒子。
作为核成分,可举出例如丁二烯橡胶、丙烯酸系橡胶、硅橡胶、丁基橡胶、NBR、SBR、IR、EPR等。
作为壳成分,可举出例如使选自丙烯酸酯系单体、甲基丙烯酸酯系单体、芳香族系乙烯基单体等中的单体聚合了的聚合物。
(D)核壳橡胶粒子的平均粒径为例如10nm~10μm,优选为100nm~500nm。
(配合比例)
本发明的氰酸酯树脂组合物需要相对于(A)氰酸酯树脂100质量份,包含(C)二氧化硅微粒1~5质量份和(D)核壳橡胶粒子2~10质量份,(C)二氧化硅微粒与(D)核壳橡胶粒子的质量比以(C)/(D)计为1/1~1/5。
如果(C)二氧化硅微粒的上述配合比例小于1质量份或(D)核壳橡胶粒子的上述配合比例小于2质量份,则树脂流动的抑制不充分,不能发挥本发明的效果。
如果(C)二氧化硅微粒的上述配合比例超过5质量份,或(D)核壳橡胶粒子的上述配合比例超过10质量份,则树脂组合物的粘度上升,操作性恶化,此外,固化物的机械特性(主要是弹性模量)降低。
在(C)二氧化硅微粒与(D)核壳橡胶粒子的质量比以(C)/(D)计超过1/1的情况下,即在相对于(C)成分而(D)成分的配合量少的情况下,树脂流动的抑制不充分,不能发挥本发明的效果。
在(C)二氧化硅微粒与(D)核壳橡胶粒子的质量比以(C)/(D)计小于1/5的情况下,即在相对于(C)成分而(D)成分的配合量过多的情况下,树脂流动抑制效果变得过高,因此预浸料成型时的操作性恶化。
在本发明中,相对于(A)氰酸酯树脂100质量份,(C)二氧化硅微粒的配合量进一步优选为2~4质量份,(D)核壳橡胶粒子的配合量进一步优选为4~8质量份,(C)二氧化硅微粒与(D)核壳橡胶粒子的质量比以(C)/(D)计进一步优选为1/1.5~1/4。
本发明的氰酸酯树脂组合物通过利用平行板在温度70℃、频率1Hz的条件下进行了粘弹性测定时,应变1%的tanδ小于1,并且应变100%的tanδ为1以上,从而加热固化时的树脂流动被抑制,树脂缺损、厚度的不均匀不易发生,操作性也特别优异。另外,粘弹性的测定可以通过使用ティー·エー·インスツルメント社制,商品名ARES等来测定。此外,该粘弹性可以通过将相对于(A)氰酸酯树脂的(C)二氧化硅微粒和(D)核壳橡胶粒子的配合量如上述那样适当设定来实现。
本发明的氰酸酯树脂组合物根据需要可以含有其它添加剂。作为添加剂,可举出例如,填充剂、防老剂、溶剂、阻燃剂、反应延迟剂、抗氧化剂、颜料(染料)、增塑剂、触变性赋予剂、紫外线吸收剂、表面活性剂(包含流平剂)、分散剂、脱水剂、增粘剂、抗静电剂等。
本发明的预浸料包含上述本发明的氰酸酯树脂组合物和强化纤维。
具体而言,本发明的预浸料通过使本发明的氰酸酯树脂组合物含浸于强化纤维而获得。
本发明的预浸料所使用的强化纤维没有特别限制,可举出例如,以往公知的强化纤维。其中,从强度的观点考虑,优选为选自碳纤维、玻璃纤维和芳族聚酰胺纤维中的至少1种。
关于纤维的形态,没有特别限制,可举出粗纱、将粗纱沿一个方向拉齐的形态、织物、无纺布、编物、薄纱等。
关于本发明的预浸料的制造方法,没有特别限制。可举出例如,使用溶剂的湿法、作为无溶剂法的热熔法。从能够缩短干燥时间这样的观点考虑,溶剂的使用量相对于氰酸酯树脂组合物的固体成分100质量份,优选为80~200质量份。
在本发明的预浸料中,从所得的纤维强化复合材料的机械性质的观点考虑,氰酸酯树脂组合物的含量优选为预浸料中的30~60质量%。
关于本发明的预浸料的用途,没有特别限制。通过使本发明的预浸料固化,可以获得例如以往公知的纤维强化复合材料。具体而言,可举出例如,整流罩、襟翼、前缘、底板、螺旋桨、机身等航空机部件;摩托车车架、前罩板、挡泥板等双轮车部件;车门、引擎盖、后背门、侧挡泥板、侧面面板、挡泥板、能量吸收构件、行李箱盖、硬顶(日文原文:ハードップ)、外后视镜罩、阻流板、扩散器、滑雪板放置架、发动机气缸盖、发动机罩、车架、空气阻流板、螺旋桨轴等汽车部件;排头车辆车头、车顶、侧板、车门、底盘盖、侧防护板等车辆用外板;行李架、座位等铁道车辆部件;内饰、翼车中的翼的内板、外板、车顶、底板等安装于汽车、单车的侧防护板等流线型零部件;笔记本个人电脑、便携电话等壳体用途;X射线暗盒、顶板等医学用途;平板扬声器、扬声器纸盆等音响制品用途;高尔夫球杆头、潜水面罩、雪地滑板、冲浪板、护具等体育用品用途;板簧、风车叶片、电梯(吊笼面板、门)那样的一般产业用途。
此外,可以将本发明的预浸料与其它构件(例如,蜂窝芯)叠层而制作纤维强化复合材料。作为可以将本发明的预浸料与其它构件叠层而制作的纤维强化复合材料,可举出例如,蜂窝夹层面板。
实施例
以下,通过实施例和比较例进一步说明本发明,但本发明不限制于下述例。
在下述例中,使用了以下材料。
(A)氰酸酯树脂:ロンザジャパン株式会社制,プリマセットPT-30、プリマセットPT-60(酚醛清漆型的氰酸酯树脂)
(B)固化剂或固化促进剂:三菱化学株式会社制DICY-15(双氰胺)
(C)二氧化硅微粒:キャボット社制CAB-O-SIL M5(亲水性热解法二氧化硅)
(D)核壳橡胶粒子:株式会社カネカ制MX-154(环氧树脂/核壳橡胶粒子母料;包含丁二烯系核壳橡胶粒子40质量%)
按照下述表1所示的配合比例(质量份),将各材料使用捏合机在70℃下混炼,调制出各种氰酸酯树脂组合物。
对所得的各种氰酸酯树脂组合物进行了以下测定。
粘弹性:使用ティー·エー·インスツルメント社制,ARES,利用平行板在温度70℃、频率1Hz的条件下,测定应变1%或100%下的tanδ。
预浸料的成型
使氰酸酯树脂组合物膜(树脂重量104g/m2)含浸于玻璃纤维织物(纤维目付量156g/m2)而成型预浸料。成型的预浸料中的氰酸酯树脂组合物为40质量%。
树脂流动:将裁切成100mm×100mm的预浸料叠层4片,在温度180℃、压力3kgf/cm2下压制30分钟后,测定从纤维溢出的树脂固化物重量,通过下式算出树脂流动。
树脂流动(%)=(溢出的树脂固化物重量)/(压制前的叠层物重量)×100操作性:通过下述评价基准评价了在制作氰酸酯树脂组合物膜时和向玻璃纤维织物的含浸时的操作性。
○:膜制作良好并且向玻璃纤维织物的含浸性良好
×:由于膜制作困难,因此不能进行预浸料的成型
尺寸稳定性:将裁切成300mm×300mm的预浸料叠层10片,利用高压釜在180℃下固化2小时,测定所得的纤维强化复合材料的厚度,在最大厚度与最小厚度之差为最大厚度的5%以下的情况下,判断为尺寸稳定性良好。
将结果示于表1中。
[表1]
由表1的结果表明,在(A)氰酸酯树脂中添加(B)固化剂或固化促进剂、(C)二氧化硅微粒和(D)核壳橡胶粒子,将相对于(A)氰酸酯树脂的(C)二氧化硅微粒和(D)核壳橡胶粒子的配合比例特定化到本发明中规定的范围内的各实施例的氰酸酯树脂组合物即使不添加用于调整粘度的热塑性树脂,也能够抑制加热固化时的树脂流动,消除树脂缺损、厚度的不均匀,并且具有优异的操作性。此外,各实施例的氰酸酯树脂组合物的利用平行板在温度70℃、频率1Hz的条件下进行了粘弹性测定时,应变1%的tanδ小于1,并且应变100%的tanδ为1以上,因此为低应变且固体(tanδ<1),能够抑制加热固化时的树脂流动,此外为高应变且液体(tanδ≥1),膜涂覆、含浸时的操作性变得良好。
与此相对,比较例1中,由于不添加(D)核壳橡胶粒子,因此树脂流动和尺寸稳定性的结果恶化了。
比较例2中,由于不添加(C)二氧化硅微粒,因此树脂流动和尺寸稳定性的结果恶化了。
比较例3中,由于(D)核壳橡胶粒子的配合量小于本发明中规定的下限,因此树脂流动和尺寸稳定性的结果恶化了。
比较例4中,由于(C)二氧化硅微粒的配合量和(D)核壳橡胶粒子的配合量都超过本发明中规定的上限,因此操作性恶化了。
Claims (8)
1.一种氰酸酯树脂组合物,其特征在于,含有:
(A)氰酸酯树脂;
(B)固化剂或固化促进剂;
(C)二氧化硅微粒;以及
(D)核壳橡胶粒子,
并且所述组合物不含有热塑性树脂,
相对于所述(A)氰酸酯树脂100质量份,包含所述(C)二氧化硅微粒1~5质量份和所述(D)核壳橡胶粒子2~10质量份,
所述(C)二氧化硅微粒与所述(D)核壳橡胶粒子的质量比以(C)/(D)计为1/1~1/5。
2.根据权利要求1所述的氰酸酯树脂组合物,其特征在于,利用平行板在温度70℃、频率1Hz的条件下进行了粘弹性测定时,应变1%的tanδ小于1,并且应变100%的tanδ为1以上。
3.根据权利要求1所述的氰酸酯树脂组合物,所述(A)氰酸酯树脂为酚醛清漆型的氰酸酯树脂。
4.根据权利要求1所述的氰酸酯树脂组合物,相对于所述(A)氰酸酯树脂100质量份,所述(C)二氧化硅微粒的配合量为2~4质量份。
5.根据权利要求1所述的氰酸酯树脂组合物,相对于所述(A)氰酸酯树脂100质量份,所述(D)核壳橡胶粒子的配合量为4~8质量份。
6.根据权利要求1所述的氰酸酯树脂组合物,所述(C)二氧化硅微粒与所述(D)核壳橡胶粒子的质量比以(C)/(D)计为1/1.5~1/4。
7.一种预浸料,其包含权利要求1~6中任一项所述的氰酸酯树脂组合物和强化纤维。
8.根据权利要求7所述的预浸料,所述预浸料中的所述氰酸酯树脂组合物的含量为30~60质量%。
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CN110431187A (zh) | 2019-11-08 |
CA3056553C (en) | 2020-11-17 |
EP3597703B1 (en) | 2021-10-06 |
CA3056553A1 (en) | 2018-09-20 |
KR20190095532A (ko) | 2019-08-14 |
AU2018233882A1 (en) | 2019-09-26 |
KR102065367B1 (ko) | 2020-01-13 |
WO2018168461A1 (ja) | 2018-09-20 |
JP6354884B1 (ja) | 2018-07-11 |
US10723880B2 (en) | 2020-07-28 |
AU2018233882B2 (en) | 2020-03-05 |
EP3597703A4 (en) | 2021-01-20 |
ES2902728T3 (es) | 2022-03-29 |
TWI671342B (zh) | 2019-09-11 |
TW201837094A (zh) | 2018-10-16 |
US20200071524A1 (en) | 2020-03-05 |
JP2018150445A (ja) | 2018-09-27 |
EP3597703A1 (en) | 2020-01-22 |
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