CN106715995B - 隔热材料及其制造方法 - Google Patents
隔热材料及其制造方法 Download PDFInfo
- Publication number
- CN106715995B CN106715995B CN201580048785.2A CN201580048785A CN106715995B CN 106715995 B CN106715995 B CN 106715995B CN 201580048785 A CN201580048785 A CN 201580048785A CN 106715995 B CN106715995 B CN 106715995B
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- Prior art keywords
- resin
- heat
- fiber
- insulating material
- laminate
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Abstract
本发明涉及一种隔热材料,其特征在于:由层叠有纤维层的层叠体构成,所述纤维层由耐热性纤维构成,所述纤维层被热固性树脂加固,所述层叠体不含或含有微量的具有比所述热固性树脂的耐热温度低的耐热温度的热塑性树脂。
Description
技术领域
本发明涉及一种隔热材料及其制造方法。
背景技术
作为如在使用前切削加工成与装置形状等相对应的形状且在使用状态下要求较高强度那样的隔热材料、例如热压制机、橡胶硫化机或注射成型机的隔热材料、用于感应电炉的外壳等的隔热材料,一直以来已知有利用波特兰水泥(portland cement)将滑石粉末和纸浆结合而成的隔热材料等(参照专利文献1)。
然而,关于上述隔热材料,由于增强纤维只是纸浆,因此,由加热而导致的机械强度的降低和尺寸变化较大,作为隔热材料韧性不够,所以,虽然切削加工性良好,但因附加高负荷或冲击负荷而容易发生龟裂或破裂等。
因此,期望韧性优异、具有更高强度、并且厚度精度优异的隔热材料。
现有技术文献
专利文献
专利文献1:日本特开昭61-109205号公报
发明内容
鉴于上述现有技术,本发明者们已经提供了一种具有良好的加工性,耐热性、机械强度、韧性等优异,并且加工精度和厚度精度优异的隔热材料(日本特愿2013-117843)。本发明的目的在于进一步提供一种耐热性和耐磨损性优异的隔热材料及其制造方法。
为了解决上述技术课题,本发明者们进行了精心研究,其结果发现,通过减少隔热材料中所含的热塑性树脂的量,能够改善耐热性和耐磨损性,基于本见解而完成了本发明。
即,本发明提供以下的隔热材料及其制造方法。
1.一种隔热材料,其特征在于:由层叠有纤维层的层叠体构成,所述纤维层由耐热性纤维构成,所述纤维层被热固性树脂加固,
所述层叠体不含或含有微量的具有比所述热固性树脂的耐热温度低的耐热温度的热塑性树脂。
2.如1所述的隔热材料,其特征在于:所述层叠体含有微量的热塑性树脂,热塑性树脂的含量为7质量%以下。
3.一种隔热材料的制造方法,其特征在于,包括:
预浸料制作工序,所述预浸料制作工序是使热固性树脂渗透于由耐热性纤维构成的片材而制作预浸料,所述预浸料不含或含有微量的具有比所述热固性树脂的耐热温度低的耐热温度的热塑性树脂;
层叠体制作工序,将多片所述预浸料层叠而制作层叠体;和
压制工序,将所述层叠体在所述热固性树脂的固化温度以上的温度下进行压制成型。
4.如3所述的隔热材料的制造方法,其特征在于:所述预浸料含有微量的热塑性树脂,热塑性树脂的含量为7质量%以下。
5.一种隔热材料,其特征在于:由层叠有纤维层的层叠体构成,所述纤维层由耐热性纤维构成,所述纤维层被热固性树脂加固,
所述层叠体不含或含有微量的热塑性树脂,
所述热固性树脂为选自热固性酚醛树脂、环氧树脂、三聚氰胺树脂、脲醛树脂、不饱和聚酯树脂、醇酸树脂、聚氨酯树脂、热固性聚酰亚胺树脂、硅酮树脂中的1种以上,
所述热塑性树脂为选自丙烯酸树脂、聚乙烯醇、聚氯乙烯、聚苯乙烯、聚乙烯、聚丙烯、PET树脂、PBT树脂中的1种以上。
根据本发明,能够提供一种耐热性和耐磨损性优异的隔热材料及其制造方法。
附图说明
图1是表示用于制造本发明的隔热材料的预浸料的制造例的示意图。
图2是表示由预浸料制造本发明的隔热材料的制造例的示意图。
图3是表示实验例1中的因热塑性树脂含量的差异而导致的耐磨损性的差异的图。
图4是表示实验例1中的因热塑性树脂含量的差异而导致的加热时的厚度的变化的图。
图5是表示实验例1中的因热塑性树脂含量的差异而导致的加热时的重量的变化的图。
具体实施方式
本发明的隔热材料由层叠有纤维层的层叠体构成,纤维层由耐热性纤维构成,纤维层被热固性树脂加固。进一步,在本发明的隔热材料中,上述纤维层不含或含有微量的具有比上述热固性树脂的耐热温度低的耐热温度的热塑性树脂。在上述纤维层含有热塑性树脂的情况下,热塑性树脂的含量优选为7质量%以下,更优选为5质量%以下,更优选为3质量%以下。
在此,上述的“耐热温度”是能够保持树脂的物理性状的上限的温度(例如,树脂材料发生软化、变形的温度、或者树脂材料发生热分解的温度等)。具体而言,所谓耐热温度,就物理上的耐热性的观点而言,是软化温度或玻璃化转变温度等的温度,就化学上的耐热性的观点而言,是发生加热时的重量减少等的温度。更详细而言,本发明的耐热温度在热塑性树脂和热固性树脂中各自不同。本发明的热塑性树脂的耐热温度是在规定的加热条件(加热时间、升温速度)下发生软化的软化温度、或者组成成分的结合断裂而树脂自身变性劣化的温度即热分解温度(具体而言,是规定比率(5%或10%)重量减少温度、载荷变形温度、规定比率(例如2%)厚度变化率温度、利用树脂材料的形状(膨胀、裂缝、弯曲)或颜色的外观判定得到的温度)。本发明的热固性树脂的耐热温度是在上述规定的加热条件下发生固化的固化温度、或者组成成分的结合断裂而树脂自身变性劣化的温度即热分解温度(具体而言,是规定比率(5%或10%)重量减少温度、载荷变形温度、规定比率(例如2%)厚度变化率温度、利用树脂材料的形状(膨胀、裂缝、弯曲)或颜色的外观判定得到的温度)。进一步,如果进行特定,则本发明的热塑性树脂和热固性树脂的耐热温度是加热一定时间时的重量减少成为10%以下的温度。
这样,在本发明中,通过不含热塑性树脂或使热塑性树脂的含量为微量,从而提高了耐热性、耐磨损性、强度(弯曲强度)。
关于此点,具体而言,在隔热材料的纤维层含有规定量的具有比热固性树脂的耐热温度低的耐热温度的热塑性树脂作为例如用于保形的上浆剂或粘合剂等的情况下,在高温下因热塑性树脂的塑性而容易发生蠕变(材料变形),因上述蠕变而产生疲劳,因此,结构的强度变弱。
另外,在隔热材料例如用作模具装置的隔热板的情况下,因模具装置的压制成型时的加热、加压而使隔热板发生蠕变时,在隔热板与模具装置的被安装体之间会产生间隙,模具装置的压力变得不稳定。
进一步,热塑性树脂因高温化而被热分解时,会因其分解时的发热而进一步促进分解。因这样的热分解而促使热塑性树脂的消失时,纤维层的粘接强度变弱,纤维层成为容易松开的状态,带来耐热性和磨损性的降低、进一步的强度降低。
因此,在本发明的隔热材料中,通过采用不含热塑性树脂或使热塑性树脂的含量成为微量这样的结构,能够抑制由热塑性树脂使隔热材料的耐热性、耐磨损性、强度(弯曲强度)降低的情况。换而言之,在本发明的隔热材料中,通过采用不含热塑性树脂或使热塑性树脂的含量成为微量这样的结构,能够提高耐热性、耐磨损性、强度(弯曲强度)。
作为耐热性纤维,可以使用具有耐热性的无机纤维和/或有机纤维。作为无机纤维,可以列举选自玻璃纤维、二氧化硅纤维、氧化铝纤维、莫来石纤维、碳化硅纤维、岩棉等中的一种以上。作为有机纤维,可以列举选自芳族聚酰胺、聚酯、聚乙烯、丙烯酸、人造丝、碳纤维等中的一种以上。
作为热固性树脂,可以列举选自热固性酚醛树脂、环氧树脂、三聚氰胺树脂、脲醛树脂、不饱和聚酯树脂、醇酸树脂、聚氨酯树脂、热固性聚酰亚胺树脂、硅酮树脂等中的一种以上。
作为热塑性树脂,可以列举选自丙烯酸树脂、聚乙烯醇、聚氯乙烯、聚苯乙烯、聚乙烯、聚丙烯、PET(聚对苯二甲酸乙二醇酯)树脂、PBT(聚对苯二甲酸丁二醇酯)树脂等中的一种以上。另外,上述热塑性树脂与上述热固性树脂相比,耐热温度低。
在此,鉴于上述的热塑性树脂和热固性树脂,本发明的隔热材料可以构成为:其由层叠有纤维层的层叠体构成,上述纤维层由耐热性纤维构成,上述纤维层被热固性树脂加固,上述层叠体不含或含有微量的热塑性树脂,上述热固性树脂为选自热固性酚醛树脂、环氧树脂、三聚氰胺树脂、脲醛树脂、不饱和聚酯树脂、醇酸树脂、聚氨酯树脂、热固性聚酰亚胺树脂、硅酮树脂中的1种以上,上述热塑性树脂为选自丙烯酸树脂、聚乙烯醇、聚氯乙烯、聚苯乙烯、聚乙烯、聚丙烯、PET树脂、PBT树脂中的1种以上。
纤维和热固性树脂在隔热材料中所占的比例,例如可以为93质量%以上、95质量%以上、97质量%以上、或99质量%以上。
本发明的隔热材料除了纤维和热固性树脂以外,还可以含有固化剂、固化促进剂、无机填充剂、催化剂等。
作为固化剂(不含热固性树脂、热塑性树脂),可以列举六亚甲基四胺等的胺类、有机过氧化物等的过氧化物等。
作为固化促进剂,可以列举选自磷系化合物、叔胺、咪唑、有机酸金属盐、路易斯酸、胺络盐等中的1种以上。
作为无机填充剂,可以列举选自二氧化硅、碳酸钙等中的一种以上。通过含有无机填充剂,能够发挥增强效果,能够容易地将密度、导热系数、蠕变性控制在所希望的范围内。例如,隔热材料可以构成为:优选含有无机填充剂0~32质量%、更优选为5~20质量%、进一步优选为7~15质量%。
在隔热材料中,对耐热性纤维和热固性树脂的含量没有特别限定。例如,隔热材料可以构成为:含有耐热性纤维10~90质量%、20~80重量%或30~70质量%。另外,隔热材料可以构成为:含有热固性树脂10~90质量%、20~80重量%或30~70质量%。
本发明的隔热材料也可以由以下的层叠体构成,所述层叠体由纤维层和非纤维层(例如含金属层)构成,但优选可以由只层叠有纤维层的层叠体(即不具有非纤维层的层叠体)构成。另外,上述非纤维层可以由例如隔热材料(层叠体)的保护用途(增强材料或耐火材料、耐水材料等)的层构成,在本发明的隔热材料中,可以不含作为外观的美观用途的装饰板用纸(钛纸等)而构成。另外,层叠体中的各纤维层和各非纤维层的厚度可以相等或大致相等地构成,也可以相互不同地构成。
本发明的隔热材料可以使热固性树脂渗透于耐热性片材(纤维制片材)中制作预浸料,将多片该预浸料层叠制作层叠体,将层叠体在热固性树脂的固化温度以上的温度下进行压制成型来进行制造。热塑性树脂可以包含在片材中,也可以与热固性树脂一起渗透。
图1是表示用于制造本发明的隔热材料的预浸料的制造例的示意图。
在图1所示的例子中,利用辊等将耐热性片材1从以卷绕的状态保持耐热性片材1的支架H上拉出,并且在充满热固性树脂2的浸渍槽T中浸渍,使规定量的热固性树脂2渗透,之后,在用干燥机D干燥之后,用切割机C切割成规定尺寸,由此能够制造作为目的的预浸料3。
本发明中使用的耐热性片材1有布、纸、垫等。布可以通过编织玻璃纤维来进行制造。
纸可以利用抄造机进行制造。可以向松散的无机纤维中加入适当少量的有机粘合剂,利用抄造机加工成纸状来进行制造。作为有机粘合剂,可以使用热塑性树脂(丙烯酸树脂、聚乙烯醇等)和/或热固性树脂。优选为热固性树脂。
无机纸中的无机纤维的含有比例优选为45~100质量%,更优选为74~94质量%,进一步优选为82~88质量%。有机粘合剂的含有比例优选为0~55质量%,更优选为6~26质量%,进一步优选为12~18质量%。
纸的平均厚度通常为0.2~6mm。在本发明中,平均厚度是指利用游标卡尺或千分尺测定任意的8个地方的厚度时的算术平均值。
纸的基重通常为20~430g/m2。在本发明中,基重(g/m2)是指根据JIS P 8124的规定算出的值。
垫是将纤维相互缠绕而成的,例如,可以利用针刺机使松散的纤维(bulk fiber)相互缠绕,加工成垫状而制造。作为上述垫,例如仅由无机纤维构成(即无机纤维100质量%),可以不含作为用于保形的上浆剂等的热塑性树脂而构成。无机纤维例如可以由玻璃纤维构成。
垫在表面具有凹凸,因此,在进行层叠时,相互缠绕,强度增加,因而优选。另外,由于可以不使用粘合剂而进行制造,因此,能够降低成本。
垫的平均厚度例如为2~20mm。垫的基重例如为100~4000g/m2。
可以使热固性树脂与固化剂、固化促进剂一起渗透于耐热性片材1。另外,也可以使热固性树脂与无机填充材料一起渗透到片材中。
在耐热性片材1由纸构成的情况下,由纸所获得的预浸料的基重例如可以设定为30~690g/m2。
在耐热性片材1由垫构成的情况下,由垫所获得的预浸料的基重例如可以设定为150~10000g/m2。
预浸料的基重(g/m2)是指由100cm见方的正方形状的预浸料的质量(g)算出的值。
图2是表示由预浸料制造本发明的隔热材料的制造例的示意图。
在图2所示的例子中,将热固性树脂渗透到耐热性片材中形成预浸料3,将所希望片数的多片该预浸料3进行层叠,形成5个层叠物L,在将所获得的5个预浸料的层叠物L以将隔离物介于各层叠物间的状态在压制机P的压制板间进行重叠之后,在构成预浸料的热固性树脂的热固化温度以上的温度条件下,以每1片预浸料的平均厚度成为所希望的厚度的方式加压并进行热压制,由此能够获得作为目的的隔热材料4。
在图2所示的实施方式中,对上述层叠物L以重叠5个的状态进行热压制成型,但层叠物L通常能够以重叠1~20个左右的状态进行热压制成型。
被热压制成型的预浸料的层叠片数没有特别限制。在片材为纸时,每10mm厚度,例如为3~200片。在片材为垫时,每10mm厚度,例如为1~20片。
另外,热压成型前后的预浸料的压缩率例如为15~50%、15~33%、或21~29%。预浸料的压缩率由下述式算出。
压缩率(%)=(热压成型后的每1片预浸料的平均厚度(mm)/供给热压成型的1片预浸料的平均厚度(mm))×100
热压制成型时的温度为构成预浸料的热固性树脂的热固化温度以上的温度,例如优选为100~200℃,更优选为130~180℃,进一步优选为145~155℃。
关于热压制成型时的加压时间,只要是构成预浸料的热固性树脂能够热固化的时间,就没有特别限制,例如优选为30分钟以上,更优选为60分钟以上,进一步优选为120分钟以上。
根据需要,可以对热压制成型后所获得的热压成型物进一步进行机械加工,另外,根据需要,也可以在适当的规定温度下加热来进行后固化。
利用上述方法所获得的隔热材料在将多片以耐热性片材为基材的预浸料层叠的状态下进行热压制成型,因此,认为均匀分散有热固性树脂的预浸料可以抑制在热压成型时热不均匀(加热温度的变动)的发生并进行压制成型。
因此,可以认为隔热材料与含有同量的纤维和热固性树脂的隔热材料相比,具有高精度的良好的加工性,并且能够发挥优异的弯曲强度、韧性、厚度精度等。
本发明的隔热材料的密度没有特别限定。例如,能够构成为:隔热材料的密度优选为400~2000kg/m3、更优选为900~1250kg/m3、进一步优选为1000~1100kg/m3。
隔热材料的密度是指由切成长120mm×宽40mm×所获得的隔热材料的厚度的试验片的尺寸(m3)和重量(kg)求出的值。
本发明的隔热材料优选具有在空气气氛下、以200℃加热24小时时不发生开裂或破裂的耐热性,更优选具有以260℃加热24小时时不发生开裂或破裂的耐热性。
本发明的隔热材料的导热系数优选为0.25W/(m·K)以下,更优选为0.18W/(m·K)以下,进一步优选为0.12W/(m·K)以下。
隔热材料的导热系数是指通过JIS A 1412-2:1999第2部热流计法HFM法测得的值。
本发明的隔热材料的弯曲强度优选为30MPa以上,更优选为45MPa以上,进一步优选为55MPa以上。
弯曲强度是指根据JIS C 2210-1975的纤维强化树脂的弯曲试验测得的值。
本发明的隔热材料根据JIS K 6911进行测定时的夏比冲击值(Charpy impactvalue)优选为10kJ/m2以上,更优选为15kJ/m2以上,进一步优选为18kJ/m2以上。
通过夏比冲击值处于上述范围内,能够发挥充分的韧性。
本发明的隔热材料在利用游标卡尺测定任意的8个地方的厚度时,优选具有厚度的差在±5mm以内的厚度精度,更优选具有厚度的差在±3mm以内的厚度精度,进一步优选具有厚度的差在±2.5mm以内的厚度精度。
实施例
接着,列举实施例对本发明进行更具体地说明,但这只是例示,并不限制本发明。
实施例1
(1)预浸料的制作
使用图1所示的装置,用辊将缠绕在支架H上的耐热性垫1(平均厚度6mm,平均宽度1050mm,平均长度30mm,密度120kg/m3)拉出,并且在充满作为热固性树脂2的甲阶型酚醛树脂(热固化温度150℃)的浸渍槽T中浸渍。耐热性垫1是利用针刺将玻璃纤维相互缠绕而获得的。之后,利用干燥机D在60~130℃下进行干燥,接着,用切割机C进行切割,由此制作多片含有来自玻璃纤维制垫的纤维40质量%、甲阶型酚醛树脂60质量%的片状(板状)预浸料3。
(2)隔热材料的制作
制作5个层叠有13片(1)中所获得的预浸料3的层叠物L,如图2所示,将所获得的5个层叠物L以将隔离物介于各层叠物间的状态在压制机P的压制板间重叠之后,在150℃的温度条件下进行热压制成型2小时(或者在200℃的温度条件下为1小时),由此获得片状或板状(例如,长2000mm、宽1000mm、厚度22mm)的隔热材料4。关于隔热材料4,垫的玻璃纤维被热固性树脂加固,不含热塑性树脂。
所获得的隔热材料4含有纤维40质量%、甲阶型酚醛树脂60质量%,密度为1050kg/m3,具有在空气气氛下200℃下加热24小时时不发生开裂或破裂的耐热性,导热系数为0.12W/(m·K),弯曲强度为60MPa,按照JIS K 6911进行测定时的夏比冲击值为20kJ/m2,具有利用游标卡尺测定任意的8个地方的厚度时厚度的差在2mm以内的厚度精度,具有在切削加工时不发生开裂或破裂等而能够容易地进行加工的优异的加工性和加工精度。
实验例1
本发明的隔热材料通过热塑性树脂的含量较少,从而耐磨损性、耐热性优异,将其以该实验例示出。
(1)隔热材料B的制造
在实施例1中,使用包含聚乙烯醇系合成树脂(热塑性树脂,耐热温度小于150℃)和丙烯酸系合成树脂(热塑性树脂,耐热温度小于150℃)16质量%的玻璃纤维制纸(平均厚度0.78mm,基重110g/m2)来代替耐热性垫1,除此以外,与实施例1同样地进行操作,制作多片平均厚度0.84mm、长2110mm、宽1050mm的预浸料。然后,制作层叠有57片所获得的预浸料的层叠物L,除此以外,与实施例1同样地进行操作,获得长2070mm、宽1020mm、厚度12mm的隔热材料B。
所获得的隔热材料B含有纤维42质量%、甲阶型酚醛树脂50质量%、热塑性树脂8质量%。
(2)耐热温度的测定
用于隔热材料的树脂的耐热温度按照以下的方式进行测定。使用通用的烘箱等加热设备和通用的重量测定装置,在规定的加热时间内对树脂材料进行加热时,测定该材料发生10%重量减少时的温度作为耐热温度。其中,也可以使用TG(热重量测定装置)对耐热温度进行测定。
(3)磨损性的评价
以下,将实施例1所获得的隔热材料称为隔热材料A。
将隔热材料A、B在240℃的气氛下加热50小时和70小时。之后,返回至常温,测定磨损量。具体而言,使用Taber型磨损试验装置,使隔热材料与磨轮接触,使隔热材料相对于磨轮旋转。由于削去与磨轮接触的部分,所以测定试验前后的隔热材料的重量变化,求出磨损量(g)。将结果示于图3中。
(4)耐热性的评价
将隔热材料A、B放入烘箱,施加180℃下16MPa、和200℃下15MPa的热和压力,测定厚度的变化。将结果示于图4中。
另外,将隔热材料A、B加热至450℃,测定重量减少(%)。将结果示于图5中。
以上,如图3~图5所示,隔热材料中所含的热塑性树脂为8质量%以上时,隔热材料的磨损性、耐热性(重量减少、厚度变化)的降低显著,隔热材料中所含的热塑性树脂优选至少为7质量%以下。
产业上的可利用性
本发明的隔热材料能够用于热压制机、橡胶硫化机或注射成型机的隔热材料、感应电炉的外壳等。
上述对本发明的几个实施方式和/或实施例进行了详细地说明,但本领域技术人员容易在实质上不脱离本发明的新的指点和效果的情况下,对这些作为例示的实施方式和/或实施例施加多个变更。因此,这些多个变更包含在本发明的范围内。
将该说明书所记载的文献和作为本申请的巴黎公约优先权基础的日本申请说明书的全部内容引入本申请中。
Claims (5)
1.一种隔热材料,其特征在于:
由层叠有纤维层的层叠体构成,所述纤维层由耐热性纤维构成,所述纤维层被热固性树脂加固,
所述层叠体不含或含有微量的具有比所述热固性树脂的耐热温度低的耐热温度的热塑性树脂,
所述耐热性纤维为选自玻璃纤维、二氧化硅纤维、氧化铝纤维、莫来石纤维、碳化硅纤维、岩棉、芳族聚酰胺、聚酯、聚乙烯、丙烯酸以及人造丝中的一种以上,
含有所述热固性树脂10~90质量%。
2.如权利要求1所述的隔热材料,其特征在于:
所述层叠体含有微量的热塑性树脂,热塑性树脂的含量为7质量%以下。
3.一种权利要求1所述的隔热材料的制造方法,其特征在于:
包括:
预浸料制作工序,所述预浸料制作工序是使热固性树脂渗透于由耐热性纤维构成的片材而制作预浸料,所述预浸料不含或含有微量的具有比所述热固性树脂的耐热温度低的耐热温度的热塑性树脂;
层叠体制作工序,将多片所述预浸料层叠而制作层叠体;和
压制工序,将所述层叠体在所述热固性树脂的固化温度以上的温度下进行压制成型,
在所述层叠体中,所述耐热性纤维和所述热固性树脂所占的比例为93质量%以上。
4.如权利要求3所述的隔热材料的制造方法,其特征在于:
所述预浸料含有微量的热塑性树脂,热塑性树脂的含量为7质量%以下。
5.一种隔热材料,其特征在于:
由层叠有纤维层的层叠体构成,所述纤维层由耐热性纤维构成,所述纤维层被热固性树脂加固,
所述层叠体不含或含有微量的热塑性树脂,
所述耐热性纤维为选自玻璃纤维、二氧化硅纤维、氧化铝纤维、莫来石纤维、碳化硅纤维、岩棉、芳族聚酰胺、聚酯、聚乙烯、丙烯酸以及人造丝中的一种以上,
所述热固性树脂为选自热固性酚醛树脂、环氧树脂、三聚氰胺树脂、脲醛树脂、不饱和聚酯树脂、醇酸树脂、聚氨酯树脂、热固性聚酰亚胺树脂、硅酮树脂中的1种以上,
所述热塑性树脂为选自丙烯酸树脂、聚乙烯醇、聚氯乙烯、聚苯乙烯、聚乙烯、聚丙烯、PET树脂、PBT树脂中的1种以上,
含有所述热固性树脂10~90质量%。
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US3897588A (en) * | 1972-02-12 | 1975-07-29 | Mitsubishi Gas Chemical Co | Process for the production of laminates utilizing pre-treating followed by impregnation |
CN101505955A (zh) * | 2006-08-22 | 2009-08-12 | 株式会社吴羽 | 含有碳纤维的叠层成型体及其制造方法 |
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JP6522912B2 (ja) | 2019-05-29 |
EP3193068A4 (en) | 2018-02-28 |
US20170259525A1 (en) | 2017-09-14 |
TWI627060B (zh) | 2018-06-21 |
CN106715995A (zh) | 2017-05-24 |
PH12017500318A1 (en) | 2017-07-03 |
KR20170047395A (ko) | 2017-05-04 |
MX2017003141A (es) | 2017-12-15 |
JP2016056914A (ja) | 2016-04-21 |
TW201630737A (zh) | 2016-09-01 |
EP3193068A1 (en) | 2017-07-19 |
RU2659855C1 (ru) | 2018-07-04 |
WO2016038806A1 (ja) | 2016-03-17 |
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