CN107848215B - 树脂组合物、其固化物及摩擦搅拌接合方法 - Google Patents

树脂组合物、其固化物及摩擦搅拌接合方法 Download PDF

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CN107848215B
CN107848215B CN201680045223.7A CN201680045223A CN107848215B CN 107848215 B CN107848215 B CN 107848215B CN 201680045223 A CN201680045223 A CN 201680045223A CN 107848215 B CN107848215 B CN 107848215B
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mass
cured product
friction stir
resin
monomer
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CN107848215A (zh
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石内隆仁
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Lishennoco Co ltd
Resonac Holdings Corp
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Zhaotai Electrical Co Ltd
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    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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Abstract

本发明提供使用了下述树脂组合物的摩擦搅拌接合方法，该树脂组合物的特征在于，包含：(A)具有烯属不饱和键的单体、(B)热固性树脂、(C)自由基聚合引发剂、以及(D)纤维增强材料，上述(B)热固性树脂为不饱和聚酯树脂或乙烯基酯树脂。

Description

树脂组合物、其固化物及摩擦搅拌接合方法
技术领域
本发明涉及树脂组合物、其固化物以及摩擦搅拌接合方法。
本申请基于2015年8月11日在日本申请的特愿2015-158830号来主张优先权，将其内容引用到本文中。
背景技术
包含不饱和聚酯树脂的组合物，特别是片状模塑料(sheet molding compound，以下称为“SMC”。)和块状模塑料(bulk molding compound，以下称为“BMC”。)是能够成型为所希望的形状，并且能够获得尺寸精度、机械特性优异的固化物的热固性树脂组合物。因此，SMC和BMC等热固性树脂复合材料被用作在各种领域中使用的结构构件、外板。
关于SMC和BMC，从机械强度的观点考虑，有时与金属组合使用。一般而言，作为将SMC、BMC和金属的构件彼此接合的方法，使用了使构件彼此嵌合的物理接合法、采用粘接剂的将构件彼此接合的化学接合法。然而，这些接合方法由于需要能够进行上述接合的接合工序，因此存在使用的工序数变多、制造成本变高这样的课题(例如，参照专利文献1、2)。
另一方面，包含热塑性树脂的热塑性树脂复合材料，与热固性树脂同样地，能够成型为所希望的形状，并且能够通过热熔合那样的方法进行摩擦搅拌接合(Friction StirWelding)(例如，参照专利文献3)。
现有技术文献
专利文献
专利文献1：日本特开2010-143009号公报
专利文献2：日本特表2013-503602号公报
专利文献3：日本特开2008-162280号公报
发明内容
发明所要解决的课题
然而，热塑性树脂复合材料存在初期的刚性低、机械强度的温度依赖性大这样的课题。
另一方面认为，热固性树脂复合材料由于成为基础的树脂为热固性，因此已经固化的复合材料不能通过因摩擦热而接合的摩擦搅拌接合来接合。
本发明是为了解决上述那样的课题而提出的，其目的是提供树脂组合物、其固化物和使用了固化物的摩擦搅拌接合方法，该树脂组合物是机械强度高，并且，温度依赖性小的热固性树脂复合材料，并且，该复合材料或该固化物与金属材料能够通过摩擦搅拌接合高效接合。
用于解决课题的方法
本发明人等为了解决上述问题而进行了深入研究，结果发现，通过将(A)具有烯属不饱和键的单体、(B)由不饱和聚酯树脂或乙烯基酯树脂构成的热固性树脂组合使用，能够使热固性树脂复合材料通过摩擦搅拌接合而与金属等构件接合，从而完成了本发明。
本发明可以提供能够很好地用于摩擦搅拌接合的树脂组合物、其固化物、以及固化物与构件的接合体的制造方法，即，固化物与构件的摩擦搅拌接合方法。本发明的摩擦搅拌接合方法也可以认为是固化物与构件的接合体的制造方法。
即，本发明的第一方案是以下的摩擦搅拌接合方法。
[1]一种摩擦搅拌接合方法，其包含下述工序：
(i)准备固化物和要与固化物接合的构件的工序，
(ii)使上述固化物与上述构件接触，形成接触部的工序，以及
(iii)使圆筒状的工具一边旋转一边按压于上述构件的至少一部分，通过搅拌和由摩擦产生的摩擦热，将上述固化物与构件接合的工序，
上述固化物是下述树脂组合物的固化物，所述树脂组合物包含：
(A)具有烯属不饱和键的单体、(B)不饱和聚酯树脂或乙烯基酯树脂、(C)自由基聚合引发剂、和(D)纤维增强材料。
本发明的摩擦搅拌接合方法优选具有以下特征。
[2].上述构件为金属构件。
[3].在[1]或[2]中，上述(D)纤维增强材料为碳纤维。
[4].在[1]～[3]的任一项中，在固化物中，以未反应的状态残存的上述(A)具有烯属不饱和键的单体的残存量相对于上述树脂组合物总量为0.1质量％～1质量％。
[5].在[1]～[4]的任一项中，
在上述树脂组合物中，
(A)具有烯属不饱和键的单体的量相对于(A)具有烯属不饱和键的单体与(B)热固性树脂的合计量为20质量％～80质量％，
(C)自由基聚合引发剂的量相对于(A)具有烯属不饱和键的单体与(B)热固性树脂的合计100质量份为0.1质量份～15质量份，
(D)纤维增强材料的量相对于(A)具有烯属不饱和键的单体与(B)热固性树脂的合计100质量份为5质量份～120质量份。
[6].在[1]～[5]的任一项中，上述(D)纤维增强材料为切断成长度25mm以下的纤维。
[7].在[1]～[6]的任一项中，上述(D)纤维增强材料为玻璃毡或玻璃布。
本发明的第2方案是作为以下结构体的结构体。
[8].一种结构物，其是上述固化物和上述构件通过[1]～[7]的任一项所述的摩擦搅拌接合方法接合而得的。
本发明的第3方案是以下树脂组合物。
[9].一种摩擦搅拌接合用树脂组合物，其特征在于，包含：
(A)具有烯属不饱和键的单体，
(B)热固性树脂，
(C)自由基聚合引发剂，以及
(D)纤维增强材料，
上述(B)热固性树脂为不饱和聚酯树脂或乙烯基酯树脂。
发明效果
根据本发明，能够提供机械强度高，并且，温度依赖性小，即不受环境温度左右的热固性树脂复合材料。该热固性树脂复合材料的固化物与由金属等构成的材料、构件能够通过摩擦搅拌接合高效接合。本发明能够提供优异的树脂组合物、其固化物以及摩擦搅拌接合方法。
附图说明
图1是显示本发明的摩擦搅拌接合的一优选例的示意图。
图2是显示实施例的接合性评价方法的示意图。
具体实施方式
对本发明的树脂组合物、其固化物以及摩擦搅拌接合方法的优选实施方式进行说明。
另外，本实施方式是为了使发明的宗旨更好地被理解而具体说明的实施方式，只要没有特别指定，就不限定本发明。在本发明的范围内，根据需要，也可以进行变更、省略、交换和/或追加。
[摩擦搅拌接合]
本发明可以使用的摩擦搅拌接合，是使用圆筒状的工具，一边使其旋转，一边用强力将位于工具前端的具有圆筒状截面的小突起部按压于例如2个构件彼此的对接面、上下重叠的2个构件中的一者的表面的接合法(作为优选例，参照图1)。通过在上述状态下使圆筒状工具或构件移动，能够增大接合区域。举出具体例，通过将圆筒状的工具的前端部压入到要接合的构件与构件(母材)的接合部，使摩擦热产生，使构件软化，并且通过工具的旋转力使接合部周边塑性流动而混炼，从而能够将多个构件一体化。例如，在将树脂固化物与构件等2个构件的叠层体接合时，摩擦热从凹陷部(压入痕迹)进一步向下方传递，能够进行树脂固化物与构件的接合。圆筒状的工具优选在前端具有突起部，通常，以突起部完全进入到构件的接触部的方式进行接合。突起部的形状可以任意选择，可举出圆筒状、圆锥台状等，可以进行螺纹加工等。突起部的尺寸也可以任意选择。作为被接合的构件，可以任意选择，优选为金属构件。其中，更优选熔化温度为500℃以上的金属。作为熔化温度为500℃以上的金属构件，可举出例如铝、铝合金等。
作为接合条件的例子，可举出圆筒状的工具(旋转器具)的形状、前端面的尺寸、旋转速度、移动速度、轴线相对于被接合的构件表面的法线的倾斜角等。它们可以根据被接合的构件和由热固性树脂组合物形成的树脂构件(固化物)的、材料的种类和厚度等来任意设定。
作为摩擦搅拌接合的旋转器具，可以使用在上述器具的前端部具有针状探针(突起部)的旋转器具、或除去了针状探针的旋转器具中的任一种。其中，具有针状探针的旋转器具能够提高接合强度，因此优选。
关于旋转器具的前端面的直径D，如果将被接合的构件的厚度设为t，则满足5t≤D≤20t的关系能够提高接合强度，因此优选。例如，在被接合的构件的厚度为2mm的情况下，直径D优选为10mm～40mm。
关于针状探针，前端直径d满足0.5t≤d≤5t的关系的针状探针可以提高接合强度，因此优选。
关于旋转器具的旋转速度，从接合强度的观点考虑，优选为1000转/min～5000转/min。关于接合速度(即旋转器具的移动速度)，从接合强度的观点考虑，优选为200mm/min～1000mm/min。
旋转器具的轴线相对于被接合的构件表面的法线的倾斜角θ如果为0°＜θ≤5°，则能够提高接合强度，因此优选。该倾斜角θ对应于摩擦搅拌接合的技术领域中的“前进角”。
[树脂组合物]
可以优选用于本发明的摩擦搅拌接合的树脂组合物包含：(A)具有烯属不饱和键的单体、(B)热固性树脂、(C)自由基聚合引发剂、和(D)纤维增强材料，(B)热固性树脂为不饱和聚酯树脂或乙烯基酯树脂。
“(A)具有烯属不饱和键的单体”
具有烯属不饱和键的单体为具有烯属碳-碳双键的化合物，根据需要选择，没有特别限定。
作为包含烯属不饱和基的化合物，可举出单官能单体和多官能单体。
单官能单体可以任意选择，可举出例如，苯乙烯、乙烯基甲苯、甲基苯乙烯和甲基丙烯酸甲酯等。这些单官能单体可以单独使用1种，也可以组合使用2种以上。优选为苯乙烯。
多官能单体可以任意选择，可举出例如，乙二醇二(甲基)丙烯酸酯、二甘醇二(甲基)丙烯酸酯、聚乙二醇#200(#400、#600)二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇(甲基)丙烯酸酯、三羟甲基丙烷(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、2-羟基-3-丙烯酰氧基丙基(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯和1,10-癸二醇二(甲基)丙烯酸酯等。这些多官能单体可以单独使用1种，也可以组合使用2种以上。
另外，在本说明书中，所谓“(甲基)丙烯酸酯”，是指甲基丙烯酸酯或丙烯酸酯。优选为乙二醇二(甲基)丙烯酸酯或三羟甲基丙烷三(甲基)丙烯酸酯。
本发明的树脂组合物中的(A)具有烯属不饱和键的单体的配合量相对于(A)具有烯属不饱和键的单体与(B)热固性树脂的合计量优选为20质量％～80质量％，更优选为25质量％～70质量％，进一步优选为30质量％～60质量％。
如果(A)具有烯属不饱和键的单体的配合量为20质量％以上，则树脂组合物的粘度变为适当的范围，成型时的操作性提高。另一方面，如果(A)具有烯属不饱和键的单体的配合量为80质量％以下，则可获得具有所希望的物性的树脂组合物的固化物。
另外，本发明的树脂组合物中的(A)具有烯属不饱和键的单体与(B)热固性树脂的合计量可以任意选择，但例如优选为20质量％～80质量％，更优选为30质量％～70质量％，进一步优选为40～60质量％。
“(B)热固性树脂”
(B)热固性树脂可以任意选择，优选使用不饱和聚酯树脂或乙烯基酯树脂。另外，这里所谓的不饱和聚酯树脂和乙烯基酯树脂，是指固化前的状态的树脂。
不饱和聚酯树脂没有特别限定，可以任意选择，可以使用在本发明的技术领域中使用于成型材料的公知材料。
此外，(B)热固性树脂可以包含上述的(A)具有烯属不饱和键的单体作为材料。
不饱和聚酯树脂一般为使多元醇、与不饱和多元酸或饱和多元酸缩聚(酯化)而获得的化合物。另外，在不损害本发明的效果的范围内，可以作为不饱和聚酯树脂的一部分使用乙烯基酯树脂。即，可以将不饱和聚酯树脂与乙烯基酯树脂组合使用。量的比可以任意选择，可举出不饱和聚酯树脂：乙烯基酯树脂＝80：20～20：80，更优选为75：15～50：50等。
不饱和聚酯树脂的重均分子量(MW)可以任意选择，没有特别限定。例如重均分子量(MW)优选为2000～50000，更优选为5000～20000。
如果不饱和聚酯树脂的重均分子量为上述范围内，则能够获得固化物的强度、电特性等充分的特性。
另外，在本说明书中，所谓“重均分子量”，是指使用凝胶渗透色谱(商品名：Shodex(注册商标)GPC-101，昭和电工社制)，在下述条件下在常温测定，使用标准聚苯乙烯标准曲线而求出的值。
柱：商品名：LF-804，昭和电工社制
柱温度：40℃
试样：共聚物的0.2质量％四氢呋喃溶液
流量：1mL/分钟
洗脱液：四氢呋喃
检测器：RI-71S
作为不饱和聚酯的合成中所使用的多元醇，没有特别限定，可以任意选择，可以使用公知的多元醇。
作为多元醇，可举出例如，乙二醇、丙二醇、丁二醇、二甘醇、双丙甘醇、三甘醇、戊二醇、己二醇、新戊二醇、氢化双酚A、双酚A和甘油等。这些多元醇可以单独使用1种，也可以组合使用2种以上。
作为不饱和聚酯的合成所使用的不饱和多元酸，没有特别限定，可以任意选择，可以使用公知的不饱和多元酸。
作为不饱和多元酸，可举出例如，马来酸酐、富马酸、柠康酸和衣康酸等。这些不饱和多元酸可以单独使用1种，也可以组合使用2种以上。
作为不饱和聚酯的合成中所使用的饱和多元酸，没有特别限定，可以任意选择，可以使用公知的饱和多元酸。
作为饱和多元酸，可举出例如，邻苯二甲酸酐、间苯二甲酸、对苯二甲酸、氯桥酸、琥珀酸、己二酸、癸二酸、四氯邻苯二甲酸酐、四溴邻苯二甲酸酐和内亚甲基四氢邻苯二甲酸酐等。这些饱和多元酸可以单独使用1种，也可以组合使用2种以上。
不饱和聚酯可以使用上述原料，通过公知的方法来合成。
不饱和聚酯的合成中的各种条件，根据使用的原料、其量来适当设定。一般而言，在氮气等非活性气体气流中，在140℃～230℃的温度下，在加压或减压下酯化较好。在该酯化反应中，根据需要，可以使用催化剂。
催化剂可以任意选择，可举出例如，乙酸锰、氧化二丁锡、草酸亚锡、乙酸锌和乙酸钴等公知的催化剂。这些催化剂可以单独使用1种，也可以组合使用2种以上。
乙烯基酯树脂可以任意选择，可举出使环氧树脂与α,β-不饱和一元羧酸通过公知的方法酯化而获得的环氧(甲基)丙烯酸酯作为优选的例子。
作为乙烯基酯树脂的合成中所使用的环氧树脂，可举出例如，双酚A、双酚AD、双酚F和双酚的二缩水甘油醚及其高分子量同系物、苯酚酚醛清漆型聚缩水甘油醚和甲酚酚醛清漆型聚缩水甘油醚类等。可以使用进一步在合成过程中使双酚A、双酚AD、双酚F和双酚S等酚类与这些的缩水甘油醚反应而获得的树脂、脂肪族环氧树脂。
乙烯基酯树脂的合成中所使用的α,β-不饱和一元羧酸可以任意选择，一般而言，可举出丙烯酸和甲基丙烯酸等。此外，作为α,β-不饱和一元羧酸，也可以使用巴豆酸、惕各酸和肉桂酸等。
乙烯基酯树脂可以通过例如将上述双酚类的缩水甘油醚与α,β-不饱和一元羧酸以羧基/环氧基＝1.05～0.95的比率在80℃～140℃进行酯化来合成。进一步，根据需要，可以使用催化剂。
作为催化剂，可举出例如，苄基二甲基胺、三乙胺、N,N-二甲基苯胺、三乙二胺和2,4,6-三(二甲基氨基甲基)苯酚等叔胺类、三甲基苄基氯化铵等季铵盐、氯化锂等金属盐等。
除了上述的由环氧(甲基)丙烯酸酯构成的乙烯基酯树脂以外，作为乙烯基酯树脂，也可以使用例如：使饱和二羧酸和不饱和二羧酸中的至少任一者与由多元醇获得的末端羧基的饱和聚酯树脂或不饱和聚酯反应而获得的树脂；使双酚A、双酚AD、双酚F和双酚S等双酚类与具有环氧基的α,β-不饱和一元羧酸衍生物反应而获得的饱和聚酯树脂或不饱和聚酯树脂的聚酯(甲基)丙烯酸酯树脂、丙烯酸酯树脂。
双酚类可以任意选择，可举出例如双酚A、双酚AD、双酚F、双酚S、双苯酚酚醛清漆和甲酚酚醛清漆等。
作为具有环氧基的α,β-不饱和一元羧酸衍生物，可举出例如，丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯等。
此外，作为饱和二羧酸、不饱和二羧酸和多元醇，可以使用与作为上述不饱和聚酯的原料成分而例示的物质同样的物质。
本发明中，优选将上述不饱和聚酯树脂或乙烯基酯树脂溶解于(A)具有烯属不饱和键的单体来使用。
“(C)自由基聚合引发剂”
自由基聚合引发剂作为固化剂使用。自由基聚合引发剂可以任意选择，没有特别限定，可以使用在本发明的技术领域中公知的自由基聚合引发剂。作为自由基聚合引发剂，可举出例如，过氧化-2-乙基己酸叔丁酯、过氧化-2-乙基己酸叔己酯、过氧化-2-乙基己酸1,1,3,3-四甲基丁酯、过氧化苯甲酰、1,1-二叔丁基过氧化环己烷、1,1-二叔己基过氧化环己烷、1,1-二叔丁基过氧化-3,3,5-三甲基环己烷、叔丁基过氧化异丙基甲酸酯、叔己基过氧化异丙基甲酸酯、过氧化苯甲酸叔丁酯、叔己基过氧化苯甲酸酯、1,6-双(叔丁基过氧化羰氧基)己烷、二异丙苯基过氧化物和二叔丁基过氧化物等有机过氧化物等。这些自由基聚合引发剂可以单独使用1种，也可以组合使用2种以上。
此外，本发明的树脂组合物中，除了自由基聚合引发剂以外，也可以使用固化促进剂。作为固化促进剂，可举出例如，环烷酸钴等。
本发明的树脂组合物中的(C)自由基聚合引发剂的配合量相对于(A)具有烯属不饱和键的单体与(B)热固性树脂的合计100质量份优选为0.1质量份～15质量份，更优选为2质量份～8质量份。
如果(C)自由基聚合引发剂的配合量为0.1质量份以上，则树脂组合物的固化时间短，固化变得充分。另一方面，如果(C)自由基聚合引发剂的配合量为15质量份以下，则可获得树脂组合物的储存稳定性。
“(D)纤维增强材料”
纤维增强材料可以任意选择。作为优选的例子，可举出玻璃纤维、纸浆纤维、テトロン(注册商标)纤维、维尼纶纤维、碳纤维、芳族聚酰胺纤维和硅灰石等各种有机纤维和无机纤维。其中，从操作性和固化物的机械强度方面考虑，优选为玻璃纤维和碳纤维。
作为纤维增强材料，优选使用长度被切断成25mm以下的纤维。
如果纤维增强材料的纤维长度为25mm以下，则不会损害树脂组合物在模具内的流动性。或者，也可以优选使用玻璃毡或玻璃布等编入了纤维增强材料的布、纤维增强材料的集合体，例如目付量300g/m2～700g/m2的玻璃毡或玻璃布等布、集合体。如果目付量为300g/m2以上，则可获得所希望的强度，如果为700g/m2以下，则不会发生在玻璃等增强材料中未含浸树脂的情况，可获得所希望的特性。
本发明的树脂组合物中的(D)纤维增强材料的配合量相对于(A)具有烯属不饱和键的单体与(B)热固性树脂的合计100质量份优选为5质量份～120质量份，更优选为10质量份～110质量份，进一步优选为20质量份～50质量份。
如果(D)纤维增强材料的配合量为5质量份以上，则固化物可获得充分的强度。
另一方面，如果(D)纤维增强材料的配合量为120质量份以下，则在(D)纤维增强材料中充分含浸(A)具有烯属不饱和键的单体、(B)热固性树脂。
“其它成分”
本发明的树脂组合物中，从改良各种物性的观点考虑，根据需要，可以含有填充材料、低收缩剂、脱模剂、增稠剂和颜料等任意成分。
填充材料、低收缩剂、脱模剂、增稠剂和颜料的种类没有特别限定，可以使用在本发明的技术领域中公知的种类。
作为填充材料，可举出例如，碳酸钙、硫酸钡、滑石、二氧化硅、中空填料、氢氧化铝、碳酸镁、氧化铝、氧化镁、氧化铍、氮化铝、氮化硼、氮化钛、碳化硅、碳化硼、碳化钛和硼化钛等无机填充材料。这些填充材料可以单独使用1种，也可以组合使用2种以上。
填充材料的平均一次粒径可以任意选择。从在树脂组合物中均匀分散的观点考虑，优选为0.5μm～30μm，更优选为1μm～20μm。
此外，填充材料的形状优选为不定形或球状的粉末状。填充材料的量可以任意选择，可举出例如相对于组合物的总量为3～30质量％，优选为5质量％～25质量％。
作为低收缩剂，可举出例如，聚苯乙烯、聚甲基丙烯酸甲酯、聚乙酸乙烯酯、饱和聚酯、苯乙烯-丁二烯系橡胶等一般作为低收缩剂使用的热塑性聚合物。这些低收缩剂可以单独使用1种，也可以组合使用2种以上。
此外，关于低收缩剂，从低收缩化和熔点的观点考虑，优选使用聚苯乙烯、聚甲基丙烯酸甲酯，从与不饱和聚酯或乙烯基酯的反应位点的观点考虑，优选使用二烯系橡胶。低收缩剂的量可以任意选择，可举出例如相对于组合物的总量为0.0～10质量％，优选为0.0～7质量％。
作为脱模剂，可举出例如，硬脂酸、硬脂酸锌、硬脂酸钙、硬脂酸铝、硬脂酸镁和巴西棕榈蜡等。脱模剂的量可以任意选择，可举出例如相对于组合物的总量为0.0质量％～7质量％，优选为0.5质量％～5质量％。
作为增稠剂，可举出例如，氧化镁、氢氧化镁、氢氧化钙和氧化钙等金属氧化物、以及异氰酸酯化合物。这些增稠剂可以单独使用1种，也可以组合使用2种以上。增稠剂的量可以任意选择，可举出例如相对于组合物的总量为0.0质量％～5质量％，优选为0.3质量％～3质量％。
另外，只要上述任意成分的配合量在不损害本发明的效果的范围内，就没有特别限定。
根据本发明的树脂组合物，由于将(A)具有烯属不饱和键的单体、与(B)由不饱和聚酯树脂或乙烯基酯树脂构成的热固性树脂组合使用，因此能够将机械强度高，温度依赖性小的热固性树脂复合材料通过摩擦搅拌接合而接合。
此外，根据本发明的树脂组合物，能够操作性和生产性好地制造由摩擦搅拌接合用树脂组合物形成的固化物。
[树脂组合物的制造方法]
本发明的树脂组合物是使(A)具有烯属不饱和键的单体、(B)热固性树脂、(C)自由基聚合引发剂和(D)纤维增强材料均匀分散而得的。
作为使(A)具有烯属不饱和键的单体、(B)热固性树脂、(C)自由基聚合引发剂和(D)纤维增强材料均匀分散的方法，只要是能够将这些成分均匀分散的方法就没有特别限定，可举出例如，使用了分散机、双臂式捏合机的方法。
树脂组合物的制造方法可以任意选择，可举出例如下述方法。使(B)热固性树脂溶解于(A)具有烯属不饱和键的单体。然后，在该溶液中加入(C)自由基聚合引发剂和(D)纤维增强材料，根据需要添加上述任意成分，进一步进行分散或溶解。
[固化物]
本发明的固化物为将本发明的树脂组合物固化而得的物质。固化温度、方法可以根据组合物而任意选择。可举出例如在5～180℃的温度下固化的方法等，根据需要也可以优选选择120℃～170℃等。
举出具体例，本发明的固化物通过将本发明的树脂组合物注入到模具等模内，在例如5～180℃的温度下，在加压下，将本发明的树脂组合物固化来获得。也可以认为是加压和加热而得的成型体。
在通过手糊成型而形成树脂组合物以及然后进行固化的情况下，优选在常温、常压下，在由玻璃毡或玻璃布形成的(D)纤维增强材料中含浸(A)具有烯属不饱和键的单体、(B)热固性树脂和(C)自由基聚合引发剂的混合物而获得本发明的树脂组合物，然后使其固化。上述树脂组合物可以作为没有变为完全固化物的中间制品来处理。为了使固化物的特性充分发挥，可以在固化后或加压固化后，进一步在60℃～120℃进行后固化。
在本发明的固化物中，以未反应的状态残存的(A)具有烯属不饱和键的单体的残存量相对于树脂组合物总量优选为0.1质量％～1质量％，更优选为0.15质量％～0.7质量％，进一步优选为0.2质量％～0.5质量％。单体的残存量可以通过例如实施例所记载的测定方法来测定。
如果具有烯属不饱和键的单体的残存量为0.1质量％以上，则在接合时，可获得充分的接合力，因此优选。另一方面，如果具有烯属不饱和键的单体的残存量为1质量％以下，则在接合时不产生由工具(旋转器具)的应力导致固化物变形等不良状况，因此优选。
本发明的固化物由于是将本发明的树脂组合物固化而成，因此机械强度高，尺寸稳定性优异。
实施例
以下，通过实施例和比较例进一步具体地说明本发明，但本发明不限定于以下实施例。
如下评价下述实施例和比较例中的各种物性。
(1)苯乙烯单体的残存量测定
从通过后述方法而获得的成型体(固化物)削出1g固化物，放入到螺纹管中，添加二甲基甲酰胺，使得固化物与二甲基甲酰胺的重量和成为10g，在23℃放置24小时。用二甲基甲酰胺提取所得的固化物中的残存单体。将作为提取剂的二甲基甲酰胺进行过滤，然后取滤液1μmL，使用气相色谱(GC)GC-14B(商品名，岛津制作所社制)，测定了苯乙烯单体的残存量。
预先，使用热固性树脂组合物所使用的苯乙烯单体来制作标准曲线。使用标准曲线对从上述滤液中检测到的苯乙烯单体的残存量定量。固化物中的苯乙烯单体的残存量(质量％)由(苯乙烯单体的残存量(质量))/(固化物的削出量(质量))×100(％)算出。
(2)接合性评价
如后所述将金属构件与树脂构件接合后，依照拉伸剪切试验(JIS-K6850：1999)，测定了金属构件与树脂构件的接合部的强度。将破坏强度小于2MPa的情况记为“×”“不可”，将破坏强度为2MPa～4MPa的情况记为“△”“可”，将破坏强度为4MPa～10MPa的情况记为“○”“良好”，将破坏强度为10MPa以上的情况记为“◎”“优异”。
(3)成型品的变形评价
通过目视观察实施例中获得的将金属构件与树脂构件接合而得的成型品，将成型品没有裂纹的情况记为裂纹“无”，将成型品有裂纹的情况记为“有”。
[实施例1]
通过将苯乙烯单体40质量份、苯乙烯单体的含量为30质量％的双酚A型乙烯基酯树脂(商品名リポキシ(注册商标)R-802，昭和电工社制)60质量份、作为自由基聚合引发剂的过氧化苯甲酸叔丁酯(以下，简称为“TBPO”。商品名：パーブチル(注册商标)Z，日油社制)1质量份、作为填充材料的碳酸钙(商品名：KS-1200A，平均粒径1.2μm，同和カルファイン社制)15质量份、氧化镁1质量份、硬脂酸锌2质量份和作为纤维增强材料的碳纤维(東レ社制)110质量份使用双臂型捏合机进行均匀地混炼，从而获得了实施例1中使用的热固性树脂组合物。
使用320mm×220mm×15mm的模具，将所得的热固性树脂组合物以成型温度150℃、成型压力10MPa、成型时间180秒进行加热加压成型，制作实施例1的成型体(固化物，长度320mm×宽度220mm×厚度2mm)。
从成型体切出长度100mm×宽度25mm×厚度2mm，使用切出的部分，按照上述评价方法(1)，进行了苯乙烯单体的残存量的测定。
作为与切出的成型体接合的构件，选择了铝板(A6060，100mm×25mm×1mm)。如图2所示，以12.5mm的宽度重合，在以下条件下，将成型体与铝板通过摩擦搅拌接合进行接合，获得了试验体。
作为旋转器具，使用了上述在器具的前端部具有针状探针(突起部)、旋转器具的前端面的直径D为15mm、针状探针的前端直径d为1mm的旋转器具。旋转器具的旋转速度设定为1000转/min，探针的移动速度设定为200mm/min，轴线相对于被接合的构件表面的法线的倾斜角θ设定为1°。
关于所得的试验体(接合体)，按照上述评价方法(2)和(3)，进行了接合性评价和成型品的变形评价。将结果示于表1中。
[实施例2]
将苯乙烯单体40质量份、苯乙烯单体的含量为30质量％的不饱和聚酯树脂A(商品名：リゴラック(注册商标)M-500D，昭和电工社制)60质量份、聚苯乙烯10质量份、作为自由基聚合引发剂的TBPO 1质量份、作为填充材料的碳酸钙(商品名：KS-1200A，平均粒径1.2μm，同和カルファイン社制)15质量份、氧化镁1质量份、硬脂酸锌2质量份和作为纤维增强材料的碳纤维(東レ社制)100质量份使用双臂型捏合机进行均匀地混炼，从而获得了实施例2中使用的热固性树脂组合物。
接下来，与实施例1同样地制作成型体，进行了评价。将结果示于表1中。
[实施例3～4]
除了如表1所示进行了配合以外，与实施例1同样地操作而制作成型体，进行了评价。将结果示于表1中。
[实施例5]
将苯乙烯单体的含量为30质量％的不饱和聚酯树脂B(商品名：リゴラック158BQTN，昭和电工社制)100质量份、作为自由基聚合引发剂的过氧化丁酮1质量份、和作为固化促进剂的5％环烷酸钴0.1质量份通过分散机均匀地分散。然后，将作为纤维增强材料的玻璃毡(目付量450g/m2，日东纺社制)60质量份，通过手糊成型使玻璃毡含浸，在23℃放置24小时，然后制作实施例5的成型体，与实施例1同样地进行了评价。将结果示于表1中。
[实施例6]
通过与实施例5同样的方法制作成型体后，将成型体进一步在120℃进行固化2小时。
关于所得的成型体，与实施例1同样地进行了评价。将结果示于表1中。
[实施例7]
通过将苯乙烯单体18质量份、苯乙烯单体的含量为30质量％的不饱和聚酯树脂A(商品名：リゴラック(注册商标)M-500D，昭和电工社制)82质量份、聚苯乙烯10质量份、作为自由基聚合引发剂的TBPO 1质量份、作为填充材料的碳酸钙(商品名：KS-1200A，平均粒径1.2μm，同和カルファイン社制)50质量份、氧化镁1质量份、硬脂酸锌2质量份、和作为纤维增强材料的玻璃纤维(日本电气硝子社制)10质量份使用双臂型捏合机均匀地混炼，从而获得了实施例7的热固性树脂组合物。
接下来，与实施例1同样地进行了评价。将结果示于表1中。
[实施例8]
与实施例3同样地操作而获得了树脂组合物后，以成型温度160℃、成型压力10MPa、成型时间300秒进行加热加压成型，制作实施例8的成型体，与实施例1同样地进行了评价。将结果示于表1中。
[实施例9]
与实施例3同样地操作而获得了树脂组合物后，以成型温度120℃、成型压力10MPa、成型时间180秒进行加热加压成型，制作实施例9的成型体，与实施例1同样地进行了评价。将结果示于表1中。
[比较例1]
通过以下方法制造酚醛树脂。
在反应容器中投入了苯酚1000g、47质量％甲醛水溶液880g、和作为催化剂的氢氧化钠10g。然后，一边搅拌一边升温，在回流温度(100℃附近)下反应1小时。
然后，将反应液冷却直到50℃，用对甲苯磺酸中和。将反应液在70mmHg的减压下脱水浓缩，调制不挥发成分为70质量％的液状甲阶型(Resol型)酚醛树脂。
所得的酚醛树脂的数均分子量为240，粘度为300mPa·s(25℃)。
相对于该酚醛树脂100g，加入作为填充材料的碳酸钙100g、作为增稠剂的氧化镁(碘吸附量20mg/g)5g、和硬脂酸锌(脱模剂)3g。然后，将它们用实验用混合机混合，获得了树脂糊料。
接着，在聚乙烯膜上涂布树脂糊料，进一步，在树脂糊料上散布长度约25mm的玻璃短切原丝，制作由聚乙烯膜、树脂糊料和玻璃短切原丝构成的片。
接着，使聚乙烯膜与该片中的包含树脂糊料和玻璃短切原丝的层侧贴合，制作具有聚乙烯膜/树脂糊料和玻璃短切原丝/聚乙烯膜这3层结构的叠层片。
然后，将该叠层片用辊压缩，使树脂糊料含浸在玻璃短切原丝中，并且脱泡而获得了SMC前体。另外，使玻璃短切原丝以在SMC前体(成型材料)中包含30质量％的方式配合。
接着，使该SMC前体在40℃熟化60小时而增稠，获得了粘度为5.6×106mPa·s(40℃)的SMC。
所得的SMC的每单位面积的质量为3.0kg/m2。另外，所谓增稠处理后的粘度，是用B型粘度计测定在与SMC前体的熟化条件相同的条件下进行了处理的树脂糊料的粘度而得的值。
此外，关于所得的SMC，按照上述评价方法，进行了接合性评价和变形评价。在接合性评价和变形评价中，使用了SMC作为树脂构件。将结果示于表2中。
[比较例2]
通过将苯乙烯单体18质量份、苯乙烯单体的含量为30质量％的不饱和聚酯树脂A(商品名：リゴラック(注册商标)M-500D，昭和电工社制)82质量份、聚苯乙烯10质量份、作为固化剂的TBPO 1质量份、作为填充材料的碳酸钙(商品名：KS-1200A，平均粒径1.2μm，同和カルファイン社制)50质量份、氧化镁1质量份和硬脂酸锌2质量份使用双臂型捏合机均匀地混炼，从而获得了比较例2的热固性树脂组合物。
接下来，与实施例1同样地操作，制作比较例2的成型体，进行了评价。将结果示于表2中。
表1
Figure BDA0001566177110000191
表2
Figure BDA0001566177110000201
根据表1、2的结果能够确认，如果将实施例1～9与比较例1、2进行比较，则实施例1～9的热固性树脂组合物的接合性优异。
此外，如果将实施例5与实施例6进行比较，则能够确认：在使用了不饱和聚酯树脂B的情况下，即使固化物的苯乙烯单体的残存量发生变化，接合性也没有差异。
此外，如果将实施例3与实施例8进行比较，则能够确认：固化物的苯乙烯单体的残存量小于0.1质量％时，接合性稍微降低。
此外，如果将实施例3与实施例9进行比较，则能够确认：固化物的苯乙烯单体的残存量超过1质量％时，虽然接合性提高，但固化物发生变形。
产业可利用性
本发明提供，在制作热固性树脂复合材料时，能够将其与金属材料通过摩擦搅拌接合而高效接合的树脂组合物及其固化物、以及摩擦搅拌接合方法。
本发明能够提供机械强度优异，并且温度依赖性小的热固性树脂复合材料，并且提供能够将该复合材料与金属材料通过摩擦搅拌接合而高效接合的树脂组合物及其固化物、使用了上述固化物的摩擦搅拌接合方法。
符号说明
1 构件
2 树脂固化物
3 圆筒状工具
4 突起部
5 压入痕迹。

Claims (8)

1.一种摩擦搅拌接合方法，其包含下述工序：
(i)准备固化物和要与固化物接合的构件的工序，
(ii)使所述固化物与所述构件接触，形成接触部的工序，以及
(iii)使圆筒状的工具一边旋转一边按压于所述构件的至少一部分，通过搅拌和由摩擦产生的摩擦热，将所述固化物与构件接合的工序，
所述固化物是下述树脂组合物的固化物，所述树脂组合物包含：(A)具有烯属不饱和键的单体、(B)不饱和聚酯树脂或乙烯基酯树脂、(C)自由基聚合引发剂、和(D)纤维增强材料。
2.根据权利要求1所述的摩擦搅拌接合方法，所述构件为金属构件。
3.根据权利要求1所述的摩擦搅拌接合方法，其特征在于，所述(D)纤维增强材料为碳纤维。
4.根据权利要求1所述的摩擦搅拌接合方法，其特征在于，在固化物中，以未反应的状态残存的所述(A)具有烯属不饱和键的单体的残存量相对于所述树脂组合物总量为0.1～1质量％。
5.根据权利要求1所述的摩擦搅拌接合方法，其特征在于，在所述树脂组合物中，
(A)具有烯属不饱和键的单体的量相对于(A)具有烯属不饱和键的单体与(B)热固性树脂的合计量为20～80质量％，
(C)自由基聚合引发剂的量相对于(A)具有烯属不饱和键的单体与(B)热固性树脂的合计100质量份为0.1～15质量份，
(D)纤维增强材料的量相对于(A)具有烯属不饱和键的单体与(B)热固性树脂的合计100质量份为5～120质量份。
6.根据权利要求1所述的摩擦搅拌接合方法，所述(D)纤维增强材料为切断成长度25mm以下的纤维。
7.根据权利要求1所述的摩擦搅拌接合方法，所述(D)纤维增强材料为玻璃毡或玻璃布。
8.一种结构物，其是固化物和构件通过权利要求1所述的摩擦搅拌接合方法接合而得的。
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