CN108300340A - 粘合结构体及其制造方法 - Google Patents
粘合结构体及其制造方法 Download PDFInfo
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- CN108300340A CN108300340A CN201711449044.2A CN201711449044A CN108300340A CN 108300340 A CN108300340 A CN 108300340A CN 201711449044 A CN201711449044 A CN 201711449044A CN 108300340 A CN108300340 A CN 108300340A
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Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
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Abstract
本发明提供一种不论是相同材料之间还是异种材料之间均以高粘合强度粘合的粘合结构体及其制造方法。本发明的粘合结构体具备第一固体构件(11)、第二固体构件(12)以及粘合构件(20)。所述第一固体构件(11)和所述第二固体构件(12)通过所述粘合构件(20)而粘合,所述粘合构件(20)含有聚合物,所述聚合物与所述第一固体构件(11)和所述第二固体构件(12)形成化学键。
Description
技术领域
本发明涉及一种粘合结构体及其制造方法。
背景技术
粘合是在以材料工学为首的各个领域中所使用的技术,以提高粘合强度以及耐久性等为目的,广泛进行着粘合技术的研究。最广为所知的粘合技术是通过将粘合剂涂布于材料表面(接合面)并使之固化而使材料彼此粘合的方法。这样的粘合剂通过利用表面的卡挂(固着效果)或范德瓦耳斯力而使材料彼此粘合。此外,近年来,还提出了一种通过化学键而使材料彼此粘合的方法(参照专利文献1等)。
现有技术文献
专利文献
专利文献1:国际公开第2008/149745号
发明内容
本发明要解决的技术问题
然而,在以往的粘合方法中,例如,容易因接合表面的凹凸状态或材料的种类等引起粘合强度的下降,此外,异种材料彼此(例如,金属与树脂)粘合时,存在达不到充分的粘合强度的问题。特别是对于金属与树脂,由于化学性质差异较大,因此两者的亲和性低的情况较多,因而以高粘合强度使金属与树脂粘合为较难的技术。
本发明鉴于上述情况而完成,其目的在于提供一种不论是相同材料之间还是异种材料之间均以高粘合强度粘合的粘合结构体及其制造方法。
解决技术问题的技术手段
本发明的发明人为了达到上述目的而反复进行深入研究,结果发现,在具备固体构件和粘合构件的粘合结构体及其制造方法中,通过由含有聚合物的材料形成粘合构件,并且使粘合构件与固体构件进行化学键合,能够达到上述目的,从而完成了本发明。
即,本发明例如包含以下项中记载的发明。
项1.一种粘合结构体,其具备第一固体构件、第二固体构件以及粘合构件,其中,
所述第一固体构件和所述第二固体构件通过所述粘合构件而粘合,
所述粘合构件含有聚合物,
所述聚合物与所述第一固体构件和所述第二固体构件形成化学键。
项2.根据项1所述的粘合结构体,其中,所述聚合物含有(甲基)丙烯酸类高分子化合物。
项3.根据项1所述的粘合结构体,其中,所述聚合物含有聚轮烷。
项4.根据项1所述的粘合结构体,其中,所述聚合物具有通过主客体相互作用(host-guest interaction)交联而成的结构。
项5.根据项1~4中任意一项所述的粘合结构体,其中,所述第一固体构件和所述第二固体构件为相同或不同的材料,为选自由金属、树脂、玻璃以及无机物组成的组中的一种。
项6.根据项1~5中任意一项所述的粘合结构体,其中,所述第一固体构件和所述第二固体构件中的一者或两者的与所述粘合构件接触的面上设置有等离子体处理部。
项7.一种制造粘合结构体的方法,其为制造具备第一固体构件、第二固体构件以及粘合构件的粘合结构体的方法,其中,
该制造粘合结构体的方法具备下述粘合工序:通过利用聚合性单体的聚合反应而形成含有聚合物的粘合构件,从而使所述第一固体构件和所述第二固体构件通过所述粘合构件而粘合;
所述第一固体构件和所述第二固体构件的表面具有聚合性的反应基团;
所述聚合物与所述反应基团进行化学键合(化学結合する)。
项8.根据项7所述的制造粘合结构体的方法,其中,所述聚合性单体含有聚合反应性的聚轮烷。
项9.根据项7所述的制造粘合结构体的方法,其中,所述聚合性单体含有含主体基团的聚合性单体和含客体基团的聚合性单体。
项10.根据项7~9中任意一项所述的制造粘合结构体的方法,其中,所述第一固体构件和所述第二固体构件为相同或不同的材料,为选自由金属、树脂、玻璃以及无机物组成的组中的一种。
项11.根据项7~10中任意一项所述的制造粘合结构体的方法,其具备:在所述粘合工序前,利用硅烷偶联剂对所述第一固体构件和第二固体构件中的一者或两者进行处理的表面处理工序A。
项12.根据项7~11中任意一项所述的制造粘合结构体的方法,其具备:在所述粘合工序前,对所述第一固体构件和第二固体构件中的一者或两者,进行选自由等离子体照射、臭氧处理、碱处理以及酸处理组成的组中的至少一种以上的处理的表面处理工序B。
项13.根据项7~12中任意一项所述的制造粘合结构体的方法,其中,所述反应基团具有自由基聚合性。
发明效果
本发明的粘合结构体,不论是相同材料之间还是异种材料之间均以高粘合强度粘合。
本发明的粘合结构体的制造方法,能够容易地制造不论是相同材料之间还是异种材料之间均以高粘合强度粘合的粘合结构体,能够得到各种结构的粘合结构体。
附图说明
图1是表示本发明的粘合结构体的实施方式的一个例子的截面的示意图。
图2是说明对固体构件进行等离子体处理的情况的示意图。
图3是说明对固体构件进行硅烷偶联剂处理从而形成硅烷偶联剂层的情况的示意图。
图4是对实施例2-1的粘合工序进行说明的示意图。
图5是对实施例7-1的粘合工序进行说明的示意图。
附图标记说明
11:第一固体构件
12:第二固体构件
20:粘合构件
具体实施方式
以下,对本发明的实施方式进行详细说明。
1.粘合结构体
图1为表示本发明的粘合结构体的实施方式的一个例子并示意性地图示出其截面。
本发明的粘合结构体具备第一固体构件11、第二固体构件12以及粘合构件20。如图1所示,第一固体构件11和第二固体构件12通过粘合构件20而粘合。在该粘合结构体中,第一固体构件11、第二固体构件12均形成为板状,层状的粘合构件20介于两者之间,由此,形成层叠体(粘合结构体)。另外,在以下的说明中,有时将第一固体构件11和第二固体构件12总合仅记作“固体构件”。
本发明的粘合结构体中,第一固体构件11和第二固体构件12通过粘合构件20而粘合,粘合构件20含有聚合物,该聚合物与第一固体构件11和第二固体构件12形成化学键。
固体构件为由固体状的材料形成的构件,其种类没有特别的限定。例如,作为固体构件,可列举出:金属、树脂、玻璃、无机物、纤维、其他材料等。此处所称的无机物是指除金属、树脂(无机高分子等)、玻璃、纤维以及其他材料以外的材料。作为纤维,例如可列举出:芳族聚酰胺、聚乙烯、Zylon(注册商标)等合成纤维;玻璃纤维;碳纤维;硼纤维等。作为其他材料,可列举出:树脂复合材料、木板、纸、粘土矿物、布、皮、陶磁器、陶瓷、瓦(tile)、合成橡胶、骨、齿等。树脂复合材料例如可列举出:有机无机复合材料、利用所述纤维而增强的复合材料、利用填料而增强的复合材料等。
作为所述金属,可例示出:铝、铁、钯、铂、金、银、铜、钛、锌等。金属也可以为含有各种金属元素的合金。此外,金属也可以为不锈钢。
关于所述树脂,可列举出各种树脂,其种类没有限定。作为树脂,可例示出:尼龙6、尼龙66、尼龙610等聚酰胺;聚甲基丙烯酸甲酯、聚丙烯酸甲酯等丙烯酸树脂;聚苯乙烯;聚乙烯、聚丙烯、聚丁二烯等聚烯烃树脂;硅酮树脂;聚氯乙烯;聚偏二氯乙烯;聚对苯二甲酸亚烷基酯;聚酯;聚砜;聚碳酸酯;脲甲醛树脂;苯酚树脂;三聚氰胺树脂;苯胍胺树脂;环氧树脂;三聚氰胺甲醛树脂;聚苯醚;聚缩醛;聚酰亚胺;尿素树脂等。树脂也可以为共聚物。
所述树脂也可以为所述树脂复合材料。即,也可以利用玻璃纤维、碳纤维、填料等添加剂增强所述树脂。此外,所述树脂也可以为弹性体等。
粘合结构体中,第一固体构件和第二固体构件可以彼此相同,或者,也可以彼此不同。特别是在本发明中,通过由特定材料形成粘合构件,并且使粘合构件与固体构件进行化学键合,从而不论第一固体构件和第二固体构件是相同材料还是异种材料,第一固体构件和第二固体构件均以高粘合强度粘合。本说明书中,“粘合结构体的粘合强度”这一记载,是指第一固体构件和第二固体构件的粘合强度。
作为第一固体构件和第二固体构件的优选组合,例如,第一固体构件和第二固体构件相同时,固体构件可列举出金属或树脂。此外,作为第一固体构件和第二固体构件的优选组合,例如,第一固体构件和第二固体构件不同时,可使一者为金属,另一者为树脂。采用这些组合时,容易得到更加优异的粘合强度。
固体构件还可以是复合材料。作为这样的复合材料,例如可列举出:含有金属、树脂、玻璃、木板、纸、无机材料以及粘土矿物等中的两种以上的材料。复合材料可以是各种材料均匀混合的状态,也可以是不均匀混合的状态。复合材料也可以具有层叠结构。复合材料为层叠结构时,固体构件的各层可由相同或不同的材料构成。
固体构件的形状没有特别的限定。例如,固体构件可列举出:基板状、膜状、棒状、块状、球状、椭圆球状、弯曲状、纤维状等。此外,例如,固体构件与粘合构件接触的部分可以为平坦状,或者也可以为非平坦状。作为非平坦状的具体例,例如为凹凸形状、粗糙面形状、波形状。
粘合构件是用于使所述第一固体构件和所述第二固体构件彼此粘合的构件,换而言之,是起到作为粘合剂的功能的构件。
粘合构件含有聚合物。相对于粘合构件的总质量,粘合构件含有50质量%以上、优选含有80质量%以上、更优选含有90质量%以上、特别优选含有99质量%以上的聚合物。此外,粘合构件也可以仅由聚合物形成。
在以下的说明中,将粘合构件中所含的聚合物记作“聚合物A”。
聚合物A的种类没有特别的限定。聚合物A例如可列举出:聚甲基丙烯酸甲酯以及聚丙烯酸甲酯等(甲基)丙烯酸酯类聚合物;丙烯酰胺、N-烷基取代丙烯酰胺等(甲基)丙烯酰胺类聚合物;聚乙烯、聚丙烯、聚丁二烯等聚烯烃树脂;聚苯乙烯;硅酮树脂;聚氯乙烯;聚偏二氯乙烯;聚异丁烯;聚对苯二甲酸亚烷基酯;聚碳酸酯;聚酰胺;苯酚甲醛树脂;三聚氰胺甲醛树脂;苯胍胺甲醛树脂;脲甲醛树脂;苯酚树脂;三聚氰胺树脂;苯胍胺树脂;尿素树脂;环氧树脂;不饱和聚酯树脂;饱和聚酯树脂;聚砜;聚苯醚;聚缩醛;聚酰亚胺;聚酰胺酰亚胺;聚醚醚酮;聚醚砜;以及使一种或两种以上的具有烯属不饱和基团的各种聚合性单体聚合而得到的聚合物等。另外,本说明书中,“(甲基)丙烯酸”是指“丙烯酸或甲基丙烯酸”。即,例如,“(甲基)丙烯酸”的记载,与“丙烯酸或甲基丙烯酸”的记载为相同的意思。
从提高粘合结构体的粘合强度这一点出发,聚合物A优选为交联体。
作为更具体的聚合物A,可列举出:(甲基)丙烯酸类高分子化合物、含有聚轮烷的聚合物、或者具有通过主客体相互作用交联而成的结构的聚合物。在本说明书中,有时将聚合物A为(甲基)丙烯酸类高分子化合物时的粘合结构体记作第一粘合结构体;将聚合物A为含有聚轮烷的聚合物时的粘合结构体记作第二粘合结构体;将聚合物A为具有通过主客体相互作用交联而成的结构的聚合物时的粘合结构体记作第三粘合结构体。
另外,在本说明书中,只要没有特别的明示,“粘合结构体”的记载包括第一粘合结构体、第二粘合结构体、第三粘合结构体的全部。
在第一粘合结构体中,粘合构件中所含的聚合物A为(甲基)丙烯酸类高分子化合物。作为(甲基)丙烯酸类高分子化合物,可列举出上述的(甲基)丙烯酸酯类聚合物、(甲基)丙烯酰胺类聚合物等。
作为(甲基)丙烯酸类高分子化合物的更具体的例子,可列举出:(甲基)丙烯酰胺的聚合物、(甲基)丙烯酰胺衍生物的聚合物、(甲基)丙烯酸-2-羟基乙酯的聚合物、N,N-二甲基(甲基)丙烯酰胺的聚合物、N,N-二甲氧基聚乙二醇(甲基)丙烯酸酯(乙二醇单元例如为1~20、优选为1~10)的聚合物。
从更加提高粘合强度的角度出发,(甲基)丙烯酸类高分子化合物优选具有交联结构、即优选为交联体。交联结构是指例如具有支链结构的聚合物、或者具有三维网状结构的聚合物等。例如,(甲基)丙烯酸类高分子化合物可以具有利用公知的交联剂交联而成的结构。
第二粘合结构体中,可将粘合构件中所含的聚合物A设为含有聚轮烷的聚合物。
聚轮烷为具有以下结构的高分子化合物:直链状分子贯通环状分子的开口部、并且在所述直链状分子的两末端键合有用于防止所述环状分子脱落的封端基团。第二粘合结构体中的粘合构件可以含有公知的聚轮烷。
作为所述直链状分子,可列举出能够贯通多个环状分子的环内的分子。作为直链状分子,可列举出聚烯烃;聚酯;聚醚;聚酰胺;聚丙烯酸;聚硅氧烷;氟聚醚、全氟聚合物等具有氟基的高分子;具有苯环的高分子等。进一步,作为具体的直链状分子,例如可列举出:聚乙二醇、聚环氧乙烷、聚丙二醇、聚己内酯、聚乙烯、聚丙烯、聚乙烯醇缩醛、聚乙烯基甲基醚、聚乙烯吡咯烷酮、聚丙烯酰胺、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚苯乙烯等。只要是以能够贯通上述环状分子的环内的方式构成,则直链状分子也可以具有支链。
直链状分子的重均分子量Mw虽没有特别的限制,但例如可以为3000~500000。此时,易于确保第二粘合结构体的粘合强度。另外,本说明书中所述的重均分子量为利用凝胶渗透色谱(GPC)测定的换算成聚乙二醇的值。
作为封端基团,例如可列举出:金刚烷基、二硝基苯基类、环糊精类、N-苄氧羰基-L-酪氨酸类(Z-L-酪氨酸类)、三苯甲基、芘基、苯基等芳基;2-丁基癸基、荧光黄类、芘类以及它们的衍生物或改性体。上述例示列举的封端基团也可以具有取代基。这样的封端基团例如可以经由酰胺键、酯键等直接或间接地与直链状分子的两末端键合。
作为环状分子,例如可列举出:环糊精、环糊精衍生物、环状低聚物等。环糊精可以为α-环糊精、β-环糊精以及γ-环糊精中的任意一种。环糊精衍生物例如可以具有环糊精的至少一个以上羟基的氢原子被其他取代基取代而成的结构。作为取代基,可列举出各种有机基团。作为有机基团,可列举出:可具有碳原子数为1以上的取代基的烃基、含有C=O键的基团等。
作为可具有碳原子数为1以上的取代基的烃基,可为直链状、支链状中的任意一种。烃基的碳原子数例如可以为1~12、优选为1~6。可具有碳原子数为1以上的取代基的烃基,可以为具有羟基的烃基或具有氨基的烃基。作为具有羟基的烃基的具体例子,可列举出羟甲基、羟乙基、羟丙基等。作为具有氨基的烃基的具体例子,可列举出氨基甲基、氨基乙基、氨基丙基等。
作为含有C=O键的基团,例如可列举出:酰基(例如乙酰基)、酯基、醛基、酮、酰胺基、氨基甲酰基、脲基等。
作为环状分子具有所述取代基时的具体方式,例如可列举出:环糊精或其衍生物所具有的羟基的氢原子被所述取代基取代而成的结构。
环状分子具有所述取代基时,由于与后述的聚合物B的亲和性容易变高,因此,在粘合构件中,聚轮烷容易均匀分散。由此,粘合构件容易发挥出聚轮烷所具有的功能,粘合性能容易提高。
环状分子与所述直链状分子形成为串状而存在于聚轮烷中。与直链状分子形成为串状的环状分子的个数、即一个直链状分子所贯通的环状分子的个数(也称为包合量)虽没有特别的限制,但若环状分子为环糊精,则将其最大包合量设为1时,可使包合量为0.15~0.4。
聚轮烷的重均分子量Mw虽没有特别的限定,但例如可以为15000~1000000,优选为20000~500000。
第二粘合结构体的粘合构件中所含的聚合物A,可以仅由聚轮烷形成,除聚轮烷以外,也可以含有其他聚合物(以下,简称为“聚合物B”)。
聚合物B可以与聚轮烷物理混合,也可以与聚轮烷进行化学键合。例如,聚合物B也可以直接或间接地与聚轮烷的环状分子键合。聚合物B与聚轮烷的环状分子进行化学键合时,能够形成通过聚合物B而使环状分子彼此交联而成的交联结构体。即,聚合物A能够成为具有聚轮烷骨架的交联结构体。
聚合物B例如可列举出:聚甲基丙烯酸甲酯以及聚丙烯酸甲酯等(甲基)丙烯酸酯类聚合物;丙烯酰胺、N-烷基取代丙烯酰胺等(甲基)丙烯酰胺类聚合物;聚乙烯、聚丙烯、聚丁二烯等聚烯烃树脂;具有氟基的高分子;聚苯乙烯;硅酮树脂;聚氯乙烯;聚偏二氯乙烯;聚异丁烯;聚对苯二甲酸亚烷基酯;聚碳酸酯;聚酰胺;苯酚甲醛树脂;三聚氰胺甲醛树脂;苯胍胺甲醛树脂;脲甲醛树脂;苯酚树脂;三聚氰胺树脂;苯胍胺树脂;尿素树脂;环氧树脂;不饱和聚酯树脂;饱和聚酯树脂;聚砜;聚苯醚;聚缩醛;聚酰亚胺;聚酰胺酰亚胺;聚醚醚酮;聚醚砜;以及使一种或两种以上的具有烯属不饱和基团的各种聚合性单体聚合而得到的聚合物等。
从容易制造的角度出发,聚合物B优选为(甲基)丙烯酸酯类聚合物、(甲基)丙烯酰胺类聚合物。作为(甲基)丙烯酸酯类聚合物,可列举出(甲基)丙烯酸的聚合物、(甲基)丙烯酸甲酯的聚合物、(甲基)丙烯酸乙酯的聚合物、(甲基)丙烯酸丙酯的聚合物、(甲基)丙烯酸-2-羟基乙酯的聚合物、(甲基)丙烯酸-2-羟基丙酯的聚合物等。作为(甲基)丙烯酰胺类聚合物,可列举出(甲基)丙烯酰胺的聚合物、N,N-二甲基丙烯酰胺的聚合物、N,N-二甲基氨基丙基丙烯酰胺的聚合物。特别是聚合物B为(甲基)丙烯酰胺的聚合物时,容易发挥出后述的聚轮烷的效果。聚合物B与第一粘合结构体的聚合物A相同,也可以为(甲基)丙烯酸类高分子化合物。
聚合物B可以为由一种重复结构单元构成的均聚物,也可以为由两种以上的重复结构单元构成的共聚物。聚合物B为共聚物时,可以为无规共聚物、嵌段共聚物、交替共聚物等中的任意一种结构。
聚合物B可以为非交联性结构和交联结构中的任意一种。聚合物B具有交联结构时,例如可以具有利用公知的交联剂交联而成的结构。
聚合物A中的聚轮烷的含量没有特别的限定。例如,相对于聚合物A的总量,可以使聚轮烷的含量为1×10-7~50mol/kg、优选为1×10-5~20mol/kg、特别优选为1×10-4~5mol/kg。
第三粘合结构体中,粘合构件中所含的聚合物A含有通过主客体相互作用交联而成的聚合物。
通过主客体相互作用交联而成的聚合物可以指,例如,含有构成聚合物的具有主链和作为侧链的主体基团和客体基团的分子、且这些主体基团和客体基团与其他分子的客体基团和主体基团进行主客体相互作用而成的交联聚合物。因此,该交联结构体能够以主客体相互作用为交联点而形成为三维网状结构。
主客体相互作用,例如,虽可以通过主体分子与客体分子的疏水性相互作用、氢键、分子间力、静电相互作用、配位键、π电子相互作用等而产生,但并不限定于此。
主体基团为通过主体分子而形成的基团。主体基团例如为通过从主体分子中去除1个原子(例如氢)而形成的基团。
作为主体分子,可例示出:选自α-环糊精、β-环糊精、γ-环糊精、杯[6]芳烃磺酸、杯[8]芳烃磺酸、12-冠-4、18-冠-6、[6]对环芳烷([6]paracyclophane)、[2,2]对环芳烷([2,2]paracyclophane)、葫芦[6]脲以及葫芦[8]脲的组中的至少一种。主体分子也可以进一步具有取代基。作为取代基,例如可列举出:卤素原子(例如氟、氯、溴等)、羧基、酯基、酰胺基、可以被保护的羟基等。
客体基团为通过客体分子而形成的基团。客体基团例如为通过从客体分子中去除1个原子(例如氢)而形成的基团。
作为客体基团,可列举出:碳原子数为1~30的直链或支链状的烃基、环烷基、芳基、杂芳基以及有机金属络合物等,它们也可以具有一个以上的取代基。作为更具体的客体基团,可列举出:碳原子数为4~18的链状或环状的烷基。环状的烷基可以为笼型的结构。作为取代基,例如可列举出:卤素原子(例如氟、氯、溴等)、羧基、酯基、酰胺基、可以被保护的羟基等。
除此之外,客体基团例如也可以为由以下所例示的客体分子形成的基团:选自醇衍生物、芳基化合物、羧酸衍生物、氨基衍生物、具有环状烷基或苯基的偶氮苯衍生物、肉桂酸衍生物、芳香族化合物及其醇衍生物、胺衍生物、二茂铁衍生物、偶氮苯、萘衍生物、蒽衍生物、芘衍生物、苝衍生物、富勒烯等的由碳原子构成的簇类、丹酰化合物的组中的至少一种。
作为主体基团,优选为来自选自α-环糊精、β-环糊精以及γ-环糊精的组中的至少一种分子或它们中的任意一者的衍生物的基团。
作为客体基团,优选为选自正丁基、正十二烷基、叔丁基以及金刚烷基的组中的至少一种。
作为主体基团与客体基团的组合,可例示出α-环糊精与正十二烷基、β-环糊精与金刚烷基。在为这些组合的情况下,容易起到稳定的主客体相互作用,特别是容易发挥出后述的自修复性能。
通过主客体相互作用交联而成的聚合物,只要具有能进行主客体相互作用的主体基团和客体基团,其种类就没有特别的限定。
例如,通过主客体相互作用交联而成的聚合物,可以由侧链上具有主体基团和客体基团的高分子链形成。这样的高分子链没有特别的限定。例如,可以将国际公开第2016/163550号中公开的用于构成自修复材料的聚合物适用作用于形成通过主客体相互作用交联而成的聚合物的高分子链。此外,通过主客体相互作用交联而成的聚合物,也可以为具有来自后述的通式(1)和通式(2)所表示的单体的结构单元的聚合物。
例如,通过主客体相互作用交联而成的聚合物,可例示出以下的高分子链:该高分子链的主链为(甲基)丙烯酰胺类骨架、(甲基)丙烯酸酯类骨架等,且其侧链上具有主体基团和客体基团。高分子链的主链具有(甲基)丙烯酰胺类骨架时,主体基团和客体基团能够直接或间接地与酰胺基的氮原子键合(酰胺的氢原子被主体基团或客体基团取代)。此外,若高分子链的主链为(甲基)丙烯酸酯类骨架,则主体基团和客体基团能够直接或间接地与酯基的氧原子键合(羧酸的氢原子被主体基团或客体基团取代)。
此外,侧链上具有主体基团和客体基团的高分子链,也可以含有不具有主体基团和客体基团这两者的结构单元(以下,称为“第三结构单元”)。由于含有第三结构单元时,进行主客体相互作用时的位阻等降低,因此,容易进行主客体相互作用。此外,只要为不阻碍主客体相互作用的程度,则高分子链也可以在主链和侧链上具有各种取代基,此外,还优选具有更加促进主客体相互作用的取代基。
第三结构单元例如可列举出:来自(甲基)丙烯酰胺及其衍生物、以及(甲基)丙烯酸和(甲基)丙烯酸酯的单元。作为(甲基)丙烯酰胺衍生物,可列举出:N,N-二甲基丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺,作为(甲基)丙烯酸酯,可列举出:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-2-羟基丙酯等。特别是第三结构单元为来自(甲基)丙烯酰胺的单元时,容易发挥出后述的通过主客体相互作用交联而成的聚合物的效果,容易具有优异的自修复性。此外,第三结构单元若为来自(甲基)丙烯酰胺和(甲基)丙烯酸酯的单元,则粘合结构体容易具有高粘合力。此时的(甲基)丙烯酸酯,例如可列举出(甲基)丙烯酸-2-羟基乙酯。在(甲基)丙烯酰胺和(甲基)丙烯酸酯的共聚物中,两者的结构单元的摩尔比可以为1:99~99:1,以20:80~80:20、40:60~60:40的顺序优选。
侧链上具有主体基团和客体基团的高分子链中,从容易进行主客体相互作用的角度出发,优选在一个高分子链上分别具有多个主体基团和客体基团。
侧链上具有主体基团和客体基团的高分子链,例如可以无规地排列、或者以嵌段状或规则地(例如交替地)排列有:侧链上具有主体基团的结构单元和侧链上具有客体基团的结构单元。从容易进行主客体相互作用、制造也容易的角度出发,优选无规地排列有:侧链上具有主体基团的结构单元和侧链上具有客体基团的结构单元。
侧链上具有主体基团和客体基团的高分子链中,该高分子链的全部结构单元中所含的、具有主体基团的结构单元和具有客体基团的结构单元的比例,各自可以为1~20摩尔%,优选为1~5摩尔%,更优选为2~4摩尔%。另外,剩余部分例如可以为所述第三结构单元。
若存在多个具有所述结构的高分子链,则某一高分子侧链的主体基团与其他高分子侧链的客体基团进行相互作用,由主体基团和客体基团形成包合化合物。该包合化合物成为交联点且高分子链彼此交联,从而能够形成通过主客体相互作用交联而成的聚合物。另外,主体基团与客体基团之间的相互作用,有时也能够在同一分子中进行。
侧链上具有主体基团和客体基团的高分子链还可以为其他种类,例如,也可以为以上述的聚合物B为骨架、且在这样的聚合物的侧链上具有主体基团和客体基团的结构。
作为通过主客体相互作用交联而成的聚合物的其他例子,例如可列举出:通过具有主体基团但不具有客体基团的高分子链与具有客体基团但不具有主体基团的高分子链之间的主客体相互作用而形成的交联聚合物。
粘合结构体中,只要为不妨碍本发明的效果的程度,则粘合构件也可以含有除聚合物以外的材料。作为这样的材料,例如可列举出公知的添加剂,具体而言,可列举出滑石、碳酸钙等填充剂。除此之外,作为添加剂,可列举出:着色剂、抗氧化剂、热稳定剂、光稳定剂、紫外线吸收剂、润滑剂、抗静电剂以及阻燃剂、固化促进剂、防腐剂等。
粘合构件的厚度没有特别的限定。例如,如图1的方式所示,粘合结构体为层叠体时,粘合构件的厚度可以为0.001~1000μm。在本发明的粘合结构体中,粘合构件中所含的聚合物通过与第一固体构件和第二固体构件形成化学键,即使粘合构件的厚度薄,也能够较强地粘合固体构件,优选还能够表现出固体构件间的自修复性(即再粘合性)。此外,由于即使粘合构件的厚度薄,也能够较强地粘合固体构件,因此,还能够强化粘合结构体的韧性。粘合构件的厚度优选为1~500μm,特别优选为5~200μm。
粘合结构体中,粘合构件与第一固体构件和第二固体构件这两者形成化学键。由此,第一固体构件和第二固体构件彼此被较强地粘合,从而发挥出本发明的效果。
具体而言,通过使粘合构件中所含的聚合物A与固体构件进行化学键合,能够形成所述化学键。
例如,在所述第一粘合结构体中,(甲基)丙烯酸类高分子化合物能够与固体构件的粘合面(粘合部)进行化学键合。在后述的粘合结构体的制造阶段中,能够在形成粘合构件的同时形成该化学键。
此外,第二粘合结构体中,粘合构件中所含的具有聚轮烷的聚合物能够与固体构件的粘合面进行化学键合。该情况下,可以是聚轮烷自身与固体构件的粘合面进行化学键合,也可以是聚合物B的侧链或末端与固体构件的粘合面进行化学键合。在后述的粘合结构体的制造阶段中,能够在形成粘合构件的同时形成这些化学键。
此外,在第三粘合结构体中,粘合构件中所含的通过主客体相互作用交联而成的聚合物,能够与固体构件的粘合面进行化学键合。在后述的粘合结构体的制造阶段中,能够在形成粘合构件的同时形成该化学键。
粘合结构体中,由于固体构件与粘合构件进行化学键合,因此不论第一固体构件与第二固体构件是相同材料还是异种材料,第一固体构件与第二固体构件均以高粘合强度粘合。特别是所述化学键的存在,能够提高固体构件与粘合构件的界面的粘合性。
通常由于金属与高分子类粘合剂的亲和性差,且根据金属的种类而具有钝化膜,因此,即使利用高分子类粘合剂粘合金属,也难以得到高粘合力,但是,在本发明中,通过所述化学键,即使固体构件为金属,也能够得到高粘合力。
此外,由于金属等的固体构件与以往的高分子类粘合剂的线膨胀系数不同的情况较多,因此,若利用高分子类粘合剂使金属粘合后材料温度上升,则两者的粘合强度下降,从而容易引起剥离。为了解决该问题,还可以考虑适当地使用热熔胶,但该情况下若材料温度下降,则由于金属等的固体构件与高分子类粘合剂的收缩度的差而产生粘合界面的断裂。相对于此,具有本发明的结构的粘合结构体,即使固体构件与粘合构件的线膨胀系数不同,由于所述化学键的存在,即使材料温度变化,也不易引起粘合界面的断裂,从而容易维持高粘合强度。
因此,粘合结构体适合于各个领域,例如适合用作用于构成汽车、飞机、船舶、铁路、鞋、太阳能电池、空调设备、电子设备、建筑构件、牙科材料(例如金属与齿的粘合)等的构件,可以使用于各个用途。
第二粘合结构体中的粘合构件中所含的聚轮烷,由于通过使环状分子沿着直链状分子自由滑动而具有优异的柔软性,因此,第二粘合结构体除了粘合强度优异以外,特别是韧性和延伸性也优异。此外,第二粘合结构体通过含有聚轮烷,从而利用环状分子的可动性来实现应力分散,不使应力局部集中于粘合构件的一部分。由此,还能够期待断裂能的提高。
第三粘合结构体中,由于粘合构件含有通过主客体相互作用交联而成的聚合物,因此,第三粘合结构体除了粘合强度优异以外,特别是再粘合后的粘合强度也优异。即,在第三粘合结构体中,以某些方法使第一固体构件和第二固体构件分离而使粘合构件断裂后,通过再次重合,能够进行再粘合。并且,再粘合后的粘合力与初期相比不易下降。这是由于粘合构件含有通过具有可逆性质的主客体相互作用交联而成的聚合物,即使粘合构件断裂,再粘合断裂面间时在断裂界面之间产生主客体相互作用的原因。其结果,再粘合后粘合结构体也具有高粘合力,此外,可以期待带来断裂能的提高。例如,若与通过以往的粘合构件粘合而成的粘合体相比,第三粘合结构体的再粘合后的粘合力的下降率变得极低,所述以往的粘合构件中不含通过主客体相互作用交联而成的聚合物。
此外,第三粘合结构体通过形成显示键合可逆性的主客体相互作用,从而实现应力分散,不使应力局部集中于粘合构件的一部分。
已断裂的粘合构件的再粘合的方法没有特别的限定。例如,通过使断裂后的粘合构件的断裂面彼此接触的再粘合方法,能够使已断裂的粘合构件再粘合。或者,通过在断裂后的粘合构件的断裂面上涂布水后使断裂面彼此接触的再粘合方法,能够使已断裂的粘合构件再粘合。在该方法中,根据需要,也可以将断裂面彼此接触后,使之干燥。
在本发明的粘合结构体中,若使用预先通过表面处理等方法而形成有反应基团的固体构件,则能够形成粘合强度更优异的粘合结构体。这是由于更容易形成固体构件与粘合构件的化学键、且化学键的数量也增加。在固体构件表面上形成反应基团的方法如后所述。
本发明的粘合结构体中,优选在固体构件与粘合构件接触的面上设置有等离子体处理部。该情况下,特别容易形成固体构件与粘合构件的化学键,其结果,容易形成粘合强度优异的粘合结构体。
在此,等离子体处理部是指,通过后述表面处理工序B等对固体构件进行了等离子体处理的部分。等离子体处理部与未形成等离子体处理部的部分相比,能够形成更多的能够形成固体构件与粘合构件的化学键的部位。此外,等离子体处理部与未形成等离子体处理部的部分相比,固体构件与粘合构件的亲和性能够变得更高。其结果,特别容易形成固体构件与粘合构件的化学键。
作为等离子体处理部与未形成等离子体处理部的部分相比,特别容易进行固体构件与粘合构件的化学键合的理由之一,可以认为其起因于,表面的亲水性、表面张力、表面的构成原子数等在等离子体处理部中发生变化。例如,等离子体处理部与未形成等离子体处理部的部分相比,氧原子的比例多。因此,关于固体构件是否具有等离子体处理部,可以通过分析固体构件的亲水性、表面张力、表面的构成原子数等来判断。表面的构成原子数例如可以由XPS测定而测量。
2.粘合结构体的制造方法
具备所述的第一固体构件、第二固体构件以及粘合构件的粘合结构体的制造方法没有特别的限定。
例如,粘合结构体能够通过以下方法制造:分别准备表面具有聚合性的反应基团的一对固体构件(第一固体构件和所述第二固体构件),并使它们通过粘合构件而粘合。更具体而言,通过具备下述的粘合工序的方法,可以制造粘合结构体。
粘合工序:通过利用聚合性单体的聚合反应而形成含有聚合物的粘合构件,从而使所述第一固体构件和所述第二固体构件通过所述粘合构件粘合。
在此,粘合工序中使用的所述第一固体构件和所述第二固体构件的表面具有聚合性的反应基团,所述聚合物与所述反应基团进行化学键合。以下,对具备该粘合工序的制造方法进行详细描述。
构成固体构件的材料、形状等,如上述的<1.粘合结构体>的项中所说明。例如,构成固体构件的材料,可以为选自由金属、树脂、玻璃以及无机物组成的组中的一种。第一固体构件和第二固体构件可以相同,也可以不同。
粘合工序中使用的固体构件的表面具有聚合性的反应基团。
在此,作为聚合性的反应基团,除烯基(alkenyl group)、乙烯基等以外,可列举出-OH、-SH、-NH2、-COOH、-SO3H、-PO4H、异氰酸酯基、缩水甘油基等。它们也可以进一步具有一个以上的取代基。此处所称的聚合性是指,例如具有自由基聚合、离子聚合、聚缩合(缩合聚合、缩聚)、加成缩合、活性聚合、活性自由基聚合等聚合反应性、及除此以外的以往以来已知的各种聚合反应性。
聚合性的反应基团优选具有自由基聚合性。该情况下,所得到的聚合物与固体构件的反应基团容易形成化学键,容易得到粘合强度优异的粘合结构体。
具有自由基聚合性的官能团,可列举出含有碳-碳双键的基团,具体而言,可列举出:丙烯酰基(CH2=CH(CO))、甲基丙烯酰基(CH2=CCH3(CO))以及除此以外的苯乙烯基、乙烯基、烯丙基等。只要为不妨碍自由基聚合性的程度,则这些含碳-碳双键的基团也可以进一步具有取代基。
表面具有聚合性的反应基团的固体构件的制造方法,没有特别的限定。例如,由于根据固体构件的种类,有时固体构件自身具有聚合性的反应基团,因此,该情况下,可以将该固体构件直接用作本发明的粘合结构体用的构件。另外,在本发明中,作为表面具有聚合性的反应基团的固体构件,也可以使用市售品。
或者,表面具有聚合性的反应基团的固体构件例如也可以通过对固体构件另外进行表面处理而得到。作为这样的表面处理,例如可以列举出以下的表面处理工序A。
表面处理工序A:在所述粘合工序前,利用硅烷偶联剂对所述第一固体构件和所述第二固体构件中的一者或两者进行处理的工序。
在所述表面处理工序A中,通过利用硅烷偶联剂对所述第一固体构件和所述第二固体构件中的一者或两者进行表面处理,能够在其表面上导入聚合性的反应基团。
硅烷偶联剂的种类没有特别的限定。例如,可以使用公知的硅烷偶联剂进行表面处理。通过选择规定的硅烷偶联剂的种类,例如,能够将所述各种聚合性的反应基团导入固体构件的表面。例如,使用具有乙烯基或丙烯酰基的硅烷偶联剂时,能够在固体构件的表面上导入乙烯基或丙烯酰基。除此之外,可以通过硅烷偶联剂的选择,将-OH、-NH2、-COOH、缩水甘油基等各种聚合性的反应基团导入固体构件上。
作为硅烷偶联剂,例如可以列举出:硅原子上键合有乙烯基或(甲基)丙烯酰基的三甲氧基硅烷;硅原子上键合有乙烯基或(甲基)丙烯酰基的三乙氧基硅烷等。利用这些硅烷偶联剂进行了处理的固体构件,能够在表面上导入自由基聚合性的反应基团。
关于固体构件的表面上是否导入有自由基聚合性的反应基团,例如,可以通过使用了接触角测定、XPS、IR、荧光X射线、ICP发光分析、TOF-SIMS等的分析来进行判断。例如,由于若在固体构件的表面上导入有自由基聚合性的反应基团则接触角发生变化,因此能够通过接触角测定确认到向固体构件的表面的自由基聚合性的反应基团的导入。此外,由于若在固体构件的表面上导入有自由基聚合性的反应基团,则能够确认到来自Si的XPS峰,因此,能够通过XPS确认到向固体构件的表面的自由基聚合性的反应基团的导入。
可以将基于硅烷偶联剂的表面处理的条件设定为,例如与公知的硅烷偶联剂处理的条件相同。
本发明中,也可以利用除表面处理工序A以外的方法,向固体构件表面导入聚合性的反应基团。例如,可列举出以下方法:使存在于固体构件的表面的OH基、SH基、COOH基等官能团与具有与它们反应的取代基以及聚合基团的化合物反应。除此之外,也可以使用阿仑膦酸等具有磷酸基的化合物向固体构件表面导入聚合性的反应基团。
至少可以对固体构件的进行粘合的部分的全部或一部分实施基于硅烷偶联剂进行的表面处理,也可以对除粘合部分以外的全部或一部分实施基于硅烷偶联剂进行的表面处理。例如,若固体构件为基板状等形状,则可以利用硅烷偶联剂对固体构件的进行粘合的面的整个面或一部分进行处理。
表面处理工序A中,可以对第一固体构件和第二固体构件中的一者或两者进行硅烷偶联剂处理,但从粘合构件与第一固体构件和第二固体构件更容易形成化学键的角度出发,优选对第一固体构件和第二固体构件这两者进行硅烷偶联剂处理。第一固体构件和第二固体构件这两者为树脂时,即使无硅烷偶联剂处理(即,即使不具备表面处理工序A),也能够实现强粘合。换言之,第一固体构件和第二固体构件这两者不是树脂时,粘合结构体的制造方法优选具备表面处理工序A。
固体构件也可以实施除所述表面处理工序A中的处理(硅烷偶联剂处理)以外的处理。作为这样的表面处理,例如可列举出以下的表面处理工序B。
表面处理工序B:在粘合工序前,对第一固体构件和第二固体构件中的一者或两者进行选自由等离子体照射、臭氧处理、碱处理以及酸处理组成的组中的至少一种以上的处理的工序。
表面处理工序B为粘合固体构件彼此之前,用于进行固体构件的表面处理以使固体构件的表面状态活化的工序。
基于等离子体照射的处理,可以通过在规定条件下对固体构件照射等离子体而进行。由此,在固体构件上形成等离子体处理部。
等离子体的种类可列举出:微波等离子体、等离子体流、电感耦合型等离子体、电子回旋共振等离子体等各种高密度等离子体,也可以例示出:氧等离子体、氮等离子体、氩等离子体等。
照射等离子体的方法没有特别的限定,例如,可以使用公知的等离子体照射装置进行。照射等离子体时,可以一边使喷嘴转动一边照射,也可以通过定点喷涂来照射等离子体。也可以适当设定输出功率以及照射时间等的等离子体照射条件。
对固体构件的等离子体照射,例如可以在大气压下、氮气氛下、氮和氢的混合气体气氛下的各种气氛下进行。在氮和氢的混合气体气氛下进行时,从安全性等的角度出发,适当设定氮与氢的混合比例即可,例如可以设为氮为100~97vol%和氢为0~3vol%的混合比例。在氮气氛下、氮和氢的气氛下进行等离子体照射时,例如,将固体构件收纳在玻璃等容器内,利用规定的气体对玻璃容器内部进行驱气后,进行等离子体照射即可。
通过适当变更等离子体照射条件,可以使固体构件的表面状态发生变化。例如,根据气氛中存在的气体的种类、固体构件的种类、等离子体照射时间、等离子体照射条件(使喷嘴转动、或定点喷涂),可以使固体构件的表面状态(例如表面的亲水性)发生变化。例如在等离子体照射前后的XPS测定中,来自碳原子的峰强度能够减少,来自氧原子的峰强度能够增大。进一步,在氮气氛下进行等离子体照射时,来自氮原子的峰强度能够增大。
臭氧处理的方法没有特别的限定,可以采用公知的臭氧处理的方法。例如,可以通过将固体构件静置于市售的臭氧清洁器内并在氧气氛下照射紫外线的方法进行臭氧处理。若固体构件经过臭氧处理,则固体构件的经臭氧处理的部分的氧原子的比例变大,此外,亲水性能够得以提高。
碱处理的方法没有特别的限定,可以采用公知的碱处理的方法。例如,可以通过使固体构件在溶解有碱的液体中浸渍规定时间的方法进行碱处理。碱的种类没有限定,例如可以列举出:氢氧化钠、氢氧化钾、碳酸氢钠、氨等。使碱溶解的溶剂,例如可列举出:水、低级醇、水和醇的混合溶剂。若固体构件经过碱处理,则固体构件的经碱处理的部分的亲水性能够得以提高。
酸处理的方法没有特别的限定,可以采用公知的酸处理的方法。例如,可以通过使固体构件在溶解有酸的液体中浸渍规定时间的方法进行酸处理。酸的种类没有限定,例如可列举出:盐酸、硝酸、硫酸等无机酸;乙酸、柠檬酸等有机酸等。也可以使使酸溶解的溶剂与所述使碱溶解的溶剂相同。若固体构件经过酸处理,则固体构件的经酸处理的部分的亲水性能够得以提高。
在表面处理工序B中,可以仅进行等离子体照射、臭氧处理、碱处理、酸处理中的任意一种处理,也可以组合两种以上的处理。从充分发挥出各表面处理的效果和简化制造工序的点出发,在表面处理工序B中,优选仅进行一种表面处理。其中,从粘合力容易增高的角度出发,在表面处理工序B中,优选进行等离子体处理。
表面处理工序B中,可以处理第一固体构件和第二固体构件中的一者或两者,但从粘合构件与第一固体构件和第二固体构件的粘合力更容易增高的角度出发,优选处理第一固体构件和第二固体构件这两者。另外,通过表面处理工序B对第一固体构件和第二固体构件这两者进行表面处理时,两者均可以进行同种的表面处理,也可以进行不同种类的表面处理。
表面处理工序A和表面处理工序B均在粘合工序前进行。表面处理工序A和表面处理工序B的顺序虽没有特别的限定,但优选在表面处理工序B后进行表面处理工序A。即,优选在表面处理工序B后进行硅烷偶联剂处理。该情况下,粘合构件与固体构件容易形成化学键,能够确保优异的粘合强度。
另外,在本发明的粘合结构体中,也可以使用预先进行了表面处理工序A和/或表面处理工序B的处理的市售的固体构件。
粘合构件在粘合工序中可以通过聚合性单体的聚合反应而形成。所形成的粘合构件含有通过聚合性单体的聚合反应而形成的聚合物。在此所形成的聚合物例如为所述聚合物A。
聚合性单体的种类没有特别的限定。例如可以列举出:能够进行聚合而形成所述聚合物A的聚合性单体。
聚合性单体优选为能够进行自由基聚合的化合物,该情况下,由于能够在简化的条件下形成聚合物,因此,能够容易地形成粘合构件,此外,容易形成粘合力高的粘合构件。
聚合性单体为能够进行自由基聚合的化合物时,其种类没有特别限定,例如可列举出:公知的各种乙烯基类单体。更具体而言,可列举出:(甲基)丙烯酸、(甲基)丙烯酰胺、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸-2-羟基甲酯、(甲基)丙烯酸-2-羟基乙酯等(甲基)丙烯酸酯;N,N-二甲基(甲基)丙烯酰胺、N,N-二甲基氨基丙基(甲基)丙烯酰胺、N-异丙基(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-羟乙基(甲基)丙烯酰胺、1-丙烯酰胺金刚烷(1-アクリルアミドアダマンタン)等(甲基)丙烯酰胺衍生物;N,N-二甲氧基聚乙二醇(甲基)丙烯酸酯(乙二醇单元例如为1~20、优选为1~10);氯乙烯;乙酸乙烯酯;苯乙烯等。它们可以使用一种或两种以上。
聚合性单体也可以含有二官能等多官能聚合性单体,即也可以含有交联剂。作为交联剂,例如可列举出:N,N-亚甲基双丙烯酰胺、(聚)乙二醇二(甲基)丙烯酸酯等、二乙烯基苯等公知的化合物。它们可以使用一种或两种以上。二官能等多官能聚合性单体,例如,相对于全部的聚合性单体,可以为0.1~20mol%。
作为用于形成所述第一粘合结构体的粘合构件的聚合性单体,可列举出:(甲基)丙烯酸、(甲基)丙烯酸酯、(甲基)丙烯酰胺、(甲基)丙烯酰胺衍生物等。该情况下,所得到的聚合物能够成为(甲基)丙烯酸类高分子化合物。作为此时的聚合性单体的具体例,可列举出:(甲基)丙烯酸、(甲基)丙烯酰胺、(甲基)丙烯酸-2-羟基乙酯、N,N-二甲氧基聚乙二醇(甲基)丙烯酸酯(乙二醇单元例如为1~20、优选为1~10)、N,N-二甲基(甲基)丙烯酰胺等。它们可以使用一种或两种以上。
作为用于形成所述第二粘合结构体的粘合构件的聚合性单体,可列举出:含有聚轮烷的聚合性单体。聚轮烷例如可以使用市售的产品,也可以另外进行合成而使用。用于制造所述第二粘合结构体的聚合性单体,与所述例示列举出的聚合性单体相同,特别优选为能够进行自由基聚合的聚合性单体。
用于制造所述第二粘合结构体的粘合构件的聚合性单体,优选含有聚合反应性的聚轮烷。该情况下,由于通过聚合而形成的聚合物成为导入有聚轮烷骨架的共聚物,因此,除了粘合强度优异以外,特别是能够形成韧性和延伸性也优异的粘合结构体。聚合性单体可以仅由聚合反应性的聚轮烷形成,也可以含有其他的聚合性单体。
聚合反应性的聚轮烷,例如可以具有环状分子上键合有聚合性官能团的结构。聚合性官能团与上述的固体构件所具有的聚合性的反应基团同义。因此,聚合性官能团优选为自由基聚合性。
聚合反应性的聚轮烷优选每一分子具有两个以上的聚合性官能团。该情况下,由于所得到的聚合物具有由聚轮烷交联而成的结构,因此,粘合构件的柔软性得以提高,特别是容易形成韧性和延伸性也优异的粘合结构体。
聚轮烷(包括聚合性聚轮烷)可以适用市售的产品,若列举出具体例,则有Advanced Softmaterials Inc.贩卖的“SeRM(注册商标)Super Polymer SM3405P”、“SeRM(注册商标)Key-Mixture SM3400C”、“Se RM(注册商标)Super Polymer SA3405P”、“SeRM(注册商标)Super Polymer SA2405P”、“SeRM(注册商标)Key-Mixture SA3400C”、“Se RM(注册商标)Key-Mixture SA2400C”、“SeRM(注册商标)Super P olymer SA3405P”、“SeRM(注册商标)Super Polymer SA2405P”等。
聚合性聚轮烷也可以另外进行合成。例如,通过使具有聚合性的反应基团的化合物与聚轮烷反应,可以合成聚合性聚轮烷。具体而言,通过以具有经2-羟丙基修饰的α-环糊精(环状分子)的、通常能得到的聚轮烷作为原料,并使(甲基)丙烯酰氯与该原料反应,可以得到聚合性聚轮烷。
即使在形成所述第二粘合结构体的粘合构件时,聚合性单体中也可含有所述交联剂。
通过使含有所述聚合性聚轮烷的聚合性单体进行聚合反应,能够得到由导入有聚轮烷骨架的共聚物形成的粘合构件。另外,制造所述第二粘合结构体时,聚合性单体也可以含有非聚合反应性的聚轮烷和聚合反应性的聚轮烷这两者。
聚合性单体中所含的聚轮烷(也包括聚合性聚轮烷,以下相同)的含量没有特别的限定。例如,相对于聚合性单体的总量(也包括聚轮烷和所述交联剂),聚轮烷的含量可以为1×10-7~50mol/kg、优选为1×10-5~20mol/kg、特别优选为1×10-4~5mol/kg。
制造所述第三粘合结构体时,使用含有含主体基团的聚合性单体和含客体基团的聚合性单体的聚合性单体即可。含主体基团的聚合性单体和含客体基团的聚合性单体优选能够进行自由基聚合。
作为含主体基团的聚合性单体,例如可列举出以下通式(1)所表示的聚合性单体。
[化学式1]
式(1)中,Ra表示氢原子或甲基,R1表示通过从选自由羟基、硫醇基、可具有1个以上取代基的烷氧基、可具有1个以上取代基的硫代烷氧基、可具有1个以上取代基的烷基、可具有1个取代基的氨基、可具有1个以上取代基的酰胺基、醛基以及羧基组成的组中的1价基团中去除1个氢原子而形成的2价基团,RA表示主体基团。主体基团的种类与上述相同。
含主体基团的聚合性单体例如优选为(甲基)丙烯酸酯衍生物、(甲基)丙烯酰胺衍生物。作为其具体例,可列举出:6-(甲基)丙烯酰胺-α-环糊精、6-(甲基)丙烯酰胺-β-环糊精、α-环糊精(甲基)丙烯酸酯、β-环糊精(甲基)丙烯酸酯、苯乙烯。含主体基团的聚合性单体可以利用公知的方法制备。
作为含客体基团的聚合性单体,例如可列举出由以下通式(2)所表示的聚合性单体。
[化学式2]
式(2)中,Ra表示氢原子或甲基,R2表示通过从选自由羟基、硫醇基、可具有1个以上取代基的烷氧基、可具有1个以上取代基的硫代烷氧基、可具有1个以上取代基的烷基、可具有1个取代基的氨基、可具有1个以上取代基的酰胺基、醛基以及羧基组成的组中的1价基团中去除1个氢原子而形成的2价基团,RB表示客体基团。客体基团的种类与上述相同。
含客体基团的聚合性单体例如优选为(甲基)丙烯酸酯衍生物、(甲基)丙烯酰胺衍生物。作为其具体例,可列举出:(甲基)丙烯酸正丁酯、(甲基)丙烯酸叔丁酯、1-丙烯酰胺金刚烷、N-(1-金刚烷基)(甲基)丙烯酰胺、N-苄基(甲基)丙烯酰胺、N-1-萘基甲基(甲基)丙烯酰胺等。含主体基团的聚合性单体可以利用公知的方法制备。主体基团与所述相同。含客体基团的聚合性单体可以利用公知的方法制备。
含有含主体基团的聚合性单体和含客体基团的聚合性单体的聚合性单体,除含有含主体基团的聚合性单体和含客体基团的聚合性单体以外,也可以含有其他的聚合性单体。其他的聚合性单体,与所述聚合性单体相同,例如为所述各种乙烯基类单体。其他的聚合性单体为能够形成所述“第三结构单元”的化合物。其他的聚合性单体若为(甲基)丙烯酰胺和(甲基)丙烯酸酯的混合物,则所得到的粘合结构体容易具有高粘合力。此时的(甲基)丙烯酸酯例如可列举出(甲基)丙烯酸-2-羟基乙酯。(甲基)丙烯酰胺和(甲基)丙烯酸酯的共聚物中,两者的结构单元的摩尔比可以为1:99~99:1,以20:80~80:20、40:60~60:40的顺序优选。此外,其他的聚合性单体为(甲基)丙烯酰胺的聚合物时,所得到的粘合结构体容易具有优异的自修复性。
制造所述第三粘合结构体时,聚合性单体中也可以含有所述交联剂。
含主体基团的聚合性单体和含客体基团的聚合性单体的含有比例没有特别的限定。例如,从容易进行主客体相互作用的角度出发,相对于聚合性单体的总量(也包括所述交联剂),含主体基团的聚合性单体和含客体基团的聚合性单体的含量各自可以为1~20摩尔%,优选为1~5摩尔%,更优选为2~4摩尔%。
粘合工序中的聚合反应的方法没有特别的限定,可以利用公知的方法进行。例如,可以使用公知的聚合引发剂,进行聚合反应。
作为聚合引发剂,若聚合反应为自由基聚合,则例如可列举出:过硫酸铵、过硫酸钠、过硫酸钾等过硫酸盐;偶氮二异丁腈、2,2’-偶氮双[2-(2-咪唑啉-2-基)丙烷]二盐酸盐(商品名称“VA-044”)、1,1’-偶氮双(环己烷甲腈)(1,1'-azobis(cyclohexanecarbonitrile))等偶氮化合物;二叔丁基过氧化物、叔丁基过氧化氢、过氧化苯甲酰等有机过氧化物;光聚合引发剂(IRGACURE(注册商标)系列等)等。
相对于聚合性单体量的总量,聚合引发剂的使用量例如优选为0.1~5摩尔%。聚合引发剂例如被添加在聚合性单体中。
上述自由基聚合反应中,可以使用聚合促进剂。作为聚合促进剂,例如可列举出N,N,N’,N’-四甲基乙二胺、[2-(二甲基氨基)乙基]二甲胺等。
聚合温度虽因所使用的聚合性单体的种类和聚合引发剂的半衰期温度而异,但例如为0~100℃,优选为20~25℃。聚合反应的时间为1~24小时,优选为12~24小时。
聚合反应也可以通过照射紫外线等的光聚合进行。该光聚合中的聚合条件,例如紫外线的种类和照射时间等没有特别的限定,可以在与公知的光聚合相同的条件下进行。
进行聚合性单体的聚合反应时,也可以使聚合性单体溶解或分散在溶剂中。该情况下,可以使用公知的溶剂,例如为水、醇、DMF、DMSO等,除此之外,也可以为酮类、酯类。
例如,聚合性单体含有溶剂时,总聚合性单体的浓度可以为0.3~30mol/kg,优选为1~20mol/kg,更优选为1~5mol/kg。更具体而言,总聚合性单体的浓度,在溶剂为水时优选为1~5mol/kg,在溶剂为DMSO时优选为1~20mol/kg。
只要为不妨碍本发明的粘合结构体的制造的程度,则聚合性单体中也可以含有其他的添加剂。添加剂与所述相同。另外,不含添加剂时,粘合构件仅由聚合物形成。
粘合工序中的聚合反应,例如可以在第一固体构件的粘合面与第二固体构件的粘合面的界面上进行。由此,一边通过聚合性单体的聚合反应形成聚合物,一边该聚合性单体还与第一固体构件和第二固体构件的聚合性的反应基团反应。其结果,在第一固体构件和第二固体构件之间形成的聚合物还与第一固体构件和第二固体构件产生化学键。
在第一固体构件的粘合面与第二固体构件的粘合面的界面上进行聚合的方法没有特别的限定。
例如,可以在一个固体构件的粘合面上,将含有进行聚合反应的聚合性单体的原料进行涂布等,进一步重叠另一个固体构件的粘合面,从而进行聚合反应。也可以使所述原料中所含的聚合性单体的一部分预先进行聚合反应,提高原料的粘度后再进行涂布。
或者,也可以在第一固体构件的粘合面与第二固体构件的粘合面之间设置规定大小的空间,向该空间中填充含有进行聚合反应的聚合性单体的原料,从而进行聚合反应。第一固体构件的粘合面与第二固体构件的粘合面之间的空间,例如可以通过使隔离物等介于第一固体构件和第二固体构件之间而形成。
粘合工序后,根据需要,也可通过干燥处理等使水分等溶剂干燥。
通过经过如上所述的粘合工序,形成粘合构件,能够得到通过该粘合构件而粘合有第一固体构件和第二固体构件的粘合结构体。粘合构件中所含的聚合物,与第一固体构件和第二固体构件的聚合性的反应基团形成化学键。
具备所述粘合工序的方法,适合作为使第一固体构件和第二固体构件彼此粘合的粘合方法。因此,这样的粘合方法,作为用于制造粘合结构体的工序特别有用,可以在各种制造现场进行使用。
实施例
以下,通过实施例对本发明进行更具体的说明,但本发明并不限定于这些实施例的方式。
(固体构件)
作为固体构件,准备了以下5种市售的基板A~E。
基板A:尼龙66
基板B:尼龙610
基板C:玻璃纤维强化尼龙66(含有30重量%的玻璃纤维)
基板D:碳纤维强化尼龙66(含有30重量%的碳纤维)
基板E:铝基板(6000类铝)
将上述基板A~E的大小设作25mm×100mm的俯视长方形状。
(固体构件的表面处理B1,大气压等离子体处理)
如图2所示,对上述基板A~E的基板,在大气压下进行了等离子体处理。具体而言,如图2所示,使进行等离子体处理的基板11、12以粘合面在表面侧露出的方式静置于大气压下,在该表面上设置等离子体照射装置50并照射了等离子体。关于等离子体,利用压缩机或气缸的压力对各种气体进行加压,并经由发生器(generator)由喷嘴进行喷涂,从而在气氛中产生等离子体,将该等离子体照射在了固体构件上。将照射面与等离子体照射口的距离保持在1cm,并且在照射面上使等离子体照射装置以0.5m/分钟的速度一边扫描一边进行了等离子体照射。在从基板的一个短边开始至20mm为止的幅度的整个面上照射了等离子体。由此,得到了形成有等离子体处理部的基板A~E。
(固体构件的表面处理B2,氮等离子体处理)
除了将等离子体的种类变更为氮等离子体以外,以与固体构件的表面处理B1相同的方式得到了具有等离子体处理部的基板A~E。
(固体构件的表面处理B3,氮气氛等离子体处理)
将进行等离子体处理的基板收纳于上方开口的玻璃容器内,使玻璃容器内为氮气氛后,从玻璃容器开口部插入等离子体照射装置,从而使玻璃容器密闭。在该状态下,通过对基板照射等离子体,得到了经等离子体处理的基板A~E。该情况下,也在从基板的一个短边开始至20mm为止的幅度的整个面上照射了等离子体。
(固体构件的表面处理B4,氮-氢气氛等离子体处理)
除了形成氮-氢混合气体(氮97vol%、氢3vol%)的气氛以代替氮气氛以外,以与固体构件的表面处理B3相同的方式得到了经等离子体处理的基板A~E。
(固体构件的表面处理B5,臭氧处理)
将进行臭氧处理的基板静置在臭氧清洁器内,向臭氧清洁器内一边吹入氧,一边照射了紫外线12小时。由此,得到了经臭氧处理的基板A~E。
(固体构件的表面处理B6,碱处理)
将进行碱处理的基板在0.1M氢氧化钠水溶液中浸渍了30分钟。由此,得到了经碱处理的基板A~E。
确认到了通过所述固体构件的表面处理B1~B6,各基板的接触角发生变化。此外,通过XPS测定,确认到了通过所述固体构件的表面处理B1~B6,各基板的表面的碳的比例减少,氮和氧的比例增大。
(固体构件的表面处理A,硅烷偶联剂处理)
如图3所示,进行了硅烷偶联剂处理。从通过固体构件的表面处理B1~B6而得到的各基板中,选择了彼此进行粘合的一对基板11、12。该一对基板11、12中,在一个基板(图3中为基板12)的已进行了上述的各表面处理的部分(特别是从短边开始至25mm为止的区域)上滴加硅烷偶联剂并进行了涂布。使用了3-(三甲氧基甲硅烷基)丙基丙烯酸酯(TPA)作为硅烷偶联剂。并以涂布后的硅烷偶联剂层的厚度成为10μm的量涂布了硅烷偶联剂。
使另一个基板(图3中为基板11)的已进行上述的各表面处理的部分(特别是从短边开始至25mm为止的区域)与涂布有所述硅烷偶联剂的部分重合,并维持该状态,在50℃下加热了3小时。之后,使一对基板分离并清洗各基板,从而洗掉了未反应的TPA。由此,形成了硅烷偶联剂层30,得到了经硅烷偶联剂处理的一对基板。对彼此进行粘合的一对基板均进行了上述操作。
如图3所示,通过硅烷偶联剂处理,在基板(固体构件)上形成了作为聚合性的反应基团的丙烯酰基。
通过使用以上述方式而得到的基板(固体构件)来进行以下实施例以及比较例的粘合,从而制作了粘合结构体。
(实施例1-1)
通过准备作为聚合性单体的丙烯酰胺(以下有时标记为“AAm”)和N,N-亚甲基双丙烯酰胺(以下有时标记为“MBAAm”),并使它们与水混合,从而以聚合性单体的浓度成为4mol/kg的方式调制了原料。相对于聚合性单体的总量,将MBAAm的含量设定为了5mol%。进一步,向该原料中添加了作为聚合引发剂的过硫酸铵(以下有时标记为“APS”)和作为聚合促进剂的N,N,N’,N’-四甲基乙二胺(以下有时标记为“TEMED”)。以相对于聚合性单体成为0.5mol%的方式添加了APS。
另一方面,准备依次经过了所述固体构件的表面处理B1和所述固体构件的表面处理A的一对基板E(第一固体构件和第二固体构件),以在经表面处理的面彼此之间形成空间的方式使之相对。另外,确认到通过基板E的表面处理B1,等离子体处理部的接触角从约80°减少至约60°,亲水性得以提高。
接着,向经表面处理的面彼此之间的空间中填充了所述原料。所述原料的填充量为10μL。在该状态下在室温(25℃)下保持24小时,进行所述原料中所含的聚合性单体的聚合反应,在一对基板间形成了含有聚合物的粘合构件。之后,通过在适当的条件下进行干燥,得到了粘合结构体。
(实施例1-2~1-6)
除了在实施例1-2中变更为依次经过了所述固体构件的表面处理B2和所述固体构件的表面处理A的一对基板E;在实施例1-3中变更为依次经过了所述固体构件的表面处理B3和所述固体构件的表面处理A的一对基板E;在实施例1-4中变更为依次经过了所述固体构件的表面处理B4和所述固体构件的表面处理A的一对基板E;在实施例1-5中变更为依次经过了所述固体构件的表面处理B5和所述固体构件的表面处理A的一对基板E;在实施例1-6中变更为依次经过了所述固体构件的表面处理B6和所述固体构件的表面处理A的一对基板E以外,均以与实施例1-1相同的方法得到了粘合结构体。另外,确认到通过基板E的表面处理B2~B6,等离子体处理部的接触角从约75°减少至约30°,亲水性得以提高。
(实施例2-1)
通过准备作为聚合性单体的丙烯酰胺(AAm)和下述式(3)所表示的聚合性聚轮烷,并向其中加入了适当的水进行混合,从而调制了原料。原料中,将作为聚合性单体的AAm和由下述式(3)表示的聚合性聚轮烷的总浓度调节为了8mol/kg。另外,作为聚合性聚轮烷,使用了重均分子量(直链状高分子)为20000、贯通率为33%、相对于每1个环状分子(α-环糊精)的丙烯酰基为1.61个、分子量为148317.8的聚合性聚轮烷。该情况下,相对于AAm和聚轮烷的总量,约含有0.25mol%的聚合性的反应基团,聚合性单体的总量中,聚轮烷的含量为1×10-4mol/kg。聚合性聚轮烷中的聚合性的反应基团为α-环糊精的氢原子被取代而形成的基团。
[化学式3]
进一步,向该原料中添加了作为聚合引发剂的APS和作为聚合促进剂的TEMED。以相对于聚合性单体成为0.15mol%的方式添加了APS。
如图4所示,准备依次经过了所述固体构件的表面处理B1和所述固体构件的表面处理A的一对基板E(第一固体构件和第二固体构件),在一个基板(在图4中为基板12)的经表面处理的部分上滴加10μL的所述原料,使另一个基板(在图4中为基板11)的经表面处理的部分与该表面重合。在该状态下在室温(25℃)下保持24小时,进行所述原料中所含的聚合性单体的聚合反应,在一对基板间形成了含有聚合物的粘合构件20。另外,如图4所示,该聚合物形成具有聚轮烷骨架的交联结构。之后,通过在适当的条件下进行干燥,得到了粘合结构体。
(实施例2-2~2-6)
除了在实施例2-2中变更为依次经过了所述固体构件的表面处理B2和所述固体构件的表面处理A的一对基板E;在实施例2-3中变更为依次经过了所述固体构件的表面处理B3和所述固体构件的表面处理A的一对基板E;在实施例2-4中变更为依次经过了所述固体构件的表面处理B4和所述固体构件的表面处理A的一对基板E;在实施例2-5中变更为依次经过了所述固体构件的表面处理B5和所述固体构件的表面处理A的一对基板E;在实施例2-6中变更为依次经过了所述固体构件的表面处理B6和所述固体构件的表面处理A的一对基板E以外,均以与实施例2-1相同的方法得到了粘合结构体。
(实施例2-7~2-12)
关于实施例2-7、2-8、2-9、2-10、2-11、2-12,除了分别将聚合性聚轮烷的含量变更为相对于聚合性单体的总量为2、4、6、7、9、10mol/kg以外,均以与实施例2-1相同的方法得到了粘合结构体。
(实施例3-1~3-6)
关于实施例3-1、3-2、3-3、3-4、3-5、3-6,除了分别将实施例2-1、2-2、2-3、2-4、2-5、2-6中的AAm变更为N,N-二甲基丙烯酰胺(以下有时标记为“DMAAm”)以外,以相同的方法得到了粘合结构体。
(实施例4-1~4-6)
关于实施例4-1、4-2、4-3、4-4、4-5、4-6,除了分别将实施例2-1、2-2、2-3、2-4、2-5、2-6的AAm变更为丙烯酸-2-羟基乙酯(以下有时标记为“HEA”)以外,以相同的方法得到了粘合结构体。
(实施例5-1~5-6)
关于实施例5-1、5-2、5-3、5-4、5-5、5-6,除了分别将实施例2-1、2-2、2-3、2-4、2-5、2-6中的AAm变更为甲基丙烯酸-2-羟基乙酯(以下有时标记为“HEMA”)以外,以相同的方法得到了粘合结构体。
(实施例6-1~6-6)
关于实施例6-1、6-2、6-3、6-4、6-5、6-6,除了分别将实施例2-1、2-2、2-3、2-4、2-5、2-6的AAm变更为N,N-二甲氧基三乙二醇丙烯酸酯(以下有时标记为“TEGAc”)以外,以相同的方法得到了粘合结构体。
(实施例7-1)
通过准备作为聚合性单体的丙烯酰胺(AAm)、6-(甲基)丙烯酰胺-β-环糊精(以下有时标记为“AAm-βCD”)以及1-丙烯酰胺金刚烷(以下有时标记为“AAm-Ad”),并使它们与水混合,从而以聚合性单体的浓度成为4mol/kg的方式调制了原料。相对于聚合性单体的总量,AAm-βCD的含量为3mol%、AAm-Ad的含量为2mol%。
进一步,向该原料中添加了作为聚合引发剂的APS和作为聚合促进剂的TEMED。以相对于聚合性单体成为0.5mol%的方式添加了APS。
如图5所示,准备依次经过了所述固体构件的表面处理B1和所述固体构件的表面处理A的一对基板E(第一固体构件11和第二固体构件12),在一个基板(在图5中为基板12)的经表面处理的部分上滴加10μL的所述原料,使另一个基板(在图5中为基板11)的经表面处理的部分与该表面重合。在该状态下在室温(25℃)下保持24小时,进行所述原料中所含的聚合性单体的聚合反应,在一对基板间形成了含有聚合物的粘合构件。另外,如图5所示,该聚合物形成通过主客体相互作用交联而成的交联结构。之后,通过在适当的条件下进行干燥,得到了粘合结构体。
(实施例7-2~7-6)
除了在实施例7-2中变更为依次经过了所述固体构件的表面处理B2和所述固体构件的表面处理A的一对基板E;在实施例7-3中变更为依次经过了所述固体构件的表面处理B3和所述固体构件的表面处理A的一对基板E;在实施例7-4中变更为依次经过了所述固体构件的表面处理B4和所述固体构件的表面处理A的一对基板E;在实施例7-5中变更为依次经过了所述固体构件的表面处理B5和所述固体构件的表面处理A的一对基板E;在实施例7-6中变更为依次经过了所述固体构件的表面处理B6和所述固体构件的表面处理A的一对基板E以外,均以与实施例7-1相同的方法得到了粘合结构体。
(实施例7-7)
除了未使用AAm-βCD以外,以与实施例7-1相同的方法得到了粘合结构体。
(实施例8-1~8-6)
关于实施例8-1、8-2、8-3、8-4、8-5、8-6,除了分别将实施例7-1、7-2、7-3、7-4、7-5、7-6中的AAm变更为丙烯酸-2-羟基乙酯(以下有时标记为“HEA”)以外,以相同的方法得到了粘合结构体。
(实施例9-1~9-6)
关于实施例9-1、9-2、9-3、9-4、9-5、9-6,除了分别将实施例7-1、7-2、7-3、7-4、7-5、7-6中的AAm变更为AAm与HEA的混合物(1:1的摩尔比)以外,以相同的方法得到了粘合结构体。
(实施例10-1~10-6)
关于实施例10-1、10-2、10-3、10-4、10-5、10-6,除了分别将实施例1-1~1-6中的一对基板变更为基板A与基板E的组合以外,以相同的方法得到了粘合结构体。
(实施例11-1~11-6)
关于实施例11-1、11-2、11-3、11-4、11-5、11-6,除了分别将实施例1-1~1-6中的一对基板变更为基板B与基板E的组合以外,以相同的方法得到了粘合结构体。
(实施例12-1~12-6)
关于实施例12-1、12-2、12-3、12-4、12-5、12-6,除了分别将实施例1-1~1-6中的一对基板变更为基板C与基板E的组合以外,以相同的方法得到了粘合结构体。
(实施例13-1~13-6)
关于实施例13-1、13-2、13-3、13-4、13-5、13-6,除了分别将实施例1-1~1-6中的一对基板变更为基板D与基板E的组合以外,以相同的方法得到了粘合结构体。
(实施例14-1~14-6)
关于实施例14-1、14-2、14-3、14-4、14-5、14-6,除了分别将实施例2-1~2-6中的一对基板变更为基板A与基板E的组合以外,以相同的方法得到了粘合结构体。
(实施例15-1~15-6)
关于实施例15-1、15-2、15-3、15-4、15-5、15-6,除了分别将实施例2-1~2-6中的一对基板变更为基板B与基板E的组合以外,以相同的方法得到了粘合结构体。
(实施例16-1~16-6)
关于实施例16-1、16-2、16-3、16-4、16-5、16-6,除了分别将实施例2-1~2-6中的一对基板变更为基板C与基板E的组合以外,以相同的方法得到了粘合结构体。
(实施例17-1~17-6)
关于实施例17-1、17-2、17-3、17-4、17-5、17-6,除了分别将实施例2-1~2-6中的一对基板变更为基板D与基板E的组合以外,以相同的方法得到了粘合结构体。
(实施例18-1~18-6)
关于实施例18-1、18-2、18-3、18-4、18-5、18-6,除了分别将实施例7-1~7-6中的一对基板变更为基板A与基板E的组合,且未对基板A实施表面处理A(即,未在基板A上形成硅烷偶联剂层)以外,以相同的方法得到了粘合结构体。
(实施例19-1~19-6)
关于实施例19-1、19-2、19-3、19-4、19-5、19-6,除了分别将实施例7-1~7-6中的一对基板变更为基板B与基板E的组合,且未对基板B实施表面处理A(即,未在基板B上形成硅烷偶联剂层)以外,以相同的方法得到了粘合结构体。
(实施例20-1~20-6)
关于实施例20-1、20-2、20-3、20-4、20-5、20-6,除了分别将实施例7-1~7-6中的一对基板变更为基板C与基板E的组合,且未对基板C实施表面处理A(即,未在基板C上形成硅烷偶联剂层)以外,以相同的方法得到了粘合结构体。
(实施例21-1~21-6)
关于实施例21-1、21-2、21-3、21-4、21-5、21-6,除了分别将实施例7-1~7-6中的一对基板变更为基板D与基板E的组合,且未对基板D实施表面处理A(即,未在基板D上形成硅烷偶联剂层)以外,以相同的方法得到了粘合结构体。
(比较例1)
使用市售的粘合剂Super-X G(スーパーXゴールド、CEMEDINE Co.,ltd.制造),使一对基板E粘合,从而得到了粘合结构体。
(粘合结构体的粘合力评价)
关于各实施例和比较例中所得到的粘合结构体的粘合力,利用依据JIS K 6850“粘合剂刚性被粘材料的拉伸剪切粘合强度试验方法(接着剤剛性被着材の引張りせん断接着強さ試験方法)”的方法进行了评价。具体而言,进行将粘合结构体的第一固体构件和第二固体构件彼此沿相反的方向大致水平地进行拉伸的试验,测定了拉伸剪切粘合强度。将该值作为了“初期粘合力”。测定中使用了Shimadzu Corporation.制造的AUTOGRAPH精密万能试验机“AG-Xplus”。
(粘合结构体的自修复性评价)
在所述粘合结构体的粘合力评价中,使用第一固体构件和第二固体构件的粘合部分已断裂的一对基板,评价了自修复性能。具体而言,在断裂了的粘合构件的一个断裂面上添加适量的水,使该表面与另一个断裂面重合。在该状态下静置24小时,之后,使之干燥,去除水分,再次使断裂面彼此粘合,由此修复了粘合结构体。
接着,对已修复的粘合结构体,在与所述粘合结构体的粘合力评价中记载的方法相同的条件下,测定了拉伸剪切粘合强度。将该值作为了“第1次修复后的粘合力”。并且,计算出了“(第1次修复后的粘合力/初期粘合力)×100”的值。
进一步,使在第1次修复后的粘合力的测定中断裂的粘合构件,以与第1次修复后的粘合力的测定相同的步骤进行再次修复,从而再次形成粘合结构体,在与所述粘合结构体的粘合力评价中记载的方法相同的条件下,测定了拉伸剪切粘合强度。将该值作为了“第2次修复后的粘合力”。并且,计算出了“(第2次修复后的粘合力/初期粘合力)×100”的值。以后,以相同的步骤,测量了直至最大第4次的修复(第4次修复后的粘合力)的粘合力。通过以上的操作,分别计算出“(第n次修复后的粘合力/初期粘合力)×100”的值(n=1、2、3、4),将这些值作为粘合结构体的第n次恢复率(n=1、2、3、4)并作为了自修复性评价的指标。测定中使用了Shimadzu Corporation.制造的AUTOGRAPH精密万能试验机“AG-Xplus”。
另外,只要第1次恢复率为10%以上,则可以判断自修复性优异,优选为20%以上,更优选为50%以上,特别优选为80%以上。
[表1]
表1中表示各实施例中制作的粘合结构体的粘合力评价和自修复性评价的结果。从表1可知,与使用了以往的粘合剂(比较例1)的粘合、即与固体构件和粘合构件未进行化学键合的粘合结构体相比,如各实施例的固体构件和粘合构件进行了化学键合的粘合结构体具有高初期粘合力。此外,由实施例7-7与实施例7-6等的对比可知,通过在粘合构件中导入主客体相互作用,还可以确认到恢复率得以提高,由此还可知其为具有自修复性的粘合结构体。
Claims (14)
1.一种粘合结构体,其具备第一固体构件、第二固体构件以及粘合构件,其中,
所述第一固体构件和所述第二固体构件通过所述粘合构件而粘合,
所述粘合构件含有聚合物,
所述聚合物与所述第一固体构件和所述第二固体构件形成化学键。
2.根据权利要求1所述的粘合结构体,其中,所述聚合物含有(甲基)丙烯酸类高分子化合物。
3.根据权利要求1所述的粘合结构体,其中,所述聚合物含有聚轮烷。
4.根据权利要求1所述的粘合结构体,其中,所述聚合物具有通过主客体相互作用交联而成的结构。
5.根据权利要求1~4中任意一项所述的粘合结构体,其中,所述第一固体构件和所述第二固体构件为相同或不同的材料,为选自由金属、树脂、玻璃以及无机物组成的组中的一种。
6.根据权利要求1~4中任意一项所述的粘合结构体,其中,所述第一固体构件和所述第二固体构件中的一者或两者的与所述粘合构件接触的面上设置有等离子体处理部。
7.根据权利要求5所述的粘合结构体,其中,所述第一固体构件和所述第二固体构件中的一者或两者的与所述粘合构件接触的面上设置有等离子体处理部。
8.一种制造粘合结构体的方法,其为制造具备第一固体构件、第二固体构件以及粘合构件的粘合结构体的方法,其中,
该制造粘合结构体的方法具备下述粘合工序:通过利用聚合性单体的聚合反应而形成含有聚合物的粘合构件,从而使所述第一固体构件和所述第二固体构件通过所述粘合构件而粘合;
所述第一固体构件和所述第二固体构件的表面具有聚合性的反应基团;
所述聚合物与所述反应基团进行化学键合。
9.根据权利要求8所述的制造粘合结构体的方法,其中,所述聚合性单体含有聚合反应性的聚轮烷。
10.根据权利要求8所述的制造粘合结构体的方法,其中,所述聚合性单体含有含主体基团的聚合性单体和含客体基团的聚合性单体。
11.根据权利要求8~10中任意一项所述的制造粘合结构体的方法,其中,所述第一固体构件和所述第二固体构件为相同或不同的材料,为选自由金属、树脂、玻璃以及无机物组成的组中的一种。
12.根据权利要求8~10中任意一项所述的制造粘合结构体的方法,其具备:在所述粘合工序前,利用硅烷偶联剂对所述第一固体构件和所述第二固体构件中的一者或两者进行处理的表面处理工序A。
13.根据权利要求8~10中任意一项所述的制造粘合结构体的方法,其具备:在所述粘合工序前,对所述第一固体构件和所述第二固体构件中的一者或两者,进行选自由等离子体照射、臭氧处理、碱处理以及酸处理组成的组中的至少一种以上的处理的表面处理工序B。
14.根据权利要求8~10中任意一项所述的制造粘合结构体的方法,其中,所述反应基团具有自由基聚合性。
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