技术领域technical field
本发明涉及易解体性的双面粘胶带以及通过上述双面粘胶带被贴合的两个以上的被粘物体的分离方法，使用该双面粘胶带进行向被粘物体的贴附、物品间的固定时，经过一定期间后可容易地解除上述贴附、固定。The present invention relates to an easily disassembled double-sided adhesive tape and a method for separating two or more adherends bonded by the double-sided adhesive tape, wherein the double-sided adhesive tape is used for sticking to an adherend , When fixing between items, the above-mentioned sticking and fixing can be easily released after a certain period of time.
背景技术Background technique
粘胶带作为作业性优异且粘接可靠性高的接合手段而被用于OA设备、IT设备、家电产品、汽车等各产业领域中的部件固定用途、部件的临时固定用途、显示产品信息的标签用途等。近年来，从保护地球环境的观点出发，在这些产业领域中，废旧产品的回收、再利用的要求不断提高。对各种产品进行回收、再利用时，需要将用于部件的固定、标签的粘胶带剥离的作业，但由于上述粘胶带设置于产品中的各处，因此期望通过简单的除去工序来降低作业成本。Adhesive tapes are used as a joining means with excellent workability and high adhesion reliability in various industrial fields such as OA equipment, IT equipment, home appliances, automobiles, etc., for parts fixing, temporary fixing of parts, and displaying product information. Label usage, etc. In recent years, from the viewpoint of protecting the global environment, in these industrial fields, the demand for recycling and recycling of waste products has been increasing. When collecting and reusing various products, it is necessary to peel off the adhesive tape used for fixing parts and labels. However, since the above-mentioned adhesive tape is installed in various places in the product, it is desired to remove it through a simple removal process. Reduce operating costs.
作为能够较容易地剥离的粘胶带，例如，公开了具有粘接力不同的2层以上的粘着层的粘着构件(参照专利文献1)。上述粘胶带为通过隔着具有重叠结构的粘着层的粘着构件中的弱粘着层对被粘物体进行接合处理，从而实现被粘物体的牢固的固着、及以该弱粘着层作为剥离面的容易的解体的粘着构件。As an adhesive tape that can be peeled relatively easily, for example, an adhesive member having two or more adhesive layers with different adhesive forces is disclosed (see Patent Document 1). The above-mentioned adhesive tape is used to bond the adherend through the weak adhesive layer in the adhesive member having the overlapping structure of the adhesive layer, so as to achieve firm fixation of the adherend and use the weak adhesive layer as the release surface. Adhesive components for easy disassembly.
但是，上述粘着构件以多个粘着剂层作为必须构成，因此存在制造成本变高的问题。另外，上述粘着构件为通过弱粘着层来进行与被粘物体的粘接的构成，因此在粘接力的提高上有限制，难以向牢固地固定物品的用途展开。However, the above-mentioned adhesive member has a problem in that the manufacturing cost becomes high because it must have a plurality of adhesive layers. In addition, since the above-mentioned adhesive member is configured to adhere to an adherend through a weak adhesive layer, there is a limit to the improvement of the adhesive force, and it is difficult to develop applications for firmly fixing articles.
现有技术文献prior art literature
专利文献patent documents
专利文献1：日本特开平10－140093号公报Patent Document 1: Japanese Patent Application Laid-Open No. 10-140093
发明内容Contents of the invention
发明所要解决的课题The problem to be solved by the invention
本发明所要解决的课题为提供一种双面粘胶带，上述双面粘胶带可用于向被粘物体的贴附、两个以上的被粘物体的固定，且在将上述两个以上的被粘物体分离时可简单地解体。The problem to be solved by the present invention is to provide a double-sided adhesive tape, which can be used for sticking to an adherend and fixing two or more adherends, and the above-mentioned two or more It can be easily disassembled when the adhered object is separated.
解决课题的手段means of solving problems
本发明涉及一种双面粘胶带，其特征在于：在含有粘合剂及热膨胀性微球的易解体层的两面，直接或隔着其他层而具有粘着剂层。The present invention relates to a double-sided adhesive tape, which is characterized in that: on both sides of an easily disassembled layer containing an adhesive and thermally expandable microspheres, there are adhesive layers directly or through other layers.
另外，本发明涉及一种物品，其特征在于：具有两个以上的被粘物体通过上述双面粘胶带被粘接而成的构成。Also, the present invention relates to an article characterized in that it has a structure in which two or more adherends are adhered by the above-mentioned double-sided adhesive tape.
另外，本发明涉及一种分离方法，通过将构成上述物品的上述易解体层加热，使上述热膨胀性微球膨胀，从而将构成上述物品的两个以上的被粘物体分离。Also, the present invention relates to a separation method for separating two or more adherends constituting the above article by heating the easily disintegrable layer constituting the above article to expand the thermally expandable microspheres.
发明效果Invention effect
本发明的双面粘胶带可贴附至被粘物体，且可牢固地贴合两个以上的被粘物体，在通过消除上述被粘物体彼此的贴合而解体上述物品时，可通过加热简单地分离上述两个以上的被粘物体。The double-sided adhesive tape of the present invention can be attached to an adherend, and can firmly bond two or more adherends. Simply separate the above two or more adherends.
根据本发明的双面粘胶带的制造方法，可制造本发明的双面粘胶带。According to the manufacturing method of the double-sided adhesive tape of this invention, the double-sided adhesive tape of this invention can be manufactured.
根据本发明的分离方法，可简单地分离被粘物体彼此的贴合。According to the separating method of the present invention, it is possible to easily separate adherends from each other.
附图说明Description of drawings
图1为表示本发明所涉及的双面粘胶带的实施方式的一例的剖面图。FIG. 1 is a cross-sectional view illustrating an example of an embodiment of a double-sided adhesive tape according to the present invention.
图2为表示本发明所涉及的双面粘胶带的实施方式的一例的剖面图。Fig. 2 is a cross-sectional view showing an example of an embodiment of the double-sided adhesive tape according to the present invention.
图3为说明本发明所涉及的双面粘胶带的制造方法的实施方式的一例的图。Fig. 3 is a diagram illustrating an example of an embodiment of a method for producing a double-sided adhesive tape according to the present invention.
图4为说明本发明所涉及的粘接方法的实施方式的一例的图。FIG. 4 is a diagram illustrating an example of an embodiment of the bonding method according to the present invention.
图5为说明本发明所涉及的分离方法的实施方式的一例的图。FIG. 5 is a diagram illustrating an example of an embodiment of the separation method according to the present invention.
图6为示意性地示出了被粘物体的分离情况的图。Fig. 6 is a diagram schematically showing a state of separation of an adherend.
图7为表示本发明所涉及的分离方法的实施方式的一例的剖面图。Fig. 7 is a cross-sectional view showing an example of an embodiment of the separation method according to the present invention.
图8为说明实施例1的双面粘胶带及比较例1的双面粘胶带的制造方法、以及实施例1的双面粘胶带及比较例1的双面粘胶带的构成的图。Fig. 8 is a diagram illustrating the method of manufacturing the double-sided adhesive tape of Example 1 and the double-sided adhesive tape of Comparative Example 1, and the configuration of the double-sided adhesive tape of Example 1 and the double-sided adhesive tape of Comparative Example 1. picture.
图9为说明实施例中的解体性试验的方法的图。Fig. 9 is a diagram illustrating a method of a disassembly test in an example.
具体实施方式detailed description
《双面粘胶带》"Double Sided Adhesive Tape"
本发明的双面粘胶带的特征在于：在含有粘合剂及热膨胀性微球的易解体层的两面，直接或隔着其他层而具有粘着剂层。The double-sided adhesive tape of the present invention is characterized in that it has an adhesive layer on both sides of the easily disassembled layer containing the adhesive and heat-expandable microspheres, directly or through other layers.
以下，对本发明的双面粘胶带的实施方式的一例进行说明。Hereinafter, an example of embodiment of the double-sided adhesive tape of this invention is demonstrated.
<第1实施方式><First Embodiment>
图1为本发明所涉及的双面粘胶带的实施方式的一例。双面粘胶带1在含有粘合剂11及热膨胀性微球12的易解体层10的两面侧具有粘着剂层20、21。在粘着剂层20、21上，可分别层叠有剥离片30、31。FIG. 1 is an example of an embodiment of the double-sided adhesive tape according to the present invention. The double-sided adhesive tape 1 has adhesive layers 20 and 21 on both sides of an easily disassembled layer 10 containing an adhesive 11 and heat-expandable microspheres 12 . Release sheets 30, 31 may be laminated on the adhesive layers 20, 21, respectively.
以下，对双面粘胶带的各构成进行说明。Hereinafter, each structure of a double-sided adhesive tape is demonstrated.
[易解体层][Easily disintegrated layer]
易解体层10含有粘合剂11及热膨胀性微球12。易解体层为，在将通过双面粘胶带被贴合的两个以上的被粘物体分离时，由于将被粘物体彼此分离等的剥离应力而被破坏的层。The easily disintegrable layer 10 contains a binder 11 and heat-expandable microspheres 12 . The easily dismantlable layer is a layer that is broken due to peeling stress such as separating the adherends when separating two or more adherends bonded by the double-sided adhesive tape.
作为上述粘合剂，可使用因上述热膨胀性微球膨胀的力而能够容易地解体的物质。另外，作为上述粘合剂，优选使用热塑性的粘合剂。此处，所谓热塑性，是指上述粘合剂的1Hz及23℃时的以动态粘弹性谱测定的储能模量G23为1.0×103～5.0×107Pa的范围、1Hz及120℃时的以动态粘弹性谱测定的储能模量G120为1.0×102～5.0×106Pa的范围。As the above-mentioned binder, one that can be easily disassembled by the force of expansion of the above-mentioned heat-expandable microspheres can be used. In addition, it is preferable to use a thermoplastic adhesive as the above-mentioned adhesive. Here, the term "thermoplasticity" means that the storage modulus G23 of the above-mentioned adhesive at 1Hz and23 °C measured by dynamic viscoelasticity spectrum is in the range of 1.0×103 to 5.0×107 Pa, 1Hz and 120°C The storage modulus G120 measured by the dynamic viscoelasticity spectrum is in the range of 1.0×102 to 5.0×106 Pa.
通常状态下，从通过本发明的双面粘胶带使被粘物体彼此牢固地粘接方面出发，优选使用构成易解体层的粘合剂的1Hz及23℃时的以动态粘弹性谱测定的储能模量G23为1.0×103～5.0×107Pa者，更优选使用为5.0×103～5.0×106Pa者，进一步优选使用为5.0×103～1.0×106Pa者，特别优选使用为1.0×104～1.0×106Pa者。Normally, from the aspect of firmly bonding the adherends to each other by the double-sided adhesive tape of the present invention, it is preferable to use the dynamic viscoelasticity spectrum measured at 1 Hz and 23° C. of the adhesive constituting the easily disintegrable layer. The storage modulus G23 is 1.0×103 to 5.0×107 Pa, more preferably 5.0×103 to 5.0×106 Pa, still more preferably 5.0×103 to 1.0×106 Pa , it is particularly preferable to use one with a pressure of 1.0×104 to 1.0×106 Pa.
另外，从通过加热使被粘物体彼此容易地分离方面出发，优选使用构成易解体层的粘合剂的1Hz及120℃时的以动态粘弹性谱测定的储能模量G120为1.0×102～5.0×106Pa者，更优选使用为5.0×102～1.0×106Pa者，进一步优选使用为5.0×102～5.0×105Pa者。In addition, from the viewpoint of easily separating the adherends by heating, it is preferable that the storage modulus G120 measured by dynamic viscoelasticity spectrum at 1 Hz and120 °C using the adhesive constituting the easily disintegrable layer is 1.0×102 to 5.0×106 Pa, more preferably 5.0×102 to 1.0×106 Pa, still more preferably 5.0×102 to 5.0×105 Pa.
易解体层的粘合剂的上述储能模量G120优选比上述储能模量G23小。The above-mentioned storage modulusG120 of the adhesive of the easily disintegrable layer is preferably smaller than the above-mentioned storage modulusG23 .
上述储能模量G23及G120，是指对使用构成易解体层的粘合剂而形成的试验片进行测定的结果。上述试验片中不含热膨胀性微球。试验片的厚度设为2mm。试验片可通过将易解体层中所含有的粘合剂涂布于片材上等而得到。The above-mentioned storage modulus G23 and G120 refer to the results of measurement on a test piece formed using an adhesive constituting the easily disintegrable layer. The above-mentioned test piece does not contain heat-expandable microspheres. The thickness of the test piece was set to 2 mm. The test piece can be obtained by applying the adhesive contained in the easily disintegrable layer to a sheet or the like.
关于储能模量G23及G120，可使用市售的粘弹性试验机，利用后述实施例中所记载的方法进行测定。The storage elastic moduli G23 and G120 can be measured by the method described in Examples described later using a commercially available viscoelasticity testing machine.
上述易解体层的厚度优选为5μm～80μm，更优选为5μm～60μm，进一步优选为10μm～50μm。易解体层的厚度设为测定在易解体层的厚度方向上随机选出的5个地方的厚度而得到的平均值。通过使易解体层的厚度为上述范围，可成为层的形成容易且易解体性优异的易解体层。The thickness of the easily disintegrable layer is preferably 5 μm to 80 μm, more preferably 5 μm to 60 μm, and even more preferably 10 μm to 50 μm. The thickness of the easily disintegrable layer was defined as an average value obtained by measuring the thicknesses at five points randomly selected in the thickness direction of the easily disintegrate layer. By making the thickness of the easily disintegrable layer into the above-mentioned range, formation of a layer is easy and the easily disintegrable layer excellent in disassembly property can be obtained.
使用例如热塑性树脂作为上述易解体层中所含有的上述粘合剂时，因热而易软化从而易解体，因此优选。When using, for example, a thermoplastic resin as the above-mentioned binder contained in the above-mentioned easily dismantlable layer, it is easy to soften and disassemble due to heat, which is preferable.
作为上述热塑性树脂，例如可列举聚氨酯(PU)、热塑性聚氨酯(TPU)等氨基甲酸酯系树脂；聚碳酸酯(PC)；聚氯乙烯(PVC)、氯乙烯－乙酸乙烯酯共聚树脂等氯乙烯系树脂；聚丙烯酸、聚甲基丙烯酸、聚丙烯酸甲酯、聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸乙酯等丙烯酸系树脂；聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯等聚酯系树脂；尼龙(注册商标)等聚酰胺系树脂；聚苯乙烯(PS)、酰亚胺改性聚苯乙烯、丙烯腈/丁二烯/苯乙烯(ABS)树脂、酰亚胺改性ABS树脂、苯乙烯/丙烯腈共聚(SAN)树脂、丙烯腈/乙烯－丙烯－二烯/苯乙烯(AES)树脂等聚苯乙烯系树脂；聚乙烯(PE)树脂、聚丙烯(PP)树脂、环烯烃树脂等烯烃系树脂；硝化纤维素、乙酸纤维素等纤维素系树脂；有机硅系树脂；氟系树脂等热塑性树脂；苯乙烯系热塑性弹性体、烯烃系热塑性弹性体、氯乙烯系热塑性弹性体、氨基甲酸酯系热塑性弹性体、酯系热塑性弹性体、酰胺系热塑性弹性体等热塑性弹性体。Examples of the above-mentioned thermoplastic resin include urethane-based resins such as polyurethane (PU) and thermoplastic polyurethane (TPU); polycarbonate (PC); polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymer resin, etc. Vinyl resins; acrylic resins such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), polyethyl methacrylate, etc.; polyethylene terephthalate (PET) , polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and other polyester resins; nylon (registered trademark) and other polyamides Resin; polystyrene (PS), imide-modified polystyrene, acrylonitrile/butadiene/styrene (ABS) resin, imide-modified ABS resin, styrene/acrylonitrile copolymer (SAN) Polystyrene-based resins such as acrylonitrile/ethylene-propylene-diene/styrene (AES) resins; olefin-based resins such as polyethylene (PE) resins, polypropylene (PP) resins, and cycloolefin resins; nitrocellulose Cellulose-based resins such as cellulose acetate, silicone-based resins, thermoplastic resins such as fluorine-based resins, styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, and urethane-based thermoplastic elastomers , Ester-based thermoplastic elastomers, amide-based thermoplastic elastomers and other thermoplastic elastomers.
作为热塑性树脂，上述这些中特别是优选使用苯乙烯系热塑性弹性体、烯烃系热塑性弹性体、氯乙烯系热塑性弹性体、酯系热塑性弹性体、氨基甲酸酯系热塑性弹性体、酰胺系热塑性弹性体或丙烯酸系树脂等，特别优选使用苯乙烯系热塑性弹性体或丙烯酸系树脂。As the thermoplastic resin, among the above, styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, ester-based thermoplastic elastomers, urethane-based thermoplastic elastomers, and amide-based thermoplastic elastomers are preferably used. polymers or acrylic resins, etc., particularly preferably styrene-based thermoplastic elastomers or acrylic resins.
作为苯乙烯系热塑性弹性体，例如可列举苯乙烯－乙烯－丁烯共聚物(SEB)等苯乙烯系二嵌段共聚物；苯乙烯－丁二烯－苯乙烯共聚物(SBS)、SBS的氢化物(苯乙烯－乙烯－丁烯－苯乙烯共聚物(SEBS))、苯乙烯－异戊二烯－苯乙烯共聚物(SIS)、SIS的氢化物(苯乙烯－乙烯－丙烯－苯乙烯共聚物(SEPS))、苯乙烯－异丁烯－苯乙烯共聚物(SIBS)等苯乙烯系三嵌段共聚物；苯乙烯－丁二烯－苯乙烯－丁二烯(SBSB)等苯乙烯系四嵌段共聚物；苯乙烯－丁二烯－苯乙烯－丁二烯－苯乙烯(SBSBS)等苯乙烯系五嵌段共聚物；具有这些以上的重复单元的苯乙烯系多嵌段共聚物；将苯乙烯－丁二烯橡胶(SBR)等苯乙烯系无规共聚物的乙烯性双键氢化后的氢化物等。苯乙烯系热塑性弹性体也可使用市售品。Examples of styrene-based thermoplastic elastomers include styrene-based diblock copolymers such as styrene-ethylene-butylene copolymer (SEB); styrene-butadiene-styrene copolymer (SBS); Hydride (styrene-ethylene-butylene-styrene copolymer (SEBS)), styrene-isoprene-styrene copolymer (SIS), hydride of SIS (styrene-ethylene-propylene-styrene Copolymer (SEPS)), styrene-isobutylene-styrene copolymer (SIBS) and other styrenic tri-block copolymers; styrene-butadiene-styrene-butadiene (SBSB) and other styrenic four-block copolymers Block copolymers; styrene-based penta-block copolymers such as styrene-butadiene-styrene-butadiene-styrene (SBSBS); styrene-based multi-block copolymers with repeating units above these; Hydrogenated products obtained by hydrogenating the ethylenic double bonds of styrene-based random copolymers such as styrene-butadiene rubber (SBR), etc. As the styrene-based thermoplastic elastomer, commercially available items can also be used.
作为上述苯乙烯系热塑性弹性体，使用上述苯乙烯系三嵌段共聚物及苯乙烯系二嵌段共聚物的混合物时，具有上述23℃时的储能模量与上述120℃时的储能模量、及上述23℃时的储能模量除以120℃时测定的储能模量所得的值，其结果为，得到在约23℃的常温区域下可将两个以上的被粘物体牢固地贴合，且通过加热至约120℃可容易地将两个以上的被粘物体分离的粘胶带，因此优选，更优选使用相对于上述苯乙烯系热塑性弹性体全体，以10质量％～90质量％的范围含有上述苯乙烯系二嵌段共聚物者，进一步优选以15质量％～80质量％的范围使用，特别优选以20质量％～75质量％的范围使用。When the above-mentioned styrenic thermoplastic elastomer is used as a mixture of the above-mentioned styrenic tri-block copolymer and styrenic di-block copolymer, it has the above-mentioned storage modulus at 23°C and the above-mentioned storage energy at 120°C. Modulus, and the value obtained by dividing the above-mentioned storage modulus at 23°C by the storage modulus measured at 120°C, the result is that two or more adherends can be bonded in the normal temperature range of about 23°C. Adhesive tape that sticks firmly and can easily separate two or more adherends by heating to about 120°C is preferred, more preferably used at 10% by mass relative to the entire styrene-based thermoplastic elastomer. Those containing the above-mentioned styrene-based diblock copolymer in a range of ˜90% by mass are more preferably used in a range of 15% by mass to 80% by mass, and particularly preferably used in a range of 20% by mass to 75% by mass.
作为上述苯乙烯系热塑性弹性体，在使加热所致的解体性更为提高方面，优选使用具有1万～80万范围的重均分子量者，更优选使用具有5万～50万范围的重均分子量者，进一步优选使用具有15万～45万范围的重均分子量者。As the above-mentioned styrene-based thermoplastic elastomer, it is preferable to use one having a weight-average molecular weight in the range of 10,000 to 800,000, and more preferably to use one having a weight-average molecular weight in the range of 50,000 to 500,000 in order to further improve the disassembly property by heating. As for the molecular weight, it is more preferable to use one having a weight average molecular weight in the range of 150,000 to 450,000.
上述丙烯酸系树脂例如可使用由含有(甲基)丙烯酸烷基酯的单体聚合而得到的物质。As the acrylic resin, for example, one obtained by polymerizing an alkyl (meth)acrylate-containing monomer can be used.
作为上述(甲基)丙烯酸烷基酯，优选使用具有碳原子数4～12的烷基的(甲基)丙烯酸酯，具体而言，优选使用(甲基)丙烯酸丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸2－乙基己酯等，更优选将丙烯酸丁酯及丙烯酸2－乙基己酯单独或组合使用。As the above-mentioned alkyl (meth)acrylate, a (meth)acrylate having an alkyl group having 4 to 12 carbon atoms is preferably used, specifically, butyl (meth)acrylate, (meth)acrylic acid Isooctyl, 2-ethylhexyl (meth)acrylate, etc., More preferably, butyl acrylate and 2-ethylhexyl acrylate are used alone or in combination.
另外，作为上述单体，除上述物质以外，还可使用丙烯腈、(甲基)丙烯酸、马来酸酐、丙烯酰胺、衣康酸、苯乙烯、乙酸乙烯酯等。Moreover, as said monomer, acrylonitrile, (meth)acrylic acid, maleic anhydride, acrylamide, itaconic acid, styrene, vinyl acetate, etc. can be used other than the above-mentioned thing.
上述易解体层中所含有的热膨胀性微球能够因热的影响而膨胀。具体而言，作为上述热膨胀性微球，优选使用120℃时的热膨胀率为150％以上者，更优选使用120℃时的热膨胀率为170％以上者，进一步优选使用120℃时的热膨胀率为200％以上者，特别优选使用120℃时的热膨胀率为220％以上者，使用250％以上者时，可容易地解体易解体层，其结果为可容易地进行被粘物体彼此的分离，因而特别优选。另外，上述膨胀率的上限并无特别限制，优选为大概5000％。此外，上述热膨胀率是指利用以下方法算出的值。The heat-expandable microspheres contained in the easily disintegrable layer can expand under the influence of heat. Specifically, as the above-mentioned heat-expandable microspheres, it is preferable to use a thermal expansion coefficient at 120°C of 150% or more, more preferably use a thermal expansion coefficient at 120°C of 170% or more, and even more preferably use a thermal expansion coefficient at 120°C. 200% or more, particularly preferably 220% or more of thermal expansion at 120°C. When 250% or more is used, the easily disassembled layer can be easily disassembled, and as a result, the adherends can be easily separated from each other. Especially preferred. In addition, the upper limit of the expansion ratio is not particularly limited, but is preferably about 5000%. In addition, the said coefficient of thermal expansion means the value calculated by the following method.
首先，将热膨胀性微球(未膨胀者)1g放入容量瓶中，利用水中置换法测定真比重。然后，将上述热膨胀性微球1g放入吉尔式烘箱(geer type oven)中，在120℃下加热2分钟使其膨胀。First, 1 g of heat-expandable microspheres (unexpanded) was placed in a volumetric flask, and the true specific gravity was measured by the water displacement method. Then, 1 g of the above-mentioned heat-expandable microspheres was placed in a Geer type oven, and heated at 120° C. for 2 minutes to expand them.
然后，将膨胀后的微球放入容量瓶中，利用水中置换法测定真比重。Then, the expanded microspheres were put into a volumetric flask, and the true specific gravity was measured by the water displacement method.
算出膨胀前的热膨胀性微球的真比重相对于热膨胀后的微球的真比重的比，将其乘以100所得到的值作为热膨胀率。The ratio of the true specific gravity of the heat-expandable microspheres before expansion to the true specific gravity of the heat-expanded microspheres was calculated, and the value obtained by multiplying this by 100 was used as the coefficient of thermal expansion.
上述热膨胀性微球的膨胀开始温度并无特别限制，优选为80℃以上，更优选为85℃～120℃，为90℃～120℃时，形成易解体层时不会发生膨胀，且不引起两个以上的被粘物体的热损伤而将它们分离，因此进一步优选。于以说明的是，上述“热膨胀性微球的膨胀开始温度”，为对热膨胀性微球使用热分析装置(“TMA/SS6100”、SII·Nanotechnology(株)制)，利用膨胀法(荷重：0.1N、探头：3mmΦ、升温速度：5℃/分钟)进行评价时热膨胀性微球开始膨胀的温度。The expansion start temperature of the above-mentioned heat-expandable microspheres is not particularly limited, but it is preferably 80°C or higher, more preferably 85°C to 120°C, and when it is 90°C to 120°C, no expansion will occur when the easily disintegrated layer is formed, and it will not cause It is more preferable to separate two or more adherends by heat damage. It should be noted that the above-mentioned "expansion start temperature of heat-expandable microspheres" is a thermal analysis device ("TMA/SS6100", manufactured by SII Nanotechnology Co., Ltd.) for heat-expandable microspheres, using the expansion method (load: 0.1N, probe: 3mmΦ, heating rate: 5°C/min) the temperature at which thermally expandable microspheres start to expand when evaluating.
上述热膨胀性微球的最大膨胀温度并无特别限制，优选为90℃以上，优选为90℃～180℃，为100℃以上～150℃时，不引起两个以上的被粘物体的热损伤而将它们分离，因此进一步优选。予以说明的是，上述“最大膨胀温度”为对热膨胀性微球使用热分析装置(“TMA/SS6100”、SII·Nanotechnology(株)制)，利用膨胀法(荷重：0.1N、探头：3mmΦ、升温速度：5℃/分钟)进行评价时热膨胀性微球的膨胀为最大时的温度。此外，加热至比最大膨胀温度更高的温度的热膨胀性微球通常会收缩而使膨胀率降低，因此优选不加热至比上述最大膨胀温度更高的温度。The maximum expansion temperature of the above-mentioned heat-expandable microspheres is not particularly limited, but is preferably 90°C or higher, preferably 90°C to 180°C, and when it is 100°C or higher to 150°C, thermal damage to two or more adherends is not caused. It is further preferable to separate them. It should be noted that the above-mentioned "maximum expansion temperature" is based on the expansion method (load: 0.1N, probe: 3mmΦ, Temperature increase rate: 5° C./min) The temperature at which the expansion of the heat-expandable microspheres reaches the maximum when evaluation is performed. In addition, since heat-expandable microspheres heated to a temperature higher than the maximum expansion temperature usually shrink to lower the expansion rate, it is preferable not to heat to a temperature higher than the above-mentioned maximum expansion temperature.
此外，制造上述热膨胀性微球时，其制造中所使用的胶囊的壁厚、气化物质的含量等难以全部均匀化，因此其膨胀开始温度及最大膨胀温度通常具有一定的范围。In addition, when producing the above-mentioned heat-expandable microspheres, it is difficult to uniformize the wall thickness of the capsules used in the production, the content of gasified substances, etc., so the expansion start temperature and maximum expansion temperature usually have a certain range.
上述热膨胀性微球的粒径(膨胀前)并无特别限制，在进行了加热时进一步提高易解体层的解体性，且实现易解体层及双面粘胶带的薄型化方面，优选为1μm～50μm的范围内，更优选为3μm～30μm的范围内，进一步优选为5μm～20μm的范围内。The particle size (before expansion) of the above-mentioned heat-expandable microspheres is not particularly limited, and is preferably 1 μm in terms of further improving the disintegration property of the easily disintegrable layer when heated, and realizing thinning of the easily disintegrate layer and the double-sided adhesive tape. It is within the range of 50 μm, more preferably within the range of 3 μm to 30 μm, even more preferably within the range of 5 μm to 20 μm.
此外，上述热膨胀性微球通常为具有不同粒径等的微球的集合。因此，测定上述热膨胀性微球的粒径时，会得到分布(粒度分布)。本发明中，关于上述热膨胀性微球的粒径(膨胀前)，使用Malvern公司制粒度分布测定装置“Mastersizer 2000”，利用激光衍射散射法进行10次测定，使用所得到的基于10个粒度分布的10点极大值的最大值与最小值，以范围来表示。具体而言，基于使用上述方法对热膨胀性微球的粒径(膨胀前)进行10次测定而得到的10个粒度分布的10点极大值的最大值为15μm，其最小值为9μm时，上述热膨胀性微球的粒径(膨胀前)表示为9μm～15μm。In addition, the above-mentioned heat-expandable microspheres are generally a collection of microspheres having different particle diameters and the like. Therefore, when the particle diameter of the thermally expandable microspheres is measured, distribution (particle size distribution) is obtained. In the present invention, the particle size (before expansion) of the above-mentioned heat-expandable microspheres is measured 10 times by the laser diffraction scattering method using a particle size distribution measuring device "Mastersizer 2000" manufactured by Malvern Corporation, and the obtained particle size distribution based on 10 particles is used. The maximum and minimum values of the 10-point maximum value are expressed in ranges. Specifically, based on the above-mentioned method, the particle size (before expansion) of the heat-expandable microspheres is measured 10 times and the maximum value of the 10-point maximum value of the 10 particle size distributions obtained is 15 μm, and when the minimum value is 9 μm, The particle size (before expansion) of the thermally expandable microspheres is indicated as 9 μm to 15 μm.
作为上述热膨胀性微球，例如可使用在具有弹性的胶囊内含有因热而气化的物质的微球。As the heat-expandable microspheres, for example, microspheres containing a substance vaporized by heat in elastic capsules can be used.
作为上述因热而能够气化的物质，优选使用通过加热至80℃～150℃程度而能够气化的物质，具体而言更优选使用丁烷、异丁烷、丙烷、异丙烷、异戊烷、异辛烷等。As the substance that can be vaporized by heat, a substance that can be vaporized by heating to about 80°C to 150°C is preferably used, and specifically, butane, isobutane, propane, isopropane, and isopentane are more preferably used. , Isooctane, etc.
作为上述具有弹性的胶囊，例如可使用由通过加热至90℃～150℃程度而软化的物质所构成的胶囊，具体而言可列举由偏二氯乙烯－丙烯腈共聚物、聚乙烯醇、聚乙烯醇缩丁醛、聚甲基丙烯酸甲酯、聚丙烯腈、聚偏二氯乙烯、聚砜等所构成的胶囊状物质。As the above-mentioned elastic capsule, for example, a capsule made of a material softened by heating to about 90°C to 150°C can be used, specifically, a vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl alcohol, Capsule-like substances composed of vinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone, etc.
上述热膨胀性微球例如可使用凝聚法(Coacervation method)、界面聚合法等公知惯用的方法进行制造。The above-mentioned heat-expandable microspheres can be produced, for example, using known and commonly used methods such as a coacervation method and an interfacial polymerization method.
作为上述热膨胀性微球，例如也可使用“Matsumoto microsphere”(商品名，松本油脂制药(株)制)、“Microsphere Expancel”(商品名，日本Fillite(株)制)、“DAIFOAM”(商品名，大日精化工业(株)制)等市售品。As the above-mentioned heat-expandable microspheres, for example, "Matsumoto microsphere" (trade name, manufactured by Matsumoto Yuyu Pharmaceutical Co., Ltd.), "Microsphere Expancel" (trade name, manufactured by Nippon Fillite Co., Ltd.), "DAIFOAM" (trade name , Dainichi Seika Co., Ltd.) and other commercially available products.
关于上述热膨胀性微球的含量(配合量)，在兼顾与粘着剂层的良好的密合性及易解体性方面，相对于上述易解体层中所含的上述粘合剂100重量份，优选为1质量份～100质量份，更优选为3质量份～50质量份，进一步优选为5质量份～30质量份。The content (compounding amount) of the thermally expandable microspheres is preferably It is 1-100 mass parts, More preferably, it is 3-50 mass parts, More preferably, it is 5-30 mass parts.
[粘着剂层][adhesive layer]
粘着剂层20、21为与被粘物体粘接的层。作为构成粘着剂层20、21的粘着剂，可使用含有天然橡胶系聚合物、合成橡胶系聚合物、丙烯酸系聚合物、有机硅系聚合物、氨基甲酸酯系聚合物、乙烯基醚系聚合物等的物质。作为上述粘着剂的形态，可列举溶剂系；乳液型粘着剂、水溶性粘着剂等水系；热熔型粘着剂、UV固化型粘着剂、EB固化型粘着剂等无溶剂系等。The adhesive layers 20 and 21 are layers to be adhered to an adherend. As the adhesives constituting the adhesive layers 20 and 21, natural rubber-based polymers, synthetic rubber-based polymers, acrylic polymers, silicone-based polymers, urethane-based polymers, and vinyl ether-based adhesives can be used. Substances such as polymers. Examples of the form of the adhesive include solvent systems; water systems such as emulsion adhesives and water-soluble adhesives; solvent-free systems such as hot-melt adhesives, UV-curable adhesives, and EB-curable adhesives.
上述粘着剂层20、21优选含有丙烯酸系共聚物。作为丙烯酸系共聚物，为赋予亲水性的(甲基)丙烯酸与可与其共聚的其他单体的共聚物，可列举使(甲基)丙烯酸与乙烯基醚反应而得到的(甲基)丙烯酸酯等。The pressure-sensitive adhesive layers 20 and 21 preferably contain an acrylic copolymer. Acrylic copolymers are copolymers of (meth)acrylic acid imparted with hydrophilicity and other monomers that can be copolymerized therewith, and examples include (meth)acrylic acid obtained by reacting (meth)acrylic acid with vinyl ether. Esters etc.
粘着剂层的厚度优选为5μm～100μm，更优选为10μm～80μm，进一步优选为30μm～70μm。粘着剂层的厚度为上述范围时，层的形成容易，被粘物体彼此的粘接性也优异，因而优选。The thickness of the adhesive layer is preferably 5 μm to 100 μm, more preferably 10 μm to 80 μm, even more preferably 30 μm to 70 μm. When the thickness of the pressure-sensitive adhesive layer is within the above range, the formation of the layer is easy, and the adhesiveness between adherends is also excellent, which is preferable.
粘着剂层20、21根据需要也可含有增粘树脂、交联剂、其他添加剂等。Adhesive layers 20 and 21 may contain tackifier resin, crosslinking agent, other additives, etc. as needed.
作为上述增粘树脂，以调节粘着剂层的强粘接性为目的，例如可例示松香系增粘树脂、聚合松香系增粘树脂、聚合松香酯系增粘树脂、松香酚系增粘树脂、稳定化松香酯系增粘树脂、歧化松香酯系增粘树脂、萜烯系增粘树脂、萜烯酚系增粘树脂、石油树脂系增粘树脂等。As the above-mentioned tackifying resin, for the purpose of adjusting the strong adhesiveness of the adhesive layer, for example, rosin-based tackifying resin, polymerized rosin-based tackifying resin, polymerized rosin ester-based tackifying resin, rosin-phenol-based tackifying resin, Stabilized rosin ester-based tackifying resins, disproportionated rosin ester-based tackifying resins, terpene-based tackifying resins, terpene-phenol-based tackifying resins, petroleum resin-based tackifying resins, etc.
作为上述交联剂，以提高粘着剂层的凝聚力为目的，可使用公知的异氰酸酯系交联剂、环氧系交联剂、氮丙啶系交联剂、多价金属盐系交联剂、金属螯合物系交联剂、酮·酰肼系交联剂、噁唑啉系交联剂、碳二亚胺系交联剂、硅烷系交联剂、缩水甘油基(烷氧基)环氧硅烷系交联剂等。As the above-mentioned cross-linking agent, for the purpose of improving the cohesive force of the adhesive layer, known isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, polyvalent metal salt-based cross-linking agents, Metal chelate crosslinking agent, ketone hydrazide crosslinking agent, oxazoline crosslinking agent, carbodiimide crosslinking agent, silane crosslinking agent, glycidyl (alkoxy) ring Oxysilane-based crosslinking agent, etc.
作为上述添加剂，可根据需要在不损害本发明所期望的效果的范围内在粘着剂中任意添加用于调节pH的碱(氨水等)或酸、发泡剂、增塑剂、软化剂、抗氧化剂、玻璃或塑料制的纤维·气球·珠粒·金属粉末等填充剂、颜料·染料等着色剂、pH调节剂、成膜助剂、流平剂、增稠剂、防水剂、消泡剂等公知的物质。另外，也可添加酸催化剂、产酸剂。As the above-mentioned additives, bases (ammonia water, etc.) or acids, foaming agents, plasticizers, softeners, and antioxidants for adjusting pH can be optionally added to the adhesive as needed within the range that does not impair the desired effect of the present invention. , glass or plastic fiber, balloon, beads, metal powder and other fillers, pigments and dyes and other coloring agents, pH regulators, film-forming aids, leveling agents, thickeners, waterproofing agents, defoaming agents, etc. known substances. In addition, an acid catalyst and an acid generator may also be added.
上述酸催化剂、产酸剂例如可以通过光、热的外部刺激而赋予解体性为目的而使用。作为该酸催化剂、产酸剂，可使用与作为上述易解体层中可使用者所例示的物质同样的物质。The above-mentioned acid catalysts and acid generators can be used for the purpose of imparting disintegration properties by external stimulation of light or heat, for example. As the acid catalyst and the acid generator, the same ones as those exemplified as usable in the above-mentioned easily disintegrable layer can be used.
作为在上述粘着剂层的形成中可使用的上述粘着剂，在维持良好的涂布作业性等方面，可使用含有溶剂的粘着剂。作为上述溶剂，例如可使用甲苯、二甲苯、乙酸乙酯、乙酸丁酯、丙酮、甲乙酮、己烷等。另外，使用水系粘着剂作为上述粘着剂时，可使用水、或以水为主体的水性溶剂作为上述溶剂。As the above-mentioned adhesive that can be used for the formation of the above-mentioned adhesive layer, from the viewpoint of maintaining good coating workability, etc., an adhesive containing a solvent can be used. As the solvent, for example, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, hexane or the like can be used. In addition, when a water-based adhesive is used as the above-mentioned adhesive, water or an aqueous solvent mainly containing water can be used as the above-mentioned solvent.
作为剥离片30及31，例如，可列举玻璃纸、牛皮纸、粘土涂层纸、将聚乙烯等的膜层压而成的纸、涂布聚乙烯醇或丙烯酸酯共聚物等树脂而成的纸、在聚酯或聚丙烯等合成树脂膜等上涂布作为剥离剂的氟树脂或有机硅树脂等而成的纸等。As the release sheets 30 and 31, for example, cellophane, kraft paper, clay-coated paper, paper laminated with films such as polyethylene, paper coated with resin such as polyvinyl alcohol or acrylate copolymer, Paper or the like in which fluororesin or silicone resin is coated as a release agent on a synthetic resin film such as polyester or polypropylene.
本实施方式的双面粘胶带所具有的一对粘着剂层可分别为相同的构成，也可分别为不同的构成。A pair of pressure-sensitive adhesive layers which the double-sided adhesive tape of this embodiment has may respectively have the same structure, and may respectively have different structures.
关于本实施方式的双面粘着胶，由于易解体层中含有热膨胀性微球，因此通过加热会发生易解体层中所含有的粘合剂的软化、及上述热膨胀性微球的膨胀，其结果为，相较于使用不含热膨胀性填料的易解体层的情况，能够以更弱的力将被粘物体彼此的粘接解体。With regard to the double-sided adhesive of this embodiment, since the thermally expandable microspheres are contained in the easily disintegrable layer, the softening of the binder contained in the easily disintegrable layer and the expansion of the above-mentioned thermally expandable microspheres will occur by heating. This is because the adherends can be disassembled with a weaker force than when using an easily dismantlable layer that does not contain a thermally expandable filler.
<第2实施方式><Second embodiment>
图2为本发明所涉及的双面粘胶带的实施方式的一例。双面粘胶带2在含有粘合剂11及热膨胀性微球12的易解体层10的两面侧具有粘着剂层20、21，在上述易解体层与上述粘着剂层之间的两者上具有基材膜40、41。在粘着剂层20、21上，可分别层叠有剥离片30、31。Fig. 2 is an example of an embodiment of the double-sided adhesive tape according to the present invention. The double-sided adhesive tape 2 has adhesive layers 20, 21 on both sides of the easily disassembled layer 10 containing the adhesive 11 and thermally expandable microspheres 12, and on both sides between the above-mentioned easily disintegrated layer and the above-mentioned adhesive layer. It has base film 40,41. Release sheets 30, 31 may be laminated on the adhesive layers 20, 21, respectively.
第2实施方式的双面粘胶带为上述<第1实施方式>的双面胶带在上述易解体层与上述粘着剂层之间的两者上进一步具有基材膜40、41的双面粘胶带。此外，关于与上述<第1实施方式>共同的点，将省略说明。The double-sided adhesive tape of the second embodiment is the double-sided adhesive tape of the above-mentioned <First Embodiment>, which further has base films 40, 41 on both of the above-mentioned easily dismantlable layer and the above-mentioned adhesive layer. adhesive tape. Note that descriptions of points common to the aforementioned <First Embodiment> will be omitted.
作为上述基材膜，例如可列举由聚烯烃(例如，聚丙烯、聚乙烯)、聚酯(例如，聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯)、聚苯乙烯、丙烯腈－丁二烯－苯乙烯树脂(ABS树脂)、聚碳酸酯、聚酰亚胺膜、聚氯乙烯、尼龙、聚乙烯醇等构成的塑料系膜；使用纸浆、人造丝、蕉麻、丙烯腈、尼龙、聚酯等得到的不织布、纸、布、或金属箔等。As the above-mentioned base film, for example, polyolefin (for example, polypropylene, polyethylene), polyester (for example, polyethylene terephthalate, polyethylene naphthalate), polystyrene , acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate, polyimide film, polyvinyl chloride, nylon, polyvinyl alcohol and other plastic film; use pulp, rayon, abaca , acrylonitrile, nylon, polyester, etc. to obtain non-woven fabrics, paper, cloth, or metal foil.
在通过双面粘胶带被贴合的被粘物体彼此解体且易解体层断裂后，将双面粘胶带从被粘物体剥离时，上述基材膜可发挥作为支撑体的作用。After the adherends bonded by the double-sided adhesive tape are disintegrated and the easily disintegrable layer is broken, the base film can function as a support when the double-sided adhesive tape is peeled from the adherend.
因此，从容易兼顾基材膜与双面粘胶带的其他层的粘接性(本实施方式中，为基材膜40、41与粘着剂层20、21的粘接性)及作为支撑体的强度出发，优选塑料系膜，更优选聚酯膜。Therefore, it is easy to balance the adhesiveness of the base film and other layers of the double-sided adhesive tape (in this embodiment, the adhesiveness of the base film 40, 41 and the adhesive layer 20, 21) and the support as a support. In terms of strength, plastic film is preferred, and polyester film is more preferred.
另外，以提高上述基材膜与粘着剂层的密合性为目的，可在基材膜的一面或两面施行电晕处理、等离子体处理、底涂处理等。Moreover, corona treatment, plasma treatment, primer treatment, etc. can be given to one side or both surfaces of a base film for the purpose of improving the adhesiveness of the said base film and an adhesive layer.
本实施方式的双面粘胶带通过加热使得易解体层中所含的粘合剂发生软化，且上述热膨胀性微球发生膨胀，从而上述易解体层的凝聚力显著降低而被容易地解体，因此上述加热后，几乎不用施加力即可解体双面粘胶带，将两个以上的被粘物体彼此分离。In the double-sided adhesive tape of this embodiment, the adhesive contained in the easily disintegrable layer is softened by heating, and the above-mentioned heat-expandable microspheres are expanded, so that the cohesive force of the above-mentioned easily disintegrate layer is significantly reduced and is easily disassembled. After the above-mentioned heating, the double-sided adhesive tape can be disassembled almost without applying force, and two or more adhered objects can be separated from each other.
另外，第2实施方式的双面粘胶带进一步在易解体层与粘着剂层之间具有基材膜。解体后的双面粘胶带存在双面粘胶带的残渣残留在被粘物体上的情况。特别是在具有易解体层那样易解体性弱的层的双面粘胶带中，存在难以除去被粘物体上残留的双面粘胶带的残渣的情况。但是，本实施方式的双面粘胶带进一步在易解体层与粘着剂层之间具有基材膜，因此通过握持基材膜部分并拉伸等，可容易地将解体后的双面粘胶带的残渣全体从被粘物体剥下。In addition, the double-sided adhesive tape of the second embodiment further includes a base film between the easily dismantlable layer and the adhesive layer. In the disassembled double-sided adhesive tape, residues of the double-sided adhesive tape may remain on the object to be adhered. In particular, in a double-sided adhesive tape having a layer having a weak disassembly property such as an easily dismantlable layer, it may be difficult to remove the residue of the double-sided adhesive tape remaining on the adherend. However, since the double-sided adhesive tape of the present embodiment further has a base film between the easily disassembled layer and the adhesive layer, the disassembled double-sided adhesive tape can be easily removed by holding and stretching the base film portion. All the residue of the tape is peeled off from the adhered object.
予以说明的是，本实施方式中，例示了由含有粘合剂11及热膨胀性微球12的易解体层10、粘着剂层20、21、基材膜40、41、及剥离片30、31构成的双面粘胶带，但除了上述层结构之外，也可进一步具有任意的层结构。It should be noted that, in this embodiment, the easily disassembled layer 10 containing the adhesive 11 and thermally expandable microspheres 12, the adhesive layer 20, 21, the base film 40, 41, and the release sheet 30, 31 are exemplified. The double-sided adhesive tape constituted may further have an arbitrary layer structure in addition to the above-mentioned layer structure.
例如，作为本发明的双面粘胶带，可使用在上述基材膜40、41与粘着剂层20、21之间，或上述基材膜40、41与易解体层10之间具有发泡体(foam材料)层的双面粘胶带。上述发泡体层发挥缓冲的作用，可对具有发泡体层的双面粘胶带赋予缓冲性。For example, as the double-sided adhesive tape of the present invention, there can be used between the above-mentioned base film 40, 41 and the adhesive layer 20, 21, or between the above-mentioned base film 40, 41 and the easily disassembled layer 10. Body (foam material) layer of double-sided adhesive tape. The foam layer functions as a cushion, and can impart cushioning properties to the double-sided adhesive tape having the foam layer.
本发明的双面粘胶带例如可适合地用于作为被粘物体的刚体与刚体的粘接、刚体与刚体彼此的分离。作为刚体的被粘物体，例如可列举金属板、金属框体、金属壳、玻璃板、塑料板等。通过本发明的双面粘胶带被粘接的两个以上的被粘物体，可为相同种类的被粘物体，也可为不同种类的被粘物体彼此。另外，通过本发明的双面粘胶带被粘接及分离的被粘物体彼此可为相同种类的被粘物体，也可为不同种类的被粘物体彼此。The double-sided adhesive tape of the present invention can be suitably used for, for example, bonding between rigid bodies as adherends and separating rigid bodies from each other. Examples of rigid adherends include metal plates, metal frames, metal shells, glass plates, plastic plates, and the like. Two or more adherends to be bonded by the double-sided adhesive tape of the present invention may be the same type of adherends, or may be different types of adherends. In addition, the adherends bonded and separated by the double-sided adhesive tape of the present invention may be the same type of adherends, or may be different types of adherends.
本发明的双面粘胶带可在再利用、回收时的构件间分离时通过加热容易地进行解体。因此，可适合地用作进行汽车、建材、OA、家电行业等工业用途中的各种产品的部件间固定的双面粘胶带。进行再利用、回收时的大量部件分离、大量标签剥离等时也具有良好的工作效率。The double-sided adhesive tape of the present invention can be easily disassembled by heating when separating members during reuse or collection. Therefore, it can be suitably used as a double-sided adhesive tape for fixing parts between various products in industrial applications such as automobiles, building materials, OA, and home appliance industries. It also has good work efficiency when a large number of parts are separated during recycling or recycling, and a large number of labels are peeled off.
本发明的双面粘胶带也可通过较低的加热温度来实现解体。因此，特别是可适合地用作进行担心因热而引起部件劣化的手机、影像显示设备、计算机等电气产品的部件间固定的双面粘胶带。The double-sided adhesive tape of the present invention can also be disassembled by lower heating temperature. Therefore, it can be suitably used especially as a double-sided adhesive tape for fixing parts of electric products, such as a mobile phone, a video display device, and a computer, in which there is a fear of deterioration of parts due to heat.
《双面粘胶带的制造方法》"Manufacturing method of double-sided adhesive tape"
本发明的双面粘胶带的制造方法如下：制作含有粘合剂及热膨胀性微球的易解体层，在上述易解体层的一侧贴合一方粘着剂层，然后，在上述易解体层的另一侧贴合另一方粘着剂层。The production method of the double-sided adhesive tape of the present invention is as follows: making an easily disassembled layer containing an adhesive and thermally expandable microspheres, laminating an adhesive layer on one side of the above-mentioned easily disassembled layer, and then, The other side of the adhesive tape is attached to the other side of the adhesive layer.
图3为本发明所涉及的双面粘胶带的制造方法的实施方式的一例。首先，准备构成粘着剂层的粘着剂、构成易解体层的粘合剂及热膨胀性微球的混合物。然后，如图3所示，使用敷料器，在剥离片32、34上涂布粘着剂而形成粘着剂层20、21，在剥离片33上涂布粘合剂及热膨胀性微球的混合物而形成易解体层10。然后，在易解体层10的一面贴合粘着剂层20后，在易解体层10的另一面贴合粘着剂层21，得到本发明的双面粘胶带。Fig. 3 is an example of an embodiment of a method for producing a double-sided adhesive tape according to the present invention. First, a mixture of an adhesive constituting the adhesive layer, an adhesive constituting the easily dismantlable layer, and heat-expandable microspheres is prepared. Then, as shown in Figure 3, use applicator, on release sheet 32,34, apply adhesive to form adhesive layer 20,21, on release sheet 33, coat the mixture of adhesive and heat-expandable microsphere to form. The easily dismantlable layer 10 is formed. Then, after bonding the adhesive layer 20 to one surface of the easily dismantlable layer 10, the adhesive layer 21 is bonded to the other surface of the easily dismantlable layer 10 to obtain the double-sided adhesive tape of the present invention.
在抑制上述热膨胀性微球的膨胀方面，上述双面粘胶带的制造优选在80℃以下的温度进行，优选在40℃～80℃的温度进行，更优选在50℃～80℃的范围进行。In terms of suppressing the expansion of the above-mentioned heat-expandable microspheres, the production of the above-mentioned double-sided adhesive tape is preferably carried out at a temperature of 80°C or lower, preferably at a temperature of 40°C to 80°C, and more preferably at a temperature of 50°C to 80°C. .
本实施方式的双面粘胶带的制造方法中，制造的双面粘胶带的两个粘着剂层20、21为相同的构成，因此通过将易解体层与粘着剂层分别成型并贴合，粘着剂层的成型工序为一次即可，能够高效率地制造双面粘胶带。In the method for manufacturing the double-sided adhesive tape of this embodiment, since the two adhesive layers 20 and 21 of the double-sided adhesive tape to be manufactured have the same structure, the easy-to-detachable layer and the adhesive layer are separately molded and bonded together. , The molding process of the adhesive layer only needs to be performed once, and the double-sided adhesive tape can be manufactured efficiently.
《粘接方法·分离方法》《Adhesion method and separation method》
本发明的粘接方法为将被粘物体彼此通过本发明的双面粘胶带进行贴合。The bonding method of the present invention is to bond to-be-adhered objects through the double-sided adhesive tape of the present invention.
另外，本发明的分离方法为，将上述易解体层加热，使通过本发明的粘接方法进行了贴合的上述被粘物体彼此分离。Moreover, the separation method of this invention heats the said easily disintegrable layer, and separates the said to-be-adhered objects bonded by the bonding method of this invention from each other.
图4为本发明的粘接方法的实施方式的一例。如图4所示，使被粘物体50、51与双面粘胶带的两面的粘着剂层20、21接触，使被粘物体彼此贴合而粘接。FIG. 4 is an example of an embodiment of the bonding method of the present invention. As shown in FIG. 4 , the adherends 50 , 51 are brought into contact with the adhesive layers 20 , 21 on both sides of the double-sided adhesive tape, and the adherends are bonded to each other.
图5为本发明所涉及的分离方法的实施方式的一例。FIG. 5 is an example of an embodiment of the separation method according to the present invention.
首先，将双面粘胶带加热。双面粘胶带的加热也可通过将已贴合的上述被粘物体及双面粘胶带全体加热而进行。于是，易解体层10的粘合剂11因热而发生软化，且热膨胀性微球12发生膨胀。此时通过沿使被粘物体50、51彼此分离的方向对双面粘胶带施加力，从而对双面粘胶带施加剥离应力。由于本发明的双面粘胶带的易解体层中含有热膨胀性微球，因此在热膨胀性微球因加热等而发生了膨胀时，能够使被粘物体彼此容易地分离。First, heat the double-sided adhesive tape. The heating of the double-sided adhesive tape can also be carried out by heating the above-mentioned to-be-adhered object and double-sided adhesive tape bonded together. Then, the binder 11 of the easily disintegrable layer 10 is softened by heat, and the heat-expandable microspheres 12 are expanded. At this time, peeling stress is applied to the double-sided adhesive tape by applying force to the double-sided adhesive tape in a direction to separate the adherends 50 , 51 from each other. Since the easily disassembled layer of the double-sided adhesive tape of the present invention contains heat-expandable microspheres, when the heat-expandable microspheres are expanded by heating or the like, adherends can be easily separated from each other.
图6为示意性地示出了本发明的分离方法与其他方法中被粘物体的分离情况的一例的图。图6(a)为本发明的分离方法的一例，示出了双面粘胶带的易解体层10中含有热膨胀性微球12的情况。图6(b)示出了双面粘胶带的易解体层10中不含热膨胀性微球12的情况。Fig. 6 is a diagram schematically showing an example of separation of an adherend in the separation method of the present invention and other methods. Fig. 6(a) is an example of the separation method of the present invention, showing a case where thermally expandable microspheres 12 are contained in the easily disassembled layer 10 of the double-sided adhesive tape. Fig. 6(b) shows the case where the thermally expandable microspheres 12 are not included in the easily disintegrable layer 10 of the double-sided adhesive tape.
如图6(b)所示，易解体层10中未配合热膨胀性微球12时，对粘合剂11所施加的应力分散，粘合剂11的层难以解体。As shown in FIG. 6( b ), when the thermally expandable microspheres 12 are not blended in the easily dismantlable layer 10 , the stress applied to the adhesive 11 is dispersed, and the layer of the adhesive 11 is hardly disassembled.
另一方面，本发明的分离方法中，由于双面粘胶带的易解体层10中含有热膨胀性微球12，因此热膨胀性微球12因加热而发生膨胀，从而如图6(a)所示，对粘合剂11所施加的应力集中，相较于易解体层中未配合热膨胀性微球12的情况，能够以较小的力将易解体层解体，其结果为可容易地分离两个以上的被粘物体。On the other hand, in the separation method of the present invention, since the heat-expandable microspheres 12 are contained in the easily disassembled layer 10 of the double-sided adhesive tape, the heat-expandable microspheres 12 expand due to heating, thereby as shown in FIG. 6( a) It has been shown that the stress concentration applied to the adhesive 11 can disassemble the easily disintegrable layer with a smaller force than the case where the thermally expandable microspheres 12 are not mixed in the easily disintegrate layer. As a result, the two parts can be easily separated. more than one adhered object.
上述分离方法中进行的加热可根据使用的热膨胀性微球、作业环境进行适宜选择，优选为85℃～150℃，更优选为90℃～120℃。本发明的双面粘胶带在通常的使用环境(大概80℃以下)下不会发生解体等，可牢固地粘接被粘物体彼此，另一方面，在加热至上述以上的温度时，可容易地将易解体层解体，其结果为可容易地分离被粘物体。The heating in the above separation method can be appropriately selected according to the heat-expandable microspheres used and the working environment, and is preferably 85°C to 150°C, more preferably 90°C to 120°C. The double-sided adhesive tape of the present invention does not disintegrate under a normal use environment (approximately 80° C. or less), and can firmly bond adherends to each other. On the other hand, when heated to a temperature above the above, it can The easily detachable layer is easily disassembled, and as a result, the adherend can be easily separated.
作为上述加热方法，例如可列举使用干燥机、卤素灯直接或间接地加热上述双面粘胶带的方法。As said heating method, the method of heating the said double-sided adhesive tape directly or indirectly using a dryer or a halogen lamp is mentioned, for example.
上述加热时，可使卤素灯接近或接触上述双面粘胶带，也可通过使卤素灯接近或接触被粘物体而间接地加热上述粘胶带。例如，上述双面粘胶带的端部与上述被粘物体的端部相比露出于外侧时，可使卤素灯接近或接触上述双面粘胶带的端部。During the above-mentioned heating, a halogen lamp may be brought close to or in contact with the above-mentioned double-sided adhesive tape, or the above-mentioned adhesive tape may be heated indirectly by making a halogen lamp close to or in contact with an adherend. For example, when the end of the double-sided adhesive tape is exposed outside the end of the adherend, the halogen lamp may be brought close to or in contact with the end of the double-sided adhesive tape.
在上述加热工序中，优选使用具备卤素灯等的加热装置，将上述双面粘胶带的温度加热至80℃～130℃，更优选加热至85℃～125℃，进一步优选加热至90℃～120℃。另外，上述加热优选在20秒以内进行，更优选为15秒以内，进一步优选在10秒以内的较短时间内进行。In the heating step, it is preferable to heat the temperature of the double-sided adhesive tape to 80°C to 130°C, more preferably to 85°C to 125°C, and even more preferably to 90°C to 90°C, using a heating device equipped with a halogen lamp or the like. 120°C. In addition, the above-mentioned heating is preferably performed within 20 seconds, more preferably within 15 seconds, and still more preferably within a relatively short period of 10 seconds.
具体而言，使用上述卤素灯、干燥机的加热工序为在20秒以内使上述双面粘胶带的温度成为100℃的工序时，可提高物品的解体效率，且可防止被粘物体的热变形等，因此优选。Specifically, when the heating process using the above-mentioned halogen lamp and dryer is a process in which the temperature of the above-mentioned double-sided adhesive tape becomes 100° C. within 20 seconds, the disassembly efficiency of the article can be improved, and the heat of the adherend can be prevented. Deformation etc. are therefore preferred.
另外，作为具备卤素灯的加热装置，例如可使用能以短时间加热一定面积的“平行光型卤素灯加热器”、可局部加热的聚光型卤素灯等，使用平行光型卤素灯加热器时，可一次加热大范围，因此可将加热时间缩短至上述时间。In addition, as a heating device equipped with a halogen lamp, for example, a "parallel light type halogen lamp heater" that can heat a certain area in a short time, a spotlight type halogen lamp that can be locally heated, etc., a parallel light type halogen lamp heater can be used. , a large area can be heated at one time, so the heating time can be shortened to the above time.
上述平行光型卤素灯加热器一次可加热的面积优选为10cm2～500cm2程度。另外，平行光型卤素灯加热器等加热装置为可携带的大小及重量时，在提高上述物品的解体作业的效率化方面优选。上述重量优选为3kg以下，更优选为2kg以下，进一步优选为0.1kg～1kg。The area that can be heated by the parallel light type halogen lamp heater at one time is preferably about 10 cm2 to 500 cm2 . In addition, when a heating device such as a parallel light type halogen lamp heater has a portable size and weight, it is preferable in terms of improving the efficiency of dismantling work of the above-mentioned article. The above-mentioned weight is preferably 3 kg or less, more preferably 2 kg or less, and still more preferably 0.1 kg to 1 kg.
以上述方法加热的上述物品，即使对构成上述物品的两个以上的被粘物体几乎不施加力，或施加较弱的力，也可容易地解体。The above-mentioned article heated by the above-mentioned method can be easily disassembled even if almost no force is applied to the two or more adherends constituting the above-mentioned article, or a relatively weak force is applied.
本发明的双面粘胶带在60℃以下的温度区域下具有非常优异的粘接力，因此例如可用于构成具备复印功能、扫描功能的复印机、多功能机等电子设备的透明顶板与其框体的固定。The double-sided adhesive tape of the present invention has very excellent adhesive force in the temperature range of 60°C or lower, so it can be used, for example, to form the transparent top plate and the frame of electronic equipment such as copiers and multi-function machines with copying and scanning functions. fixed.
作为上述透明顶板，可使用一般的搭载有复印机能、扫描功能的复印机、多功能机中所设置的透明顶板。As the above-mentioned transparent top plate, a transparent top plate installed in a general copier equipped with a copier function or a scanner function, or a multi-function machine can be used.
作为上述透明顶板，例如可使用由玻璃或塑料构成的透明板状刚体。作为上述塑料，例如可使用压克力板、聚碳酸酯板等。As the transparent top plate, for example, a transparent plate-shaped rigid body made of glass or plastic can be used. As said plastic, an acrylic board, a polycarbonate board, etc. can be used, for example.
作为上述透明顶板，可使用与设置有上述透明顶板的复印机等的形状吻合的透明顶板，通常优选使用正方形或长方形者。As the above-mentioned transparent top plate, a transparent top plate conforming to the shape of a copying machine or the like provided with the above-mentioned transparent top plate can be used, and usually a square or rectangular one is preferably used.
上述双面粘胶带若为例如长方形的上述透明顶板，则优选沿着相对的两边的端部进行贴附。此时，上述粘胶带可使用裁切成与上述透明顶板的边的长度相符的大小的粘胶带，例如优选使用宽度为0.5mm～20mm、长度为0.1mm～2.0mm者。If the above-mentioned double-sided adhesive tape is, for example, the above-mentioned rectangular transparent top plate, it is preferable to affix along the ends of both sides facing each other. In this case, the adhesive tape can be cut to a size corresponding to the length of the side of the transparent top plate, for example, it is preferably used with a width of 0.5 mm to 20 mm and a length of 0.1 mm to 2.0 mm.
另外，本发明的双面粘胶带可专门用于构成便携式电子设备的构件的固定。作为上述构件，例如可列举构成电子设备的两个以上的框体或透镜构件。In addition, the double-sided adhesive tape of the present invention can be used exclusively for fixing members constituting portable electronic devices. Examples of the above-mentioned members include two or more housings or lens members constituting an electronic device.
作为上述便携式电子设备，例如可列举具有作为上述构件的框体与透镜构件或其他框体的一者通过上述双面粘胶带而接合的结构的电子设备。As said portable electronic device, the electronic device which has the structure which has the structure which is the housing|casing which is the said member, and one of a lens member or another housing|casing are bonded by the said double-sided adhesive tape is mentioned, for example.
关于上述构件的固定，例如可列举将上述框体或透镜构件的一者与其他框体或透镜构件隔着上述双面粘胶带进行层叠后，使其熟化一定期间的方法。Regarding the fixation of the above-mentioned members, for example, a method of laminating one of the above-mentioned frame body or lens member and the other frame body or lens member through the above-mentioned double-sided adhesive tape, and then aging for a certain period of time is exemplified.
图7为本发明所涉及的分离方法的实施方式的一例。首先，进行上述图6所示的分离方法。此时在被粘物体50、51上残留有解体后的双面粘胶带的残渣。然后，将双面粘胶带冷却。然后，拉伸基材膜41部分，从而能够在基材膜与双面粘胶带的其他层成为一体的状态下将双面粘胶带的残渣全体从被粘物体剥下。FIG. 7 is an example of an embodiment of the separation method according to the present invention. First, the separation method shown in FIG. 6 described above is carried out. At this time, residues of the disassembled double-sided adhesive tape remain on the adherends 50 and 51 . Then, the double-sided adhesive tape was allowed to cool. Then, by stretching the base film 41 portion, the entire residue of the double-sided adhesive tape can be peeled off from the adherend in a state where the base film and other layers of the double-sided adhesive tape are integrated.
关于冷却，只要适当冷却至因加热而软化的双面粘胶带的残渣中的粘合剂的软化程度降低且成为易除去双面粘胶带的残渣而进行处理的状态的温度即可，优选为35℃以下，更优选为25℃以下。About cooling, as long as it is properly cooled to a temperature at which the degree of softening of the adhesive in the residue of the double-sided adhesive tape softened by heating is reduced and the residue of the double-sided adhesive tape is easily removed and processed, preferably It is 35°C or lower, more preferably 25°C or lower.
实施例Example
[制造例1]易解体层(1)[Manufacturing example 1] Easily disassembled layer (1)
以重均分子量为20万的苯乙烯－异戊二烯嵌段共聚物S(三嵌段共聚物与二嵌段共聚物的混合物。上述二嵌段共聚物相对于上述混合物的总量所占的比例为52质量％。相对于上述苯乙烯－异戊二烯嵌段共聚物的全体，聚苯乙烯单元所占的质量比例为15质量％，聚异戊二烯单元的质量比例为85质量％)100质量份、C5石油系增粘树脂(软化点100℃、数均分子量885)40质量份、聚合松香酯系增粘树脂(软化点125℃、数均分子量880)30质量份、作为液状增粘树脂的HV－100(JX日矿日石株式会社制，低分子量聚丁烯)5质量份、作为热膨胀性微球的Matsumoto microsphere F－48(松本油脂制药株式会社制，120℃时的热膨胀率为370％，膨胀开始温度为90℃～100℃，最大膨胀温度为125℃～135℃，粒径(膨胀前)为9μm～15μm)10质量份的配合比进行混合后溶解于甲苯中，从而得到合成橡胶溶液。Styrene-isoprene block copolymer S (a mixture of triblock copolymer and diblock copolymer) with a weight average molecular weight of 200,000. The proportion of the above diblock copolymer relative to the total amount of the above mixture The ratio is 52% by mass. With respect to the whole of the above-mentioned styrene-isoprene block copolymer, the mass ratio of polystyrene units is 15% by mass, and the mass ratio of polyisoprene units is 85% by mass %) 100 parts by mass, 40 parts by mass of C5 petroleum-based tackifying resin (100°C softening point, 885 number average molecular weight), 30 parts by mass of polymerized rosin ester-based tackifying resin (125°C softening point, 880 number average molecular weight), as Liquid tackifier HV-100 (manufactured by JX Nippon Oil Co., Ltd., low-molecular-weight polybutene) 5 parts by mass, Matsumoto microsphere F-48 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) as heat-expandable microspheres The thermal expansion rate is 370%, the expansion start temperature is 90 ° C ~ 100 ° C, the maximum expansion temperature is 125 ° C ~ 135 ° C, the particle size (before expansion) is 9 μm ~ 15 μm) 10 parts by mass are mixed and dissolved in toluene to obtain a synthetic rubber solution.
以使干燥后的厚度成为40μm的方式，使用敷料器将上述溶液涂布于剥离片的表面，在85℃干燥5分钟，从而制造易解体层(1)。The above-mentioned solution was applied to the surface of the release sheet using an applicator so that the thickness after drying would be 40 μm, and dried at 85° C. for 5 minutes to manufacture the easily disintegrable layer (1).
[制造例2]易解体层(2)[Manufacturing example 2] Easily disassembled layer (2)
代替Matsumoto microsphere F－48而使用Microsphere Expancel 053－40(日本Fillite株式会社制，120℃时的热膨胀率为350％，膨胀开始温度为96℃～103℃，最大膨胀温度为138℃～146℃，粒径(膨胀前)为10μm～16μm)10质量份，除此以外，利用与上述制造例1同样的方法制造易解体层(2)。Instead of Matsumoto microsphere F-48, use Microsphere Expancel 053-40 (manufactured by Japan Fillite Co., Ltd., with a thermal expansion rate of 350% at 120°C, an expansion start temperature of 96°C to 103°C, and a maximum expansion temperature of 138°C to 146°C. The easily disintegrable layer (2) was manufactured by the method similar to the said manufacture example 1 except the particle diameter (before swelling) being 10 micrometers - 16 micrometers) and 10 mass parts.
[制造例3]易解体层(3)[Manufacturing example 3] Easily disassembled layer (3)
代替Matsumoto microsphere F－48而使用Microsphere Expancel 031－40(日本Fillite株式会社制、120℃时的热膨胀率为450％，膨胀开始温度为81℃～95℃，最大膨胀温度为120℃～135℃，粒径(膨胀前)为10μm～16μm)10质量份，除此以外，利用与上述制造例1同样的方法制造易解体层(3)。Instead of Matsumoto microsphere F-48, use Microsphere Expancel 031-40 (manufactured by Japan Fillite Co., Ltd., with a thermal expansion rate of 450% at 120°C, an expansion start temperature of 81°C to 95°C, and a maximum expansion temperature of 120°C to 135°C. The easily disintegrable layer (3) was manufactured by the method similar to the said manufacture example 1 except the particle diameter (before expansion) being 10 micrometers - 16 micrometers) and 10 mass parts.
[制造例4]易解体层(4)[Manufacturing Example 4] Easily disassembled layer (4)
代替Matsumoto microsphere F－48而使用Matsumoto microsphere FN－80GSD(松本油脂制药株式会社制，120℃时的热膨胀率为220％，膨胀开始温度为100℃～110℃，最大膨胀温度为125℃～135℃，粒径(膨胀前)为6μm～10μm)10质量份，除此以外，利用与上述制造例1同样的方法制造易解体层(4)。Instead of Matsumoto microsphere F-48, use Matsumoto microsphere FN-80GSD (manufactured by Matsumoto Yuyu Pharmaceutical Co., Ltd., thermal expansion rate at 120°C is 220%, expansion start temperature is 100°C to 110°C, maximum expansion temperature is 125°C to 135°C , particle size (before expansion) is 6 μm-10 μm) 10 mass parts, by the method similar to the above-mentioned Production Example 1, the easily disintegrable layer (4) was produced.
[制造例5]易解体层(5)[Manufacturing Example 5] Easily disassembled layer (5)
代替苯乙烯－异戊二烯嵌段共聚物S而使用重均分子量为30万的苯乙烯－异戊二烯嵌段共聚物T(三嵌段共聚物与二嵌段共聚物的混合物。上述二嵌段共聚物相对于上述混合物的总量所占的比例为20质量％。聚苯乙烯单元在上述苯乙烯－异戊二烯嵌段共聚物的全体中所占的质量比例为15质量％，聚异戊二烯单元的质量比例为85质量％)，除此以外，利用与制造例1同样的方法制造易解体层(5)。Instead of the styrene-isoprene block copolymer S, a styrene-isoprene block copolymer T (a mixture of a triblock copolymer and a diblock copolymer. The above-mentioned The ratio of the diblock copolymer to the total amount of the above mixture is 20 mass %. The mass ratio of the polystyrene unit in the whole of the above-mentioned styrene-isoprene block copolymer is 15 mass % , the mass ratio of the polyisoprene unit was 85% by mass), and the easily disintegrable layer (5) was produced in the same manner as in Production Example 1 except that.
[制造例6]易解体层(6)[Manufacturing Example 6] Easily disassembled layer (6)
将Matsumoto microsphere F－48(松本油脂制药株式会社制)的使用量由10质量份变更为20质量份，除此以外，利用与制造例1同样的方法制造易解体层(6)。The easily disintegrable layer ( 6 ) was produced in the same manner as in Production Example 1 except that the amount of Matsumoto microsphere F-48 (manufactured by Matsumoto Yuyu Pharmaceutical Co., Ltd.) used was changed from 10 parts by mass to 20 parts by mass.
[制造例7]易解体层(7)[Manufacturing Example 7] Easily disassembled layer (7)
将Matsumoto microsphere F－48(松本油脂制药株式会社制)的使用量由10质量份变更为5质量份，除此以外，利用与制造例1同样的方法制造易解体层(7)。The easily disintegrable layer ( 7 ) was produced in the same manner as Production Example 1 except that the usage-amount of Matsumoto microsphere F-48 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) was changed from 10 parts by mass to 5 parts by mass.
[制造例8]易解体层(8)[Manufacturing Example 8] Easily disassembled layer (8)
将易解体层的厚度由40μm变更为20μm，除此以外，利用与制造例1同样的方法制造易解体层(8)。The easily disintegrable layer (8) was produced by the method similar to manufacture example 1 except having changed the thickness of the easily disintegrate layer from 40 micrometers to 20 micrometers.
[制造例9]易解体层(9)[Manufacturing Example 9] Easily disassembled layer (9)
将LA2250(株式会社Kurary制，丙烯酸系热塑性弹性体)100质量份、Matsumotomicrosphere F－48(松本油脂制药株式会社制，120℃时的热膨胀率为370％，膨胀开始温度为90℃～100℃，最大膨胀温度为125℃～135℃，粒径(膨胀前)为9μm～15μm)10质量份与甲苯混合，从而得到不挥发成分为40质量％的丙烯酸树脂组合物。LA2250 (manufactured by Kurary Co., Ltd., acrylic thermoplastic elastomer) 100 parts by mass, Matsumotomicrosphere F-48 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., thermal expansion rate at 120°C is 370%, expansion start temperature is 90°C to 100°C, The maximum expansion temperature is 125° C. to 135° C., and the particle diameter (before expansion) is 9 μm to 15 μm) is mixed with 10 mass parts of toluene to obtain an acrylic resin composition having a nonvolatile content of 40 mass %.
以使干燥后的厚度成为40μm的方式，使用敷料器将上述丙烯酸树脂组合物涂布于剥离片的表面，在85℃干燥5分钟，从而制造易解体层(9)。The above-mentioned acrylic resin composition was applied to the surface of the release sheet using an applicator so that the thickness after drying would be 40 μm, and dried at 85° C. for 5 minutes to manufacture an easily disintegrable layer (9).
[制造例10]易解体层(10)[Manufacturing Example 10] Easily disassembled layer (10)
在具备搅拌机、回流冷凝器、温度计、滴液漏斗及氮气导入口的反应容器内，将丙烯酸丁酯44.9质量份、丙烯酸2－乙基己酯50质量份、丙烯酸2质量份、乙酸乙烯酯3质量份、丙烯酸4－羟基丁酯0.1质量份、及作为聚合引发剂的2,2'－偶氮双异丁腈0.1质量份溶解于乙酸乙酯100质量份中，在70℃聚合10小时，从而得到重均分子量为80万的丙烯酸系共聚物溶液。然后，相对于上述丙烯酸系共聚物100质量份，添加聚合松香酯系增粘树脂(软化点为125℃，数均分子量为880)30质量份，加入乙酸乙酯并混合，从而得到不挥发成分为45质量％的丙烯酸系共聚物组合物(1)。44.9 parts by mass of butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of acrylic acid, 3 parts by mass of vinyl acetate, and Parts by mass, 0.1 part by mass of 4-hydroxybutyl acrylate, and 0.1 part by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator were dissolved in 100 parts by mass of ethyl acetate, and polymerized at 70°C for 10 hours, Thus, an acrylic copolymer solution having a weight average molecular weight of 800,000 was obtained. Then, 30 parts by mass of a polymerized rosin ester-based tackifier resin (softening point: 125° C., number average molecular weight: 880) was added to 100 parts by mass of the above-mentioned acrylic copolymer, and ethyl acetate was added and mixed to obtain a non-volatile component It is an acrylic copolymer composition (1) of 45% by mass.
将上述丙烯酸系共聚物组合物(1)100质量份、“CORONATE L－45”(日本聚氨酯工业(株)制，异氰酸酯系交联剂，固体成分为45质量％)1.1质量份、Matsumoto microsphereF－48(松本油脂制药株式会社制，120℃时的热膨胀率为370％，膨胀开始温度为90℃～100℃，最大膨胀温度为125℃～135℃，粒径(膨胀前)为9μm～15μm)10质量份混合后，以使干燥后的厚度成为40μm的方式，使用敷料器涂布于剥离片的表面，在85℃干燥5分钟，从而形成易解体层(10)。100 parts by mass of the above-mentioned acrylic copolymer composition (1), 1.1 parts by mass of "CORONATE L-45" (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based crosslinking agent, solid content: 45 mass %), Matsumoto microsphere F- 48 (manufactured by Matsumoto Yuyu Pharmaceutical Co., Ltd., thermal expansion rate at 120°C is 370%, expansion start temperature is 90°C to 100°C, maximum expansion temperature is 125°C to 135°C, particle size (before expansion) is 9 μm to 15 μm) After mixing 10 parts by mass, it was applied to the surface of a release sheet using an applicator so that the thickness after drying would be 40 μm, and dried at 85° C. for 5 minutes to form an easily disintegrable layer (10).
[制造例11]易解体层(11)[Manufacturing Example 11] Easily disassembled layer (11)
代替丙烯酸丁酯44.9质量份、丙烯酸2－乙基己酯50质量份、丙烯酸2质量份、乙酸乙烯酯3质量份与丙烯酸4－羟基丁酯0.1质量份而使用丙烯酸丁酯20质量份及丙烯酸2－乙基己酯74.9质量份，除此以外，利用与制造例10同样的方法形成易解体层(11)。Instead of 44.9 parts by mass of butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of acrylic acid, 3 parts by mass of vinyl acetate, and 0.1 part by mass of 4-hydroxybutyl acrylate, 20 parts by mass of butyl acrylate and acrylic acid The easily disintegrable layer (11) was formed by the method similar to manufacture example 10 except 74.9 mass parts of 2-ethylhexyl esters.
[比较制造例1]中芯层(1)[Comparative Manufacturing Example 1] Core Layer (1)
未使用Matsumoto microsphere F－48(松本油脂制药株式会社制)，除此以外，利用与制造例1同样的方法制造中芯层(1)。The core layer ( 1 ) was produced in the same manner as in Production Example 1 except that Matsumoto microsphere F-48 (manufactured by Matsumoto Yuyu Pharmaceutical Co., Ltd.) was not used.
[比较制造例2]中芯层(2)[Comparative Manufacturing Example 2] Core Layer (2)
未使用Matsumoto microsphere F－48(松本油脂制药株式会社制)，除此以外，利用与制造例9同样的方法制造中芯层(2)。The core layer (2) was produced in the same manner as in Production Example 9 except that Matsumoto microsphere F-48 (manufactured by Matsumoto Yuyu Pharmaceutical Co., Ltd.) was not used.
[比较制造例3]中芯层(3)[Comparative Manufacturing Example 3] Core Layer (3)
未使用Matsumoto microsphere F－48(松本油脂制药株式会社制)，除此以外，利用与制造例10同样的方法制造中芯层(3)。The core layer (3) was produced by the same method as in Production Example 10 except that Matsumoto microsphere F-48 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) was not used.
[比较制造例4]中芯层(4)[Comparative Manufacturing Example 4] Core Layer (4)
未使用Matsumoto microsphere F－48(松本油脂制药株式会社制)，除此以外，利用与制造例11同样的方法制造中芯层(4)。A core layer ( 4 ) was produced in the same manner as in Production Example 11 except that Matsumoto microsphere F-48 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) was not used.
[调制例1]贴着剂层(1)[Preparation example 1] Adhesive layer (1)
在具备搅拌机、回流冷凝器、温度计、滴液漏斗及氮气导入口的反应容器内，将丙烯酸丁酯44.9质量份、丙烯酸2－乙基己酯50质量份、丙烯酸2质量份、乙酸乙烯酯3质量份、丙烯酸4－羟基丁酯0.1质量份、及作为聚合引发剂的2,2'－偶氮双异丁腈0.1质量份溶解于乙酸乙酯100质量份中，在70℃聚合10小时，从而得到重均分子量为80万的丙烯酸系共聚物溶液。然后，相对于上述丙烯酸系共聚物100质量份，添加聚合松香酯系增粘树脂(软化点为125℃，数均分子量为880)30质量份，加入乙酸乙酯并混合，从而得到不挥发成分为45质量％的丙烯酸系共聚物组合物(1)。44.9 parts by mass of butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of acrylic acid, 3 parts by mass of vinyl acetate, and Parts by mass, 0.1 part by mass of 4-hydroxybutyl acrylate, and 0.1 part by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator were dissolved in 100 parts by mass of ethyl acetate, and polymerized at 70°C for 10 hours, Thus, an acrylic copolymer solution having a weight average molecular weight of 800,000 was obtained. Then, 30 parts by mass of a polymerized rosin ester-based tackifier resin (softening point: 125° C., number average molecular weight: 880) was added to 100 parts by mass of the above-mentioned acrylic copolymer, and ethyl acetate was added and mixed to obtain a non-volatile component It is an acrylic copolymer composition (1) of 45% by mass.
将上述丙烯酸系共聚物组合物(1)100质量份与“CORONATE L－45”(日本聚氨酯工业(株)制、异氰酸酯系交联剂、固体成分为45质量％)1.1质量份混合而得到粘着剂，以使干燥后的厚度成为50μm的方式，使用敷料器涂布于剥离片的表面，在85℃干燥5分钟，从而形成粘着剂层(1)。Adhesion was obtained by mixing 100 parts by mass of the above acrylic copolymer composition (1) with 1.1 parts by mass of "CORONATE L-45" (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based crosslinking agent, solid content: 45% by mass). The adhesive was applied to the surface of the release sheet using an applicator so that the thickness after drying would be 50 μm, and dried at 85° C. for 5 minutes to form an adhesive layer (1).
(实施例1)(Example 1)
如图8(a)所示，将上述粘着剂层(1)22贴合于厚度为16μm的聚对苯二甲酸乙二醇酯膜42上(贴合品)。As shown in FIG. 8( a ), the adhesive layer ( 1 ) 22 was bonded to a polyethylene terephthalate film 42 having a thickness of 16 μm (bonded product).
另一方面，将另一粘着剂层(1)23与易解体层(1)15分别贴合于厚度为16μm的聚对苯二甲酸乙二醇酯膜43的两面。然后，将上述易解体层(1)15表面的剥离片除去，并贴合于预先制作的上述聚对苯二甲酸乙二醇酯膜42及粘着剂层(1)22的贴合品后，以4kgf/cm2进行加压而层压，从而制作实施例1的双面粘胶带。On the other hand, the other adhesive layer (1) 23 and the easily dismantlable layer (1) 15 were bonded to both surfaces of a polyethylene terephthalate film 43 having a thickness of 16 μm, respectively. Then, the peeling sheet on the surface of the above-mentioned easily disintegrable layer (1) 15 is removed, and after bonding to the bonded product of the above-mentioned polyethylene terephthalate film 42 and the adhesive layer (1) 22 prepared in advance, The double-sided adhesive tape of Example 1 was produced by laminating under pressure at 4 kgf/cm2 .
(实施例2)(Example 2)
代替上述易解体层(1)而使用上述易解体层(2)，除此以外，与上述实施例1同样地操作，制作实施例2的双面粘胶带。Except having used the said easily dismantlable layer (2) instead of the said easily dismantlable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of Example 2.
(实施例3)(Example 3)
代替上述易解体层(1)而使用上述易解体层(3)，除此以外，与上述实施例1同样地操作，制作实施例3的双面粘胶带。The double-sided adhesive tape of Example 3 was produced in the same manner as in Example 1 above except that the above-mentioned easily-detachable layer (3) was used instead of the above-mentioned easily-detachable layer (1).
(实施例4)(Example 4)
代替上述易解体层(1)而使用上述易解体层(4)，除此以外，与上述实施例1同样地操作，制作实施例4的双面粘胶带。Except having used the said easily dismantlable layer (4) instead of the said easily dismantlable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of Example 4.
(实施例5)(Example 5)
代替上述易解体层(1)而使用上述易解体层(5)，除此以外，与上述实施例1同样地操作，制作实施例5的双面粘胶带。Except having used the said easily dismantlable layer (5) instead of the said easily dismantlable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of Example 5.
(实施例6)(Example 6)
代替单侧的16μm的聚对苯二甲酸乙二醇酯膜而使用厚度为16μm的聚对苯二甲酸乙二醇酯膜与厚度为100μm的聚烯烃系发泡体的层叠体，并使发泡体侧接触易解体层，除此以外，与上述实施例1同样地操作，制作实施例6的双面粘胶带。Instead of the 16 μm polyethylene terephthalate film on one side, a laminate of a polyethylene terephthalate film with a thickness of 16 μm and a polyolefin-based foam with a thickness of 100 μm was used, and the foam The double-sided adhesive tape of Example 6 was produced in the same manner as in Example 1 above, except that the foam side was in contact with the easily disassembled layer.
(实施例7)(Example 7)
代替上述易解体层(1)而使用上述易解体层(6)，除此以外，与上述实施例1同样地操作，制作实施例7的双面粘胶带。Except having used the said easily dismantlable layer (6) instead of the said easily dismantlable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of Example 7.
(实施例8)(Embodiment 8)
代替上述易解体层(1)而使用上述易解体层(7)，除此以外，与上述实施例1同样地操作，制作实施例8的双面粘胶带。The double-sided adhesive tape of Example 8 was produced in the same manner as in Example 1 above except that the above-mentioned easily-detachable layer (7) was used instead of the above-mentioned easily-detachable layer (1).
(实施例9)(Example 9)
代替上述易解体层(1)而使用上述易解体层(8)，除此以外，与上述实施例1同样地操作，制作实施例9的双面粘胶带。Except having used the said easily dismantlable layer (8) instead of the said easily dismantlable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of Example 9.
(实施例10)(Example 10)
代替上述易解体层(1)而使用上述易解体层(9)，除此以外，与上述实施例1同样地操作，制作实施例10的双面粘胶带。Except having used the said easily dismantlable layer (9) instead of the said easily dismantlable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of Example 10.
(实施例11)(Example 11)
代替上述易解体层(1)而使用上述易解体层(10)，除此以外，与上述实施例1同样地操作，制作实施例11的双面粘胶带。The double-sided adhesive tape of Example 11 was produced in the same manner as in Example 1 above except that the above-mentioned easily-detachable layer (10) was used instead of the above-mentioned easily-detachable layer (1).
(实施例12)(Example 12)
代替上述易解体层(1)而使用上述易解体层(11)，除此以外，与上述实施例1同样地操作，制作实施例12的双面粘胶带。Except having used the above-mentioned easily-disintegrable layer (11) instead of the above-mentioned easily-disintegrable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of Example 12.
(比较例1)(comparative example 1)
代替上述易解体层(1)而使用上述中芯层(1)，除此以外，与上述实施例1同样地操作，制作比较例1的双面粘胶带。Except having used the said core layer (1) instead of the said easily disintegrable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of the comparative example 1.
(比较例2)(comparative example 2)
代替上述易解体层(1)而使用上述中芯层(2)，除此以外，与上述实施例1同样地操作，制作比较例2的双面粘胶带。Except having used the said core layer (2) instead of the said easily dismantlable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of the comparative example 2.
(比较例3)(comparative example 3)
代替上述易解体层(1)而使用上述中芯层(3)，除此以外，与上述实施例1同样地操作，制作比较例3的双面粘胶带。Except having used the said core layer (3) instead of the said easily dismantlable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of the comparative example 3.
(比较例4)(comparative example 4)
代替上述易解体层(1)而使用上述中芯层(4)，除此以外，与上述实施例1同样地操作，制作比较例4的双面粘胶带。Except having used the said core layer (4) instead of the said easily dismantlable layer (1), it carried out similarly to the said Example 1, and produced the double-sided adhesive tape of the comparative example 4.
对上述实施例及比较例中得到的双面粘胶带进行以下的评价。得到的结果如表1、表2所示。The following evaluations were performed on the double-sided adhesive tapes obtained in the above Examples and Comparative Examples. The obtained results are shown in Table 1 and Table 2.
<常温时的180度剥离粘接力><180°C Peel Adhesion at Room Temperature>
180度剥离粘接力根据JIS Z 0237进行测定。The 180-degree peel adhesive force was measured in accordance with JIS Z 0237.
将双面粘胶带的其中一面的剥离片剥下，以厚度为50μm的铝箔支持其粘着剂层。将上述有支持的粘胶带切成20mm宽度后，将另一面的剥离片剥下，将此粘着剂层贴合于SUS板的经脱脂处理的平滑表面，制成试验片。The release sheet on one side of the double-sided adhesive tape was peeled off, and the adhesive layer was supported by an aluminum foil having a thickness of 50 μm. After cutting the above-mentioned backed adhesive tape to a width of 20 mm, the release sheet on the other side was peeled off, and this adhesive layer was attached to the degreased smooth surface of the SUS board to prepare a test piece.
将上述试验片在23℃环境下放置30分钟后，在相同环境下使用TENSILON拉伸试验机[株式会社A&D制，型号：RTM－100]，测定将构成上述试验片的双面粘胶带从SUS板沿180度方向以300mm/分钟的速度剥离时的粘接力。After leaving the above test piece in an environment of 23°C for 30 minutes, use a TENSILON tensile testing machine [manufactured by A&D Co., Ltd., model: RTM-100] under the same environment to measure the thickness of the double-sided adhesive tape constituting the above test piece. The adhesive force when the SUS board is peeled at a speed of 300mm/min along the direction of 180 degrees.
<加热后的180度剥离粘接力><180 degree peel adhesion after heating>
180度剥离粘接力根据JIS Z 0237进行测定。The 180-degree peel adhesive force was measured in accordance with JIS Z 0237.
将双面粘胶带的其中一面的剥离片剥下，以厚度为50μm的铝箔支持其粘着剂层。将上述有支持的粘胶带切成20mm宽度后，将另一面的剥离片剥下，将此粘着剂层贴合于SUS板的经脱脂处理的平滑表面，制成试验片。The release sheet on one side of the double-sided adhesive tape was peeled off, and the adhesive layer was supported by an aluminum foil having a thickness of 50 μm. After cutting the above-mentioned backed adhesive tape to a width of 20 mm, the release sheet on the other side was peeled off, and this adhesive layer was attached to the degreased smooth surface of the SUS board to prepare a test piece.
将上述试验片在120℃环境下放置30分钟后，在相同环境下使用TENSILON拉伸试验机[株式会社A&D制，型号：RTM－100]，测定将构成上述试验片的双面粘胶带从SUS板沿180度方向以300mm/分钟的速度剥离时的粘接力。After leaving the above test piece in an environment of 120°C for 30 minutes, use a TENSILON tensile testing machine [manufactured by A&D Co., Ltd., model: RTM-100] under the same environment to measure the The adhesive force when the SUS board is peeled at a speed of 300mm/min along the direction of 180 degrees.
<加热后的解体性试验><Disassembly test after heating>
图9为说明解体性试验的方法的图。首先，将实施例及比较例中得到的双面粘胶带切成一边(外形)的长度为20mm的正方形。将上述切断后的双面粘胶带202贴附于长度为100mm、宽度为30mm及厚度为1mm的SUS板201的经脱脂处理的平滑表面。Fig. 9 is a diagram illustrating a method of a disassembly test. First, the double-sided adhesive tapes obtained in Examples and Comparative Examples were cut into squares with a length of one side (outer shape) of 20 mm. The cut double-sided adhesive tape 202 was attached to the degreasing smooth surface of the SUS board 201 having a length of 100 mm, a width of 30 mm, and a thickness of 1 mm.
然后，将SUS板201’的经脱脂处理的平滑表面贴附于上述双面粘胶带202的与贴附SUS板201的面相反侧的面，以5kg荷重辊进行1次往复加压，制成试验片。Then, the degreased smooth surface of the SUS plate 201' was attached to the surface of the double-sided adhesive tape 202 opposite to the surface on which the SUS plate 201 was attached, and a 5 kg load roller was used to perform reciprocating pressure once to produce into a test piece.
将制作的试验片在120℃环境下放置30分钟后，在23℃下取出，在15秒以内手持SUS板201及201’的两端，在垂直方向进行剥离，对此时SUS板的分离容易程度进行评价。Put the produced test piece at 120°C for 30 minutes, take it out at 23°C, hold both ends of the SUS plate 201 and 201' within 15 seconds, and peel it off in the vertical direction. At this time, the separation of the SUS plate is easy degree is evaluated.
○：双面粘胶带在易解体层内发生了断裂，从而不用施加任何力就使2块SUS板分离。其结果为不用施加任何力即可解体试验片。◯: The double-sided adhesive tape was broken in the easily disassembled layer, and the two SUS boards were separated without applying any force. As a result, the test piece can be disassembled without applying any force.
△：2块SUS板虽然粘接，但通过施加很小的力就可将它们分离，并可解体上述试验片。△: Although two SUS plates were bonded, they could be separated by applying a small force, and the above-mentioned test piece could be disassembled.
×：若不用两手施加够大的力则不能分离2块SUS板并解体上述试验片。×: The above-mentioned test piece cannot be separated without applying a sufficiently large force with both hands and dismantling the two SUS plates.
<构成易解体层及中芯层的粘合剂的动态粘弹性(储能模量)测定><Measurement of dynamic viscoelasticity (storage modulus) of the adhesive constituting the easily disintegrated layer and the core layer>
将易解体层及中芯层的制造中所使用的粘合剂溶解于甲苯后，以使干燥后的厚度成为100μm的方式，使用敷料器涂布于脱模衬垫的表面，在85℃干燥5分钟，从而形成多片厚度为100μm的粘合剂层。After dissolving the binder used in the production of the easily disintegrable layer and the core layer in toluene, apply it on the surface of the release liner with an applicator so that the thickness after drying becomes 100 μm, and dry at 85°C 5 minutes, thereby forming a plurality of adhesive layers with a thickness of 100 μm.
然后，将使用相同的粘合剂所得到的粘合剂层重叠，从而制成厚度为2mm的由粘合剂层构成的试验片。Then, the adhesive layer obtained using the same adhesive was laminated|stacked, and the test piece which consists of an adhesive layer with a thickness of 2 mm was produced.
在TA Instruments日本公司制的粘弹性试验机(ARES 2kSTD)上安装直径为7.9mm的平行板。将上述试验片以压缩荷重50g夹入上述平行板，在频率1Hz、温度范围－60～150℃、及升温速度2℃/min的条件下，对23℃下的储能模量(G23)及120℃下的储能模量(G120)进行测定。A parallel plate with a diameter of 7.9 mm was attached to a viscoelasticity testing machine (ARES 2kSTD) manufactured by TA Instruments Japan. The above-mentioned test piece is clamped into the above-mentioned parallel plate with a compression load of 50g, and the storage modulus (G23 ) at 23°C is compared under the conditions of frequency 1Hz, temperature range -60-150°C, and heating rate 2°C/min. and the storage modulus (G120 ) at 120°C were measured.
[表1][Table 1]
[表2][Table 2]
[表3][table 3]
符号说明Symbol Description
1、2：双面粘胶带1, 2: Double-sided adhesive tape
10：易解体层10: Detachable layer
11：粘合剂11: Adhesive
12：热膨胀性微球(膨胀前)12: Thermally expandable microspheres (before expansion)
12’：热膨胀性微球(膨胀后)12': Heat-expandable microspheres (after expansion)
20、21：粘着剂层(1)20, 21: Adhesive layer (1)
30、31、32、33、34：剥离片30, 31, 32, 33, 34: Release sheet
40、41：基材膜40, 41: substrate film
50、51：被粘物体50, 51: sticky object
3、4：双面粘胶带3, 4: Double-sided adhesive tape
14：热膨胀性微球(膨胀前)14: Thermally expandable microspheres (before expansion)
15：易解体层(1)15: Detachable layer (1)
16：中芯层(1)16: core layer(1)
22、23：粘着剂层(1)22, 23: Adhesive layer (1)
42、43：聚对苯二甲酸乙二醇酯膜42, 43: Polyethylene terephthalate film
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014230681 | 2014-11-13 | ||
| JP2014-230681 | 2014-11-13 | ||
| PCT/JP2015/080553WO2016076131A1 (en) | 2014-11-13 | 2015-10-29 | Double-sided adhesive tape, article, and separation method |
| Publication Number | Publication Date |
|---|---|
| CN107075323Atrue CN107075323A (en) | 2017-08-18 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580056803.1APendingCN107075323A (en) | 2014-11-13 | 2015-10-29 | Double-sided adhesive tape, article and separation method |
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| JP (2) | JP6120123B2 (en) |
| CN (1) | CN107075323A (en) |
| TW (1) | TWI669373B (en) |
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| SE01 | Entry into force of request for substantive examination | ||
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| RJ01 | Rejection of invention patent application after publication | Application publication date:20170818 |