JP6690416B2 - Laminate having hot-melt adhesive layer for electromagnetic induction heating, adhesive structure using the same, and peeling method - Google Patents
Laminate having hot-melt adhesive layer for electromagnetic induction heating, adhesive structure using the same, and peeling method Download PDFInfo
- Publication number
- JP6690416B2 JP6690416B2 JP2016113216A JP2016113216A JP6690416B2 JP 6690416 B2 JP6690416 B2 JP 6690416B2 JP 2016113216 A JP2016113216 A JP 2016113216A JP 2016113216 A JP2016113216 A JP 2016113216A JP 6690416 B2 JP6690416 B2 JP 6690416B2
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- JP
- Japan
- Prior art keywords
- melt adhesive
- hot melt
- adhesive layer
- electromagnetic induction
- induction heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Images
Description
本発明は、厚みが１ｍｍ以上である支持体、金属層（Ａ）、熱可塑性ホットメルト接着剤層（Ｃ）の順で積層されてなる電磁誘導加熱用ホットメルト接着シート、それを用いた物と、被着体と、を接着してなる接着構造物に関する。
また、電磁誘導加熱用ホットメルト接着シート、接着構造物の剥離方法に関する。
なお、本明細書において、電磁誘導加熱用ホットメルト接着シートとは、電磁誘導加熱用ホットメルト接着剤層を有する積層物のことである。
The present invention relates to a hot melt adhesive sheet for electromagnetic induction heating, which is formed by laminating a support having a thickness of 1 mm or more, a metal layer (A), and a thermoplastic hot melt adhesive layer (C) in this order, and a product using the same. And an adherend.
Further, the present invention relates to a hot melt adhesive sheet for electromagnetic induction heating and a method for separating an adhesive structure.
In the present specification, the hot melt adhesive sheet for electromagnetic induction heating is a laminate having a hot melt adhesive layer for electromagnetic induction heating.
ホットメルト接着シートとは、溶剤不含の接着剤であり、加熱されて溶融した状態で接着すべき基材に塗布され、そして固化後に接着作用を発揮するものである。乾燥不要等の多彩な利点から、ホットメルト接着シートは、慣用の溶剤に基づく接着剤に対する経済的でかつ環境に優しい代替品として、特にラベル、包装、家具、繊維材料及び履き物など工業的に益々使用されつつある。
例えば、プリン、ゼリー、みつ豆、ヨーグルト、乳酸飲料、豆腐などの食品の包装分野には、ポリエチレン、ポリプロピレン、ポリスチレン、ポリエステルなどの硬質乃至半硬質樹脂のブロー成形、インジエクシヨン成形、インジエクシヨンブロー成形法などによる容器、更にはこれらの樹脂やポリ塩化ビニル樹脂などの単層シートまたはこれらの樹脂をそれの一層とする共押出法などによる積層シートを、真空成形、圧空成形などの適当な二次成形法によって成形したカツプやトレーなどの容器が使用されており、これらの容器の蓋材のシール層には、ホットメルト接着シートが用いられている（特許文献１）。しかし、支持体の厚みが１ｍｍ未満の樹脂フィルムやシート状の物のみである。
The hot-melt adhesive sheet is a solvent-free adhesive agent, which is applied in a heated and molten state to a substrate to be adhered, and exhibits an adhesive action after solidification. Due to its versatile advantages such as no drying, hot melt adhesive sheets are an increasingly economical and environmentally friendly alternative to conventional solvent-based adhesives, especially in industrial applications such as labels, packaging, furniture, textile materials and footwear. It is being used.
For example, in the packaging field of foods such as pudding, jelly, bean beans, yogurt, lactic acid beverages, tofu, blow molding of rigid or semi-rigid resin such as polyethylene, polypropylene, polystyrene and polyester, infusion molding, infusion blow molding method. Suitable containers such as vacuum molding, air pressure molding, etc., containers, and also single-layer sheets of these resins and polyvinyl chloride resins, or laminated sheets of these resins as a single layer by coextrusion method, etc. Containers such as cups and trays formed by the method are used, and a hot-melt adhesive sheet is used for the sealing layer of the lid material of these containers (Patent Document 1). However, the support is only a resin film or sheet-like product having a thickness of less than 1 mm.
その一方、ホットメルト接着シートが建築やリフォームや木工などの分野に使用される例もある。
従来、建築物、構造物の外表面、内壁、間仕切壁等の表面に合板、石膏ボード、珪酸カルシュウム板、陶磁器タイル、金属板等の内外装材を接合する方法としては、釘やボルト等の接合部品を用いる方法が古くから用いられている。この接合方法は、作業が比較的簡易ではあるが、点接合であるために応力がその一点に集中してしまい、これを分散させるには広範囲に釘やボルトを打ち込まなければならないし、作業的にも煩雑になる。また、接合部分に突起や肉盛が表れて美観を損ねる。これらの方法に変わって、溶剤系、水系又はエポキシ樹脂等の液状接着剤を使用した接合方法が用いられるようになってきた。この接着剤による接合方法では、面接合になるため接合部分全体に応力が均一になり、耐久性が向上した。しかも接合部分の表面が平滑になり、美観の面からも好ましい。しかし、これらの液状接着剤を使用した接合方法は、接着剤を塗布した後、接着力が発現するまでに一定の時間が必要であり、接着剤塗布後に所定時間の養生が必要である。このために大量作業をする場合には連続的な接合作業が行なえない問題がある。このような問題を改善する接合方法として、両面粘着テープを使用する方法が行なわれるようになってきた。しかし、この接合方法は、両面粘着テープの貼着と同時に接着性が発現するため、所望の位置からずれた際の修正が困難である。さらに被着体の表面が粗面になっている場合に、粘着面との接触面積が充分ではなく、材料の重量による応力や、接着後の温度、湿度等の気候変化による建築材料の伸縮や反りにより発生する応力によって、貼着した粘着テープが経時的に剥がれやすくなる等の問題がある。従って、両面粘着テープを使用した接合方法においても、長時間の接合力には信頼性が得られないといった問題があった。
On the other hand, there are cases where hot-melt adhesive sheets are used in fields such as construction, remodeling and woodworking.
Conventionally, as a method of joining interior / exterior materials such as plywood, gypsum board, calcium silicate board, ceramic tile, and metal plate to the surface of the building, structure outer surface, inner wall, partition wall, etc., nails, bolts, etc. The method of using joined parts has been used for a long time. This joining method is relatively simple in work, but since it is point joining, stress concentrates at one point, and to disperse this, it is necessary to drive nails and bolts over a wide range, Becomes complicated. In addition, protrusions and build-up appear at the joints, which spoils the appearance. Instead of these methods, a joining method using a liquid adhesive such as a solvent type, an aqueous type or an epoxy resin has come to be used. With this bonding method using an adhesive, surface bonding is performed, so that stress is uniform over the entire bonded portion, and durability is improved. Moreover, the surface of the joint is smooth, which is preferable from the viewpoint of aesthetics. However, the joining method using these liquid adhesives requires a certain period of time after application of the adhesive until the adhesive strength is developed, and a certain period of curing is required after the application of the adhesive. Therefore, there is a problem that continuous joining work cannot be performed when a large amount of work is performed. As a joining method for improving such a problem, a method using a double-sided adhesive tape has come to be used. However, in this joining method, since the adhesiveness is exhibited at the same time as the double-sided adhesive tape is attached, it is difficult to correct it when it is displaced from a desired position. Furthermore, when the surface of the adherend is rough, the contact area with the adhesive surface is not sufficient, and stress due to the weight of the material, expansion and contraction of building materials due to climate change such as temperature and humidity after adhesion, Due to the stress generated by the warp, there is a problem that the adhered adhesive tape is easily peeled off with time. Therefore, even in the joining method using the double-sided adhesive tape, there is a problem that reliability cannot be obtained for long-term joining force.
以上のような問題点を改善する方法として、導電性材料と熱可塑性樹脂系接着剤層を予め建築基材に設けておくか、またはテープ或いはフィルム状の接着剤と導電性シートを建築基材と内外装材の間に挟んで、電磁誘導加熱による接合方法が最近行なわれている。この方法は、電磁誘導で生じる渦電流によって導電性材料が発熱し、この発熱によって熱可塑性樹脂系接着剤が溶融して被着体と接着される方法である。この方法によると、建築基材面と内外装材面の中間に熱可塑性樹脂を介在させ、その上部から高周波発信機を接触させるだけで、熱可塑性樹脂が加熱溶融し、発信機を取り去れば直ちに涸結して接着されるために、短時間で接合が完了し、作業が簡便であるばかりでなく、解体の場合にも使用済みの材料を再利用できる等のメリットが大きい。
電磁誘導加熱方式を用いた接着剤の溶融装置（特許文献２）が開発された。しかし、特許文献２で提案されている方法では、部材と部材との接合強度が十分なものではなく、優れた施工性および貼り直し性の記載もないといった問題もあった。また、解体する（剥がす）時は、再度電磁誘導装置を用いて接着剤層を加熱させホットメルト接着シートを再加熱させて、ホットメルト接着剤層が固化する前に被着体同士を引き剥がすことできたと報告もあった（特許文献３）が、水性エマルジョン系接着剤から成ることを特徴とする熱膨張性微粒中空体を含む接着剤が使用されており、接着剤の種類も限定される。
As a method for improving the above problems, a conductive material and a thermoplastic resin adhesive layer are provided in advance on a building substrate, or a tape or film adhesive and a conductive sheet are used as a building substrate. A joining method by electromagnetic induction heating has recently been carried out by sandwiching it between the interior and exterior materials. This method is a method in which a conductive material generates heat due to an eddy current generated by electromagnetic induction, and the heat generation causes the thermoplastic resin adhesive to melt and adhere to an adherend. According to this method, the thermoplastic resin is interposed between the building base material surface and the interior / exterior material surface, and the high-frequency transmitter is simply contacted from above, and the thermoplastic resin is heated and melted, and the transmitter is removed. Since they are immediately bonded and bonded, the joining is completed in a short time, and not only the work is simple, but also when disassembling, the used materials can be reused, which is a great advantage.
An adhesive melting device (Patent Document 2) using an electromagnetic induction heating method has been developed. However, the method proposed in Patent Document 2 has a problem that the joining strength between members is not sufficient and excellent workability and reattachability are not described. When disassembling (peeling), the adhesive layer is heated again using the electromagnetic induction device to reheat the hot-melt adhesive sheet, and the adherends are peeled off before the hot-melt adhesive layer solidifies. Although it was reported that it was possible (Patent Document 3), an adhesive containing a heat-expandable fine particle hollow body characterized by comprising an aqueous emulsion adhesive is used, and the kind of the adhesive is also limited. .
本発明の目的は、厚みが１ｍｍ以上である支持体、金属層（Ａ）、熱可塑性ホットメルト接着剤層（Ｃ）の順で積層されてなる電磁誘導加熱用ホットメルト接着シート、および上記接着シートと、被着体と、を接着することにより、優れた施工性、貼り直し性を有し、被着体に十分な接着力を付与できる電磁誘導加熱用ホットメルト接着シート、および接着構造物を提供することである。
また、電磁誘導加熱用ホットメルト接着シートを用いた接着構造物の剥離方法を提供することである。
An object of the present invention is to provide a hot melt adhesive sheet for electromagnetic induction heating in which a support having a thickness of 1 mm or more, a metal layer (A), and a thermoplastic hot melt adhesive layer (C) are laminated in this order, and the above-mentioned adhesive. A hot melt adhesive sheet for electromagnetic induction heating, which has excellent workability and reattachability and can impart sufficient adhesive force to an adherend by adhering a sheet and an adherend, and an adhesive structure Is to provide.
Another object of the present invention is to provide a method for separating an adhesive structure using a hot melt adhesive sheet for electromagnetic induction heating.
本発明者らは、鋭利研究を重ねた結果、課題を解決するホットメルト接着シート、および上記接着シートを用いた接着構造物を見出した。 As a result of repeated sharp research, the present inventors have found a hot-melt adhesive sheet that solves the problem, and an adhesive structure using the adhesive sheet.
すなまち、本発明は、厚みが１ｍｍ以上である支持体、金属層（Ａ）、熱可塑性ホットメルト接着剤層（Ｃ）の順で積層されてなる電磁誘導加熱用ホットメルト接着シート関する。 That is, the present invention relates to a hot melt adhesive sheet for electromagnetic induction heating, in which a support having a thickness of 1 mm or more, a metal layer (A), and a thermoplastic hot melt adhesive layer (C) are laminated in this order.
また、本発明は、厚みが１ｍｍ以上である支持体、金属層（Ａ）、熱硬化した接着剤層（Ｂ）、熱可塑性ホットメルト接着剤層（Ｃ）の順で積層されてなる電磁誘導加熱用ホットメルト接着シートに関する。 The present invention also provides an electromagnetic induction in which a support having a thickness of 1 mm or more, a metal layer (A), a thermosetting adhesive layer (B), and a thermoplastic hot melt adhesive layer (C) are laminated in this order. The present invention relates to a hot melt adhesive sheet for heating.
また、本発明は、熱可塑性ホットメルト接着剤層（Ｃ）の厚さが、１０μｍ以上５００μｍ以下であることを特徴とする電磁誘導加熱用ホットメルト接着シートに関する。 The present invention also relates to a hot melt adhesive sheet for electromagnetic induction heating, wherein the thickness of the thermoplastic hot melt adhesive layer (C) is 10 μm or more and 500 μm or less.
また、本発明は、金属層（Ａ）の厚さが、１μｍ以上１０００μｍ以下であることを特徴とする電磁誘導加熱用ホットメルト接着シートに関する。
また、本発明は、熱可塑性ホットメルト接着剤層（Ｃ）の表面粗さ（Ｒａ）が０．０１μｍ以上１００μｍ以下であることを特徴とした電磁誘導加熱用ホットメルト接着シートに関する。
The present invention also relates to a hot melt adhesive sheet for electromagnetic induction heating, wherein the metal layer (A) has a thickness of 1 μm or more and 1000 μm or less.
Further, the present invention relates to a hot melt adhesive sheet for electromagnetic induction heating, wherein the surface roughness (Ra) of the thermoplastic hot melt adhesive layer (C) is 0.01 μm or more and 100 μm or less.
また、本発明は、電磁誘導加熱用ホットメルト接着シートと、被着体とを接着してなる接着構造物に関する。 The present invention also relates to an adhesive structure obtained by adhering a hot melt adhesive sheet for electromagnetic induction heating and an adherend.
更に、本発明は、接着構造物を、電磁誘導加熱装置により加熱し、熱可塑性ホットメルト接着剤層（Ｃ）を、軟化ないし溶融させ、被着体とホットメルト接着剤層（Ｃ）とを、剥離方法に関する。
Further, in the present invention, the adhesive structure is heated by an electromagnetic induction heating device to soften or melt the thermoplastic hot melt adhesive layer (C), thereby forming an adherend and a hot melt adhesive layer (C). , Peeling method.
本発明により、優れた施工性、貼り直し性を有し、被着体に十分な接着力の付与ができる電磁誘導加熱用ホットメルト接着シート、及びそれを用いた接着構造物の提供が可能となる。
また、電磁誘導加熱用ホットメルト接着シートを用いた接着構造物の剥離方法の提供が可能となる。
According to the present invention, it is possible to provide a hot melt adhesive sheet for electromagnetic induction heating, which has excellent workability and reattachability and is capable of imparting sufficient adhesive force to an adherend, and an adhesive structure using the same. Become.
Further, it is possible to provide a method for peeling an adhesive structure using a hot melt adhesive sheet for electromagnetic induction heating.
以下、本発明の電磁誘導加熱用ホットメルト接着シートについて、更に詳細に説明する。 Hereinafter, the hot-melt adhesive sheet for electromagnetic induction heating of the present invention will be described in more detail.
［熱可塑性ホットメルト接着剤層（Ｃ）］
熱可塑性ホットメルト接着剤層（Ｃ）の樹脂構成としては、ＡＢＳ、ポリアミド、ポリエステル、ポリウレタン、アクリル、ポリカーボネート、ポリスチレン、ポリエチレン、ポリプロピレン、ポリ−１−ブテン、ポリイソブチレン、ポリメチルペンテン、プロピレン−エチレン共重合体、エチレン−プロピレン−ジエン共重合体、エチレン／ブテン−１共重合体、エチレン／オクテン共重合体などのポリオレフィン、シクロペンタジエンとエチレンおよび／またはプロピレンとの共重合体などの環状ポリオレフィン、エチレン／酢酸ビニル共重合体（ＥＶＡ）、エチレン／アクリル酸エチル共重合体（ＥＥＡ）、イソブチレン／無水マレイン酸共重合体などの極性基が導入されたポリオレフィン、無水マレイン酸変性ポリプロピレン、マレイン酸変性ポリプロピレン、アクリル酸変性ポリプロピレン、スチレン系エラストマー、ゴムなどの酸変性ポリプロピレンなどがあげられる。
[Thermoplastic hot melt adhesive layer (C)]
The resin composition of the thermoplastic hot melt adhesive layer (C) may be ABS, polyamide, polyester, polyurethane, acrylic, polycarbonate, polystyrene, polyethylene, polypropylene, poly-1-butene, polyisobutylene, polymethylpentene, propylene-ethylene. Polyolefins such as copolymers, ethylene-propylene-diene copolymers, ethylene / butene-1 copolymers, ethylene / octene copolymers, cyclic polyolefins such as copolymers of cyclopentadiene and ethylene and / or propylene, Polyolefins with introduced polar groups such as ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate copolymer (EEA), isobutylene / maleic anhydride copolymer, maleic anhydride modified polypropylene, male Phosphate-modified polypropylene, acrylic acid modified polypropylene, styrene elastomers, such as acid-modified polypropylene, such as rubber.
本発明の熱可塑性ホットメルト接着剤層（Ｃ）は熱可塑性ホットメルト接着剤からなる物である。熱可塑性ホットメルト接着剤により接着性を向上させる為に粘着付与剤などを添加しても良い。主な粘着付与剤は、特に限定されないがフェノール樹脂、変性フェノール樹脂、テルペンフェノール樹脂、キシレンフェノール樹脂、シクロペンタジエン−フェノール樹脂、キシレン樹脂、脂肪族系、脂環族系、芳香族系等の石油樹脂、水素添加された脂肪族系、脂環族系、芳香族系等の石油樹脂、フェノール−変性石油樹脂、ロジンエステル樹脂、水素添加されたロジンエステル樹脂、低分子量ポリスチレン系樹脂、テルペン樹脂、水素添加されたテルペン樹脂などの粘着付与樹脂が含まれていることが好ましい。
粘着付与樹脂は、単独で用いても、２種類以上を併用してもよい。
The thermoplastic hot melt adhesive layer (C) of the present invention is composed of a thermoplastic hot melt adhesive. A tackifier or the like may be added to improve the adhesiveness of the thermoplastic hot melt adhesive. The main tackifier is not particularly limited, but is a petroleum resin such as phenol resin, modified phenol resin, terpene phenol resin, xylene phenol resin, cyclopentadiene-phenol resin, xylene resin, aliphatic type, alicyclic type, aromatic type, etc. Resin, hydrogenated aliphatic, alicyclic, aromatic petroleum resin, phenol-modified petroleum resin, rosin ester resin, hydrogenated rosin ester resin, low molecular weight polystyrene resin, terpene resin, It is preferred to include a tackifying resin such as a hydrogenated terpene resin.
The tackifier resins may be used alone or in combination of two or more.
本発明の熱可塑性ホットメルト接着剤層（Ｃ）に使われた熱可塑性ホットメルト接着剤層の粘度を低粘度化するなどの目的でワックスなどを添加しても良い。主なワックスは、特に限定されないが、カルナバワックス、キャンデリアワックス、モンタンワックス、パラフィンワックス、マイクロワックス、フィッシャートロプシュワックス、ポリエチレンワックス、ポリプロピレンワックス、これらのワックスの酸化物、エチレンーアクリル酸共重合体、エチレンーメタクリル酸共重合体等が挙げられる。ワックスは、単独もしくは２種類以上を組み合わせて使用できる。 Wax or the like may be added for the purpose of lowering the viscosity of the thermoplastic hot melt adhesive layer used in the thermoplastic hot melt adhesive layer (C) of the present invention. Main waxes include, but are not limited to, carnauba wax, candelia wax, montan wax, paraffin wax, microwax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, oxides of these waxes, ethylene-acrylic acid copolymers. , Ethylene-methacrylic acid copolymer and the like. The wax can be used alone or in combination of two or more kinds.
本発明の熱可塑性ホットメルト接着剤層（Ｃ）の厚さは、１０μｍ以上５００μｍ以下であることが好ましい。さらに好ましくは２０μｍ以上３００μｍ以下である。熱可塑性ホットメルト接着剤層（Ｃ）の厚さが１０μｍ未満であると接着不良が発生することがある。熱可塑性ホットメルト接着剤層（Ｃ）の厚さが５００μｍより厚いと電磁誘導加熱でホットメルト接着シートを加熱しても熱可塑性ホットメルト接着剤層（Ｃ）の表面まで加熱・溶融するまでに時間がかかり、金属層に近傍にある熱可塑性ホットメルト接着層が加熱劣化し、接着力が低下することがある。 The thickness of the thermoplastic hot melt adhesive layer (C) of the present invention is preferably 10 μm or more and 500 μm or less. More preferably, it is 20 μm or more and 300 μm or less. If the thickness of the thermoplastic hot melt adhesive layer (C) is less than 10 μm, poor adhesion may occur. When the thickness of the thermoplastic hot-melt adhesive layer (C) is thicker than 500 μm, even if the hot-melt adhesive sheet is heated by electromagnetic induction heating, the surface of the thermoplastic hot-melt adhesive layer (C) is heated and melted. It may take time, the thermoplastic hot melt adhesive layer in the vicinity of the metal layer may deteriorate due to heat, and the adhesive strength may decrease.
熱可塑性ホットメルト接着剤層（Ｃ）に使われた添加剤として、必要により各種のものが使用可能である。例えば着色剤やブロッキング防止剤、無機フィラー、酸化防止剤、充填剤、難燃剤、可塑剤、帯電防止剤、光安定剤、紫外線吸収剤、重金属不活性化剤などである。 As the additive used for the thermoplastic hot melt adhesive layer (C), various kinds of additives can be used if necessary. Examples thereof include colorants, antiblocking agents, inorganic fillers, antioxidants, fillers, flame retardants, plasticizers, antistatic agents, light stabilizers, ultraviolet absorbers and heavy metal deactivators.
着色剤としては、赤、青、緑、黄などの慣用公知の着色剤を使用することができ、顔料、染料、色素のいずれでもよく、例えば、モノアゾ系、ジズアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系、フタロシアニン系、アントラキノン系があり、顔料系はピグメント、ペリレン系、モノアゾ系、縮合アゾ系、イソインドリノン系、酸化チタン、カーボンなどが挙げられる。
ブロッキング防止剤としてはシリコーン、エルカ酸アミドやオレイン酸アミドなどの不飽和脂肪酸アミド、ステアリン酸アミドやベヘニン酸アミドなどの飽和脂肪酸アミドなどが挙げられる。
As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used, for example, monoazo type, diazo type, azo lake type, benzimidazolone. System, perylene system, diketopyrrolopyrrole system, condensed azo system, anthraquinone system, quinacridone system, phthalocyanine system, anthraquinone system, pigment system is pigment, perylene system, monoazo system, condensed azo system, isoindolinone system, oxidation system. Examples include titanium and carbon.
Examples of antiblocking agents include silicone, unsaturated fatty acid amides such as erucic acid amide and oleic acid amide, and saturated fatty acid amides such as stearic acid amide and behenic acid amide.
無機フィラーとしては、金属、金属酸化物及び金属水酸化物など粒子、繊維状などが挙げられる。具体的には、ガラス繊維、炭素繊維、珪酸カルシウム、チタン酸カルシウム、ホウ酸アルミニウム繊維、フレーク状ガラス、タルク、カオリン、マイカ、ハイドロタルサイト、炭酸カルシウム、炭酸亜鉛、酸化亜鉛、リン酸一水素カルシウム、ワラストナイト、シリカ、ゼオライト、アルミナ、ベーマイト、水酸化アルミニウム、酸化チタン、酸化ケイ素、酸化マグネシウム、珪酸カルシウム、アルミナ珪酸ナトリウム、珪酸マグネシウム、カーボンナノチーブ、グラファイト、銅、銀、アルミニウム、ニッケル、鉄、フッ
化カルシウム、雲母、モンモリナイト、アパタイトなどが挙げられる。
酸化防止剤としては、高分子量ヒンダード多価フェノール、トリアジン誘導体、高分子量ヒンダード・フェノール、ジアルキル・フェノール・スルフィド、２，２−メチレン−ビス−（４−メチル−６−第三−ブチルフェノール）、４，４−メチレン−ビス−（２，６−ジ−第三−ブチルフェノール）、２，６−ジ−第三−ブチルフェノール−ｐ−クレゾール、２，５−ジ−第三−ブチルヒドロキノン、２，２，４−トリメチル−１，２−ジヒドロキノン、２，２，４−トリメチル−１，２−ジヒドロキノン、ジブチル・ジチオカルバミン酸ニッケル、１−オキシ−３−メチル−４−イソプロピルベンゼン、４，４−ブチ
リデンビス−（３−メチル−６−第三−ブチルフェノール）、２−メルカプトベンゾイミダゾールなどが挙げられる。
Examples of the inorganic filler include particles such as metals, metal oxides and metal hydroxides, and fibrous substances. Specifically, glass fiber, carbon fiber, calcium silicate, calcium titanate, aluminum borate fiber, glass flakes, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, monohydrogen phosphate. Calcium, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium alumina silicate, magnesium silicate, carbon nanotube, graphite, copper, silver, aluminum, nickel , Iron, calcium fluoride, mica, montmorillonite, apatite and the like.
As antioxidants, high molecular weight hindered polyphenols, triazine derivatives, high molecular weight hindered phenols, dialkyl phenol sulfides, 2,2-methylene-bis- (4-methyl-6-tert-butylphenol), 4 , 4-methylene-bis- (2,6-di-tert-butylphenol), 2,6-di-tert-butylphenol-p-cresol, 2,5-di-tert-butylhydroquinone, 2,2 , 4-trimethyl-1,2-dihydroquinone, 2,2,4-trimethyl-1,2-dihydroquinone, nickel dibutyl dithiocarbamate, 1-oxy-3-methyl-4-isopropylbenzene, 4,4- Butylidene bis- (3-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like can be mentioned.
充填剤としては、湿式シリカ、水酸化アルミニウム、酸化アルミニウム、酸化マグネシウム、モンモリロナイト、マイカ、スメクタイト、有機化モンモリロナイト、有機化マイカ、有機化スメクタイト等が挙げられる。
難燃剤としては、燐含有化合物系難燃剤、ハロゲン含有化合物系難燃剤、スルホン酸金属塩系難燃剤、珪素含有化合物系難燃剤等が挙げられる。
Examples of the filler include wet silica, aluminum hydroxide, aluminum oxide, magnesium oxide, montmorillonite, mica, smectite, organized montmorillonite, organized mica, organized smectite and the like.
Examples of the flame retardant include phosphorus-containing compound flame retardants, halogen-containing compound flame retardants, sulfonic acid metal salt flame retardants, silicon-containing compound flame retardants, and the like.
可塑剤としては、フタル酸エステル系可塑剤、ポリエステル系可塑剤、脂肪族二塩基酸エステル系可塑剤、脂肪族一塩基酸エステル系可塑剤、リン酸エステル系可塑剤、クエン酸エステル系可塑剤、エポキシ系可塑剤、トリメリット酸エステル系可塑剤、テトラヒドロフタル酸エステル系可塑剤、グリコール系可塑剤、およびビスフェノールＡアルキレンオキサイド誘導体などが挙げられる。
帯電防止剤としては、プラスチックの帯電防止剤として汎用されているものでよく、具体的には、非イオン界面活性剤（例えば、多価アルコールの脂肪酸エステル、アルキルアミンのエチレンオキサイド付加物、及びアルキルアミンのエチレンオキサイド付加物の脂肪酸エステルなど）、陰イオン界面活性剤（例えば、アルキルベンゼンスルホン酸塩、高級アルコール硫酸エステル塩など）、陽イオン界面活性剤（例えば、脂肪族アミン塩、４級アンモニウム塩など）、両性界面活性剤（例えばイミダゾリン型、ベタイン型など）が挙げられる。
Examples of the plasticizer include phthalic acid ester plasticizers, polyester plasticizers, aliphatic dibasic acid ester plasticizers, aliphatic monobasic acid ester plasticizers, phosphoric acid ester plasticizers, and citric acid ester plasticizers. , Epoxy-based plasticizers, trimellitic acid ester-based plasticizers, tetrahydrophthalic acid ester-based plasticizers, glycol-based plasticizers, and bisphenol A alkylene oxide derivatives.
The antistatic agent may be one that is widely used as an antistatic agent for plastics, and specifically, a nonionic surfactant (for example, fatty acid ester of polyhydric alcohol, ethylene oxide adduct of alkylamine, and alkyl). Fatty acid ester of ethylene oxide adduct of amine), anionic surfactant (eg, alkylbenzene sulfonate, higher alcohol sulfate ester salt, etc.), cationic surfactant (eg, aliphatic amine salt, quaternary ammonium salt) Etc.) and amphoteric surfactants (eg, imidazoline type, betaine type, etc.).
光安定剤としては、ヒンダードアミン系化合物及びベンゾエイト系化合物などが挙げられる。
紫外線吸収剤としては、ベンゾフェノン系紫外線吸収剤、トリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤などが挙げられる。
重金属不活性化剤としては、サリチル酸誘導体、ヒドラジド誘導体又はシュウ酸アミド誘導体などが挙げられる。
Examples of the light stabilizer include hindered amine compounds and benzoate compounds.
Examples of the UV absorber include benzophenone-based UV absorbers, triazine-based UV absorbers, and benzotriazole-based UV absorbers.
Examples of the heavy metal deactivator include salicylic acid derivatives, hydrazide derivatives, oxalic acid amide derivatives, and the like.
［熱硬化した接着層（Ｂ）］
本発明の熱硬化した接着層（Ｂ）には、熱硬化しうる接着剤を用いることができる。熱硬化しうる接着剤の一例について説明する。熱硬化しうる接着剤としては、例えば、ポリエステル樹脂、ポリウレタン樹脂、アクリル系樹脂、エポキシ樹脂等の官能基を有する主剤と硬化剤とをベース樹脂とした熱硬化しうる接着剤が挙げられる。
[Heat cured adhesive layer (B)]
For the thermosetting adhesive layer (B) of the present invention, a thermosetting adhesive can be used. An example of the thermosetting adhesive will be described. Examples of the heat-curable adhesive include heat-curable adhesives containing a base resin having a main agent having a functional group such as polyester resin, polyurethane resin, acrylic resin, and epoxy resin as a base resin.
ポリエステル樹脂として、モノマー組成の酸成分としては、例えばジメチルテレフタル酸、テレフタル酸、イソフタル酸、フタル酸などの芳香族二塩基性酸や、コハク酸、グルタル酸、アジピン酸、β−メチルアジピン酸、ピメリン酸、1,6−ヘキサンジカルボン酸、アゼライン酸、セバチン酸、ノナンジカルボン酸、デカンジカルボン酸、ヘキサデカンジカルボン酸などの脂肪族二塩基性酸と、グルコール成分としては、エチレングリール、1,2−プロパンジオール、1,3−プロパンジオール、1,3ブタンジオール、1,4−ブタンジオール、1,2−ペンタジオール、1,5−ペンタジオール、３−メチルペンタジオール、1,3−ヘキサンジオール、1,6−ヘキサンジオール、1,4−シクロヘキサンジオール、水添ビスフ
ェノールＡ、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどのグリコールもしくはその残基形成誘導体もしくはカプロラクトンなどのα，ω−オキシ酸もしくはその残基形成誘導体よりなる飽和二官能性モノマーとを適宜選択して常法により共重合して得ることが可能である。
As the polyester resin, as the acid component of the monomer composition, for example, dimethyl terephthalic acid, terephthalic acid, isophthalic acid, aromatic dibasic acids such as phthalic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, Pimelic acid, 1,6-hexanedicarboxylic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, hexadecanedicarboxylic acid and other aliphatic dibasic acids, and glycol components include ethylene glycol, 1,2 -Propanediol, 1,3-propanediol, 1,3 butanediol, 1,4-butanediol, 1,2-pentadiol, 1,5-pentadiol, 3-methylpentadiol, 1,3-hexanediol , 1,6-hexanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A, diethylene glycol, trie A saturated bifunctional monomer comprising a glycol such as len glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol or a residue-forming derivative thereof, or an α, ω-oxy acid such as caprolactone or a residue-forming derivative thereof; Can be appropriately selected and copolymerized by a conventional method.
ポリウレタン樹脂としては、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリマーポリオール等のポリオールとポリイソシアネートからなるイソシアネート化合物を上記ポリオール過剰で反応させて得られるが、上記エーテル系ポリオールとしては、例えば、ビスフェノールＡ、エチレングリコール、プロピレングリコール、ブチレングリコール、1,6−ヘキサンジオール等のジオール類、グリセリン、トリメチロールプロパン等のトリオール類、エチレンジアミン、ブチレンジアミン等のアミン類等からなる活性水素２個以上を有する低分子量活性水素化合物の１種又は２種以上の存在下に、プロピレンオキサイド、エチレンオキサイド、テトラヒドロフラン等のアルキレンオキサイドの１種又は２種以上を開環重合させて得られる重合体が挙げられる。
上記ポリエステル系ポリオールとしては、例えばアジピン酸、アゼライン酸、セバシン酸、テレフタル酸、イソフタル酸、コハク酸等の多塩基性酸と、例えばビスフェノールＡ、エチレングリコール、1,2−プロピレングリコール、1,4−ブタンジオール、ジエチレングリコール、1,6−ヘキサンジオール、ネオペンチルグリコール等の多価アルコールとを脱水縮合して得られる重合体、又、例えばε−カプロラクトン、α−メチル−ε−カプロラクトン等のラクトンの重合体、又、例えばひまし油、ひまし油とエチレングリコールの反応生成物等のヒドロキシカルボン酸と上記多価アルコールなどの縮合物が挙げられる。
上記ポリマーポリオールとしては、例えば前記ポリエーテル系ポリオールないしはポリエステル系ポリオールにアクリロニトリル、スチレン、メチル（メタ）アクリレートなどのエチレン性不飽和化合物をグラフト重合させたものや、1,2−もしくは1,4−ポリブタジエンポリオール、又はこれらの水素添加物が挙げられる。
上記ポリイソシアネートとしては、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート等のジイソシアネート類、又、上記ジイソシアネート類の３量体、トリフェニルメタントリイソシアネート等のトリイソシアネート類、又、ジフェニルメタンジイソシアネート、トリフェニルメタントリイソシアネート等の混合物であるクルードMDIなどが挙げられる。これらのポリイソシアネートは１種類で使用されてもよいが、２種類以上を併用してもよい。上記水酸基末端ポリウレタンポリマーの水酸基１に対し、イソシアネート化合物のイソシアネート基２〜８となるように配合されて上記熱硬化しうる接着剤として使用される。
The polyurethane resin is obtained by reacting a polyol such as a polyether-based polyol, a polyester-based polyol, or a polymer polyol with an isocyanate compound composed of polyisocyanate in the excess of the polyol. Examples of the ether-based polyol include bisphenol A, Low molecular weight with 2 or more active hydrogen consisting of ethylene glycol, propylene glycol, butylene glycol, diols such as 1,6-hexanediol, triols such as glycerin and trimethylolpropane, amines such as ethylenediamine and butylenediamine Obtained by ring-opening polymerization of one or more alkylene oxides such as propylene oxide, ethylene oxide and tetrahydrofuran in the presence of one or more active hydrogen compounds. That the polymer and the like.
Examples of the polyester-based polyol include polybasic acids such as adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid and succinic acid, and bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4 A polymer obtained by dehydration condensation with a polyhydric alcohol such as butanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, or a lactone such as ε-caprolactone or α-methyl-ε-caprolactone Examples thereof include polymers, and condensates of hydroxycarboxylic acids such as castor oil, a reaction product of castor oil and ethylene glycol, and the above polyhydric alcohols.
Examples of the above-mentioned polymer polyol include those obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, and methyl (meth) acrylate onto the above polyether-based polyol or polyester-based polyol, or 1,2- or 1,4- Examples thereof include polybutadiene polyol and hydrogenated products thereof.
Examples of the polyisocyanate include diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate, trimers of the above diisocyanates, and triisocyanates such as triphenylmethane triisocyanate. In addition, crude MDI, which is a mixture of diphenylmethane diisocyanate, triphenylmethane triisocyanate, and the like, can be mentioned. These polyisocyanates may be used alone or in combination of two or more. It is blended so that the isocyanate groups of the isocyanate compound are 2 to 8 with respect to 1 hydroxyl group of the hydroxyl group-terminated polyurethane polymer, and is used as the thermosetting adhesive.
エポキシ樹脂としては、１分子中にエポキシ基を２個以上有するものであればよく、具体的には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレートエポキシ樹脂、アクリル酸変性エポキシ樹脂（エポキシアクリレート）、リン含有エポキシ樹脂及びこれらハロゲン樹脂（臭素化エポキシ樹脂など）や水素添加物などが挙げられる。これらのエポキシ樹脂は、単独で用いてもよ
く、２種以上を併用してもよい。臭素化エポキシ樹脂などは、接着剤に難燃性が要求される場合に、特に有効である。アクリル酸変性エポキシ（エポキシアクリレート）は、感光性を有する為エポキシ系樹脂組成物に光硬化性を付与する為に有効である。
Any epoxy resin may be used as long as it has two or more epoxy groups in one molecule, and specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin. , Alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate epoxy resin, acrylic acid modified epoxy resin (epoxy acrylate), phosphorus-containing epoxy resin and these halogen resins (bromination Epoxy resin, etc.) and hydrogenated substances. These epoxy resins may be used alone or in combination of two or more. Brominated epoxy resin and the like are particularly effective when flame retardancy is required for the adhesive. Acrylic acid-modified epoxy (epoxy acrylate) is effective for imparting photocurability to the epoxy resin composition because it has photosensitivity.
硬化剤としては、エポキシ樹脂の硬化に用い得るものであれば、特に制限なく使用することが可能であるが、例えば、脂肪族アミン系硬化剤、脂環式アミン系硬化剤、芳香族アミン系硬化剤、酸無水物硬化剤、ジシアンジアミド、三フッ化ホウ素アミン錯塩、イミダゾール化合物などが挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。硬化剤の配合量はエポキシ樹脂に応じて定めることができる。 The curing agent can be used without particular limitation as long as it can be used for curing the epoxy resin, and examples thereof include an aliphatic amine curing agent, an alicyclic amine curing agent, and an aromatic amine curing agent. Examples thereof include curing agents, acid anhydride curing agents, dicyandiamide, boron trifluoride amine complex salts, and imidazole compounds. These may be used alone or in combination of two or more. The compounding amount of the curing agent can be determined according to the epoxy resin.
熱硬化しうる接着剤の添加剤としてシランカップリング剤、酸化防止剤等などが挙げられる。シランカップリング剤としては、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、ビニルトリアセチルシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトエチルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−クロロプロピルトリエトキシシラン、ビニルトリクロロシランなどが挙げられる。
酸化防止剤としては、上記記載の熱可塑性ホットメルト接着層に用いられる酸化防止剤が用いられる。
Examples of additives for heat-curable adhesives include silane coupling agents and antioxidants. As the silane coupling agent, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) ) Silane, vinyltriacetylsilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptoethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloro Examples include propyltriethoxysilane and vinyltrichlorosilane.
As the antioxidant, the antioxidant used in the thermoplastic hot melt adhesive layer described above is used.
本発明の熱硬化しうる接着剤は、各種の溶剤を含有しても良い。例えば、アセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトンなどのケトン系化合物、テトラヒドロフラン（ＴＨＦ）、ジオキソランなどの環状エーテル系化合物、酢酸エチル、酢酸エチル、酢酸ブチルなどのエステル系化合物、トルエン、キシレンなどの芳香族系化合物、カルビトール、セロソルブ、メタノール、イソプロパノール、ブタノール、プロピレンコールモノメチルエーテルなどのアルコール系化合物などが挙げられる。これらは、単独でも使用しても二種類以上を併用しても良い。 The thermosetting adhesive of the present invention may contain various solvents. For example, ketone compounds such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone, cyclic ether compounds such as tetrahydrofuran (THF) and dioxolane, ester compounds such as ethyl acetate, ethyl acetate and butyl acetate, toluene and xylene. Examples thereof include aromatic compounds, carbitol, cellosolve, methanol, isopropanol, butanol, alcohol compounds such as propylenechol monomethyl ether, and the like. These may be used alone or in combination of two or more.
エポキシ接着剤を金属単層フィルムまたは、熱可塑性ホットメルト単層フィルムに塗工する装置としては、コンマコーター、ロールナイフコーター、ダイコーター、ロールコーター、バーコーター、グラビアロールコーター、リバースロールコーター、ブレードコーター、グラビアコーター、マイクログラビアコーターなどが挙げられる。熱硬化しうる接着剤の塗布量は、乾燥膜厚で１〜５０μｍ程度であることが好ましい。さらに好ましくは２〜２５μｍである。さらに好ましくは２〜１０μｍである。 As an apparatus for applying an epoxy adhesive to a metal single layer film or a thermoplastic hot melt single layer film, a comma coater, a roll knife coater, a die coater, a roll coater, a bar coater, a gravure roll coater, a reverse roll coater, a blade A coater, a gravure coater, a micro gravure coater, etc. are mentioned. The amount of the heat-curable adhesive applied is preferably about 1 to 50 μm as a dry film thickness. More preferably, it is 2 to 25 μm. More preferably, it is 2 to 10 μm.
［金属層（Ａ）］
本発明の金属層（Ａ）とは、電誘導加熱装置により高周波磁束によって渦電流が誘導され、上記金属層のジュール加熱により、熱可塑性ホットメルト接着層が溶融し接着する。この金属層は、鉄，アルミニウム，ニッケル，ステンレス，亜鉛，銅，錫，亜鉛，マグネシウム及びそれらの合金などから選ばれる導電性金属をフィルム状にしたものであればよい。
[Metal layer (A)]
With the metal layer (A) of the present invention, an eddy current is induced by a high frequency magnetic flux by an electric induction heating device, and the thermoplastic hot melt adhesive layer is melted and adhered by Joule heating of the metal layer. The metal layer may be made of a conductive metal selected from the group consisting of iron, aluminum, nickel, stainless steel, zinc, copper, tin, zinc, magnesium and alloys thereof in the form of a film.
本発明の金属層の厚みは、１μｍ以上１０００μｍ以下が好ましく、さらに好ましくは１０μｍ以上５００μｍ以下が好ましく、さらに好ましくは２０μｍ以上１００μｍ以下である。１μｍ以下の場合電磁誘導加熱を行っても発熱温度が上がらなく電磁誘導加熱が出来なかったり、１０００μｍよりも厚い場合は、電磁誘導加熱を行っても金属層が加熱するのに時間がかかったり、熱可塑性ホットメルト層が溶融する温度にならず、接着しないことがある。 The thickness of the metal layer of the present invention is preferably 1 μm or more and 1000 μm or less, more preferably 10 μm or more and 500 μm or less, and further preferably 20 μm or more and 100 μm or less. When the thickness is 1 μm or less, the heat generation temperature does not rise even if the electromagnetic induction heating is performed and the electromagnetic induction heating cannot be performed. The thermoplastic hot melt layer may not reach a melting temperature and may not adhere.
［支持体］
本発明の支持体は、厚さが１ｍｍ以上であることを特徴とする。支持体の厚みが１ｍｍ未満の場合は電磁誘導加熱を行った時に電磁誘導加熱装置により発生する熱が支持体にダメージを与える可能性があるため、支持体の厚みが、１ｍｍ以上が好ましい。
支持体としては、プラスチック、紙、紙とプラスチックの複合体、コンクリート、タイル、舗装材、木材、布、皮革、ゴム、ガラスなどが挙げられる。
[Support]
The support of the present invention is characterized by having a thickness of 1 mm or more. When the thickness of the support is less than 1 mm, the heat generated by the electromagnetic induction heating device during electromagnetic induction heating may damage the support, so the thickness of the support is preferably 1 mm or more.
Examples of the support include plastic, paper, a composite of paper and plastic, concrete, tile, paving material, wood, cloth, leather, rubber, glass and the like.
また、電磁誘導加熱用ホットメルト接着シートを製造する場合、支持体と金属層の間を仮固定又は固定させるために、支持体には、粘接着層などが設けられていることが好ましい。粘接着層は両面テープのように機能させることができる。粘接着層のＳ１面と金属層、及び粘接着層のＳ２面と支持体の基材を貼り付けることができる。或いは、粘接着層形成用組成物を支持体の基材に塗工し、更に支持体の粘接着層面と金属層と、を接着させることができる。
本願において、「粘接着」とは、粘着性能と接着性能を併せ持つことを意味し、粘着は一時的な接着現象を意味するものとして用いられるのに対し、接着は永久的な接着現象を意味するものとして用いられる点で区別されることがある（岩波書店 理化学辞典第５版）。貼り合わされた後の粘接着層を硬化させる。
手段としては、加熱、紫外線照射、電子線照射等を挙げることができる。
粘接着層形成用組成物とは、粘接着層を塗布等によって形成する樹脂組成物のことである。粘着剤層を構成する粘接着層形成用組成物としては、ポリアクリル系、エポキシ系、ポリウレタン、フッ素系などが挙げられる。
Further, in the case of producing a hot melt adhesive sheet for electromagnetic induction heating, it is preferable that the support is provided with a viscous adhesive layer or the like in order to temporarily fix or fix between the support and the metal layer. The adhesive layer can function like a double-sided tape. The S1 surface of the adhesive layer and the metal layer, and the S2 surface of the adhesive layer and the base material of the support can be attached. Alternatively, the adhesive / bonding layer forming composition can be applied to the base material of the support, and the adhesive / adhesive layer surface of the support and the metal layer can be further bonded.
In the present application, "adhesive" means having both adhesive performance and adhesive performance, and adhesive is used as meaning a temporary adhesive phenomenon, whereas adhesive means a permanent adhesive phenomenon. It is sometimes distinguished in that it is used as a thing (Iwanami Shoten, Physics and Chemistry Dictionary, 5th edition). The adhesive layer after being bonded is cured.
Examples of the means include heating, ultraviolet irradiation, and electron beam irradiation.
The composition for forming a tacky adhesive layer is a resin composition that forms a tacky adhesive layer by coating or the like. Examples of the adhesive / adhesive layer-forming composition constituting the pressure-sensitive adhesive layer include polyacrylic type, epoxy type, polyurethane, and fluorine type.
接着シートを電磁誘導加熱装置により加熱する場合、熱が支持体にダメージを与える可能性があるため、耐熱性が高い支持体が特に好ましい。
そのため、支持体を製造する際、耐熱性を向上させるために、粘接着層形成用組成物を厚さが１ｍｍ以上の基材に塗工する（貼り付ける）ことが好ましい。基材としては特に限定されず、例えば、以下のもの等が挙げられる。フェノール樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、エポキシ樹脂、ケイ素樹脂、アルキド樹脂、フラン樹脂、ウレタン樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、酢酸ビニル樹脂、ＡＢＳ樹脂、メタクリル樹脂、ポリフェニレンオキシド、アイオノマー樹脂、フッ素樹脂、セルロース系プラスチック、ポリエチレン、ポリプロピレン、ポリアミド、ポリイミド、ポリスチレン、ポリカーボネート、ポリアセタール、ポリフェニレンサルファイド、ポリエチレンテレフタレート等のプラスチック又はその混合物。
When the adhesive sheet is heated by the electromagnetic induction heating device, heat may damage the support, and thus a support having high heat resistance is particularly preferable.
Therefore, when the support is manufactured, in order to improve heat resistance, it is preferable to apply (stick) the composition for forming a tacky adhesive layer onto a substrate having a thickness of 1 mm or more. The base material is not particularly limited, and examples thereof include the following. Phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicon resin, alkyd resin, furan resin, urethane resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, ABS resin, methacrylic resin , Polyphenylene oxide, ionomer resin, fluororesin, cellulosic plastic, polyethylene, polypropylene, polyamide, polyimide, polystyrene, polycarbonate, polyacetal, polyphenylene sulfide, polyethylene terephthalate, and other plastics or mixtures thereof.
支持体の基材の形態としては板状、シート状、繊維状など等が挙げられる。
粘接着層形成用組成物を基材に塗布する（貼り付ける）方法も特に限定されない、印刷による形成方法としては、例えば、グラビア印刷法、フレキソ印刷法、オフセット印刷法等を挙げることができる。コーティングによる方法としては、例えば、ロールコート、リバースコート、コンマコート、ナイフコート、ダイコート、グラビアコート等を挙げることができる。
粘接着層形成用組成物を基材上に塗布し（貼り付ける）、塗布後の粘接着層形成用組成物を乾燥して形成し、厚さが１ｍｍ以上の支持体を得ることができる。
Examples of the form of the base material of the support include a plate shape, a sheet shape, and a fiber shape.
The method of applying (attaching) the composition for forming an adhesive layer to a substrate is not particularly limited, and examples of the forming method by printing include a gravure printing method, a flexo printing method, an offset printing method, and the like. . Examples of the coating method include roll coating, reverse coating, comma coating, knife coating, die coating and gravure coating.
A support having a thickness of 1 mm or more can be obtained by applying (adhering) the composition for forming an adhesive layer onto a substrate and drying the composition for forming an adhesive layer after application. it can.
［被着体］
被着体とは、プラスチック、紙、紙とプラスチックの複合体、金属板、コンクリート、タイル、舗装材、木材、布、皮革、ゴム、ガラスなどが挙げられる。
[Substrate]
Examples of the adherend include plastic, paper, a composite of paper and plastic, metal plate, concrete, tile, paving material, wood, cloth, leather, rubber and glass.
［電磁誘導加熱用ホットメルト接着シートの製造方法］
電磁誘導加熱用ホットメルト接着シートの製造は、上記の熱可塑性ホットメルト接着剤をインフレーション法、Ｔダイ法、溶液流延法、カレンダー法などの他、離型紙又はフィルムなどの上にスリットコーティングして得られた熱可塑性ホットメルト接着剤フィルムを、金属層に接着し、さらに粘接着層のＳ１面と金属層と、及び粘接着層のＳ２面と支持体を接着させ、熱可塑性ホットメルト接着剤層、金属層、支持体の順で積層した電磁誘導加熱用ホットメルト接着シートが得られる。または、支持体と金属層との接着の際、まず粘接着層形成用組成物を支持体の基材に塗工し、支持体の粘接着層面と熱可塑性ホットメルト接着剤フィルムと接着した金属層と、を接着させることもできる。
[Method for producing hot melt adhesive sheet for electromagnetic induction heating]
The production of the hot melt adhesive sheet for electromagnetic induction heating is carried out by slit coating the thermoplastic hot melt adhesive on the release paper or film in addition to the inflation method, T-die method, solution casting method, calendering method, etc. The thermoplastic hot melt adhesive film thus obtained is adhered to a metal layer, and then the S1 side of the adhesive layer and the metal layer, and the S2 surface of the adhesive layer are adhered to the support to form a thermoplastic hot film. A hot-melt adhesive sheet for electromagnetic induction heating in which a melt adhesive layer, a metal layer and a support are laminated in this order is obtained. Alternatively, when adhering the support and the metal layer, first the composition for forming an adhesive layer is applied to the base material of the support, and the adhesive layer surface of the support is adhered to the thermoplastic hot melt adhesive film. It is also possible to adhere the formed metal layer.
また、熱硬化しうる接着剤を用いることが好ましい。この場合の電磁誘導加熱用ホットメルト接着シートの製造は、熱可塑性ホットメルト接着剤層または金属層どちらかに熱硬化しうる接着剤を塗工して、乾燥させた後に最表面が熱可塑性ホットメルト接着剤層になるように金属層を貼り合せた後に、熱硬化しうる接着剤は硬化速度が遅い為、熱硬化しうる接着剤を硬化させる目的でエージングを行う必要がある。
具体的にいえば、熱硬化しうる接着剤を介して熱可塑性ホットメルト層と熱硬化した接着剤層を貼り合わせた後３５〜８０℃の保温室にて３〜５日間程度保存してエージングすることにより熱硬化した接着剤層の接着剤を硬化させる。この際、保存温度が高すぎると例えばロール状にした時に接している熱可塑性ホットメルト接着剤層同士がブロッキングを起こすことがあるので巻圧と保存温度は注意する必要がある。また、エージング条件によって熱硬化性接着剤の硬化の度合いが変わってくる為、ホットメルト接着シートの熱可塑性ホットメルト接着剤層と金属層の接着強度に影響を及ぼすことがあり、エージングが不十分な場合には、接着剤の硬化不良によるデラミネーション（層剥離）を引き起こすことがある。
In addition, it is preferable to use a thermosetting adhesive. In this case, the hot melt adhesive sheet for electromagnetic induction heating is manufactured by applying a thermosetting adhesive to either the thermoplastic hot melt adhesive layer or the metal layer, and drying the outermost surface of the thermoplastic hot adhesive sheet. Since the thermosetting adhesive has a slow curing speed after the metal layers are bonded to each other to form the melt adhesive layer, it is necessary to perform aging for the purpose of curing the thermosetting adhesive.
Specifically, the thermoplastic hot melt layer and the thermosetting adhesive layer are bonded together via a thermosetting adhesive, and then stored in a greenhouse at 35 to 80 ° C. for about 3 to 5 days for aging. By doing so, the adhesive of the thermosetting adhesive layer is cured. At this time, if the storage temperature is too high, for example, the thermoplastic hot melt adhesive layers that are in contact with each other when rolled may cause blocking, so care must be taken regarding the winding pressure and the storage temperature. Also, since the degree of curing of the thermosetting adhesive changes depending on the aging conditions, the adhesive strength between the thermoplastic hot melt adhesive layer and the metal layer of the hot melt adhesive sheet may be affected, resulting in insufficient aging. In such cases, delamination (layer separation) may occur due to poor curing of the adhesive.
ブロッキングを防止する為に熱硬化した接着剤層の表面にエンボス処理，剥離紙又は剥離フィルムを入れるなどすると効果的である。電磁誘導加熱用ホットメルト接着シートの表面粗さが０．０１μｍ以上１００μｍ以下であることが好ましい。熱可塑性ホットメルト接着シートの表面粗さＲａが０．０１μｍ未満の場合は、熱可塑性ホットメルト接着シートがブロッキングして、使用できなくなることがあり、電磁誘導加熱用ホットメルト接着シートの表面粗さ１００μｍより大きい場合電磁誘導加熱用ホットメルト接着シートの強度が低くなり、塗工する時熱可塑性ホットメルト接着シートが切れてしまうなど問題が生じることがある。 In order to prevent blocking, it is effective to emboss the surface of the heat-cured adhesive layer, or put release paper or release film on it. The surface roughness of the hot melt adhesive sheet for electromagnetic induction heating is preferably 0.01 μm or more and 100 μm or less. When the surface roughness Ra of the thermoplastic hot melt adhesive sheet is less than 0.01 μm, the thermoplastic hot melt adhesive sheet may be blocked and may not be used, and the surface roughness of the hot melt adhesive sheet for electromagnetic induction heating may become unusable. If it is larger than 100 μm, the strength of the hot-melt adhesive sheet for electromagnetic induction heating becomes low, and problems may occur such that the thermoplastic hot-melt adhesive sheet is cut off during coating.
熱可塑性ホットメルト接着層と熱硬化接着層の接着強度を強くする為に熱可塑性ホットメルト接着剤層面にコロナ処理を行うことは、有効である。特に、ポリエチレンフィルム、ポリプロピレンフィルムなど極性が低いフィルムを金属層と接着させるには、効果がある。 It is effective to perform corona treatment on the surface of the thermoplastic hot melt adhesive layer in order to increase the adhesive strength between the thermoplastic hot melt adhesive layer and the thermosetting adhesive layer. In particular, it is effective in adhering a film having low polarity such as a polyethylene film or a polypropylene film to the metal layer.
［接着構造物の製造方法］
電磁誘導加熱用ホットメルト接着シートと、被着体と接着する際には、電磁誘導加熱の熱を利用し、接着構造物を得る。
具体的にいえば、電磁誘導加熱用ホットメルト接着シートの支持体の外側から、電磁誘導加熱用ホットメルト接着シート、被着体の順で入力電圧：１００Ｖ、消費電力：５５０Ｗの電磁誘導加熱装置により加熱し、電磁誘導加熱用ホットメルト接着シートの熱可塑性ホットメルト接着剤を軟化させ、加熱を終了することにより、熱可塑性ホットメルト接着剤を固化させ、被着体と電磁誘導加熱用ホットメルト接着シートとを密着させ、接着構造物が得られる。
（接着構造物の構造：被着体/熱可塑性ホットメルト接着剤/金属層/支持体））
[Method for manufacturing bonded structure]
When the hot melt adhesive sheet for electromagnetic induction heating is adhered to the adherend, the heat of electromagnetic induction heating is used to obtain an adhesive structure.
Specifically, an electromagnetic induction heating device having an input voltage of 100 V and a power consumption of 550 W in that order from the outside of the support of the hot melt adhesive sheet for electromagnetic induction heating to the hot melt adhesive sheet for electromagnetic induction heating and the adherend. By heating to soften the thermoplastic hot melt adhesive of the hot melt adhesive sheet for electromagnetic induction heating and solidify the thermoplastic hot melt adhesive by terminating the heating, the adherend and the hot melt for electromagnetic induction heating. The adhesive sheet is brought into close contact with the adhesive sheet to obtain an adhesive structure.
(Structure of bonded structure: adherend / thermoplastic hot melt adhesive / metal layer / support)
［接着構造物からホットメルト接着シートの剥離方法］
接着構造物を、電磁誘導加熱用ホットメルト接着シートの支持体の外側から電磁誘導加熱装置により加熱し、固体状態にある熱可塑性ホットメルト接着剤層を、軟化ないし溶融させ、被着体と電磁誘導加熱用ホットメルト接着シートを剥がす。
[Peeling method of hot melt adhesive sheet from adhesive structure]
The adhesive structure is heated from the outside of the support of the hot-melt adhesive sheet for electromagnetic induction heating by an electromagnetic induction heating device to soften or melt the thermoplastic hot-melt adhesive layer in the solid state, and the adherend and the electromagnetic Peel off the hot melt adhesive sheet for induction heating.
以下、本発明を、実施例を挙げてさらに具体的に説明する。しかし、本発明は、以下の実施例に限定されるものではない。なお、本発明では、特に断らない限り、部は重量部、％は重量％を表す。 Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to the following examples. In addition, in this invention, a part represents a weight part and% represents weight% unless there is particular notice.
＜熱可塑性ホットメルト接着剤層（Ｃ）＞
実施例１〜２に使用された熱可塑性ホットメルト接着剤層は、下記の通りである。
・ＬＤＰＥフィルム（コロナ処理有） 膜厚：５０μｍ 北越化成（株）社製
・ＬＤＰＥフィルム（コロナ処理有） 膜厚：１００μｍ 北越化成（株）社製
実施例３〜１７に使用された熱可塑性ホットメルト接着剤層は、下記ポリマーを製膜することによって得られた。
・ポリアミド（ナイロンベース） アルケマ社（株）製プラタミドＭ１２７６
・ポリアミド（ダイマー酸ベース） ヘンケル社（株）製マクロメルト６２３９
・結晶性ポリエステル東洋紡社（株）製バイロンＧＡ６３００
・非結晶ポリエステル東洋紡社（株）製バイロン６００
・ポリウレタン（ポリエーテルタイプ） ＢＡＳＦ（株）社製エラストランＥＴ−３７０
・アクリル（メタクリル酸メチル） 住友化学（株）社製スミペックスＥＸ
・エチレン-酢酸ビニル共重合体東ソー（株）社製ウルトラセン５４０
・変性ポリオレフィン三井化学（株）社製アドマーＳＥ８１０
<Thermoplastic hot melt adhesive layer (C)>
The thermoplastic hot melt adhesive layers used in Examples 1-2 are as follows.
・ LDPE film (with corona treatment) Film thickness: 50 μm, manufactured by Hokuetsu Chemical Co., Ltd. ・ LDPE film (with corona treatment) Film thickness: 100 μm, manufactured by Hokuetsu Chemical Co., Ltd.
The thermoplastic hot melt adhesive layers used in Examples 3 to 17 were obtained by forming the following polymers.
-Polyamide (nylon base) Arkema Corporation Pratamide M1276
-Polyamide (based on dimer acid) Macromelt 6239 manufactured by Henkel Co., Ltd.
-Crystalline Polyester Toyobo Co., Ltd. Byron GA6300
・ Amorphous polyester Byron 600 manufactured by Toyobo Co., Ltd.
Polyurethane (polyether type) BASF Corporation Elastollan ET-370
・ Acrylic (methyl methacrylate) Sumipex EX manufactured by Sumitomo Chemical Co., Ltd.
・ Ethylene-vinyl acetate copolymer Tosoh Corp. Ultrasen 540
-Modified Polyolefin Mitsui Chemicals, Inc. Admer SE810
＜熱硬化しうる接着剤（Ｂ）＞
本発明に使用した熱硬化しうる接着剤は、下記の通りである。
（主剤）
・ＴＭ−５８５−６０（ポリエステル系）不揮発分60% 東洋モートン（株）社製
・ＴＭ−Ｋ５５（ポリエステル系）不揮発分30% 東洋モートン（株）社製
・ＴＭ−Ｋ７６（ポリエステル系）不揮発分51% 東洋モートン（株）社製
（硬化剤）
・ＣＡＴ−１０Ｌ（芳香族系）不揮発分52.5% 東洋モートン（株）社製
・ＣＡＴ−ＲＴ８５（脂肪族系）不揮発分70% 東洋モートン（株）社製
（熱硬化した接着剤層に用いられる熱硬化しうる接着剤の作製方法）
・接着剤Ａ
熱硬化性接着剤の主剤ＴＭ−Ｋ５５と硬化剤ＣＡＴ-１０Ｌを重量比１７／３の割合で配合し、固形分が３０％になるように酢酸エチルで希釈した。
・接着剤Ｂ
熱硬化性接着剤の主剤ＴＭ−５８５−６０と硬化剤ＣＡＴ-１０Ｌを重量比１００／７の割合で配合し、固形分が３０％になるように酢酸エチルで希釈した。
・接着剤Ｃ
熱硬化性接着剤の主剤ＴＭ−Ｋ７６と硬化剤ＣＡＴ-１０Ｌを重量比１００／7の割合で配合し、固形分が３０％になるように酢酸エチルで希釈した。
・接着剤Ｄ
熱硬化性接着剤の主剤ＴＭ−Ｋ７６と硬化剤ＣＡＴ-ＲＴ８５を重量比１００／7の割合で配合し、固形分が３０％になるように酢酸エチルで希釈した。
<Heat-curable adhesive (B)>
The thermosetting adhesive used in the present invention is as follows.
(Main agent)
TM-585-60 (polyester type) non-volatile content 60% Toyo Morton Co., Ltd.-TM-K55 (polyester type) non-volatile content 30% Toyo Morton Co., Ltd.-TM-K76 (polyester type) non-volatile content 51% Made by Toyo Morton Co., Ltd. (hardening agent)
-CAT-10L (aromatic) non-volatile content 52.5% manufactured by Toyo Morton Co., Ltd.-CAT-RT85 (aliphatic-based) non-volatile content 70% manufactured by Toyo Morton Co., Ltd.
(Method for producing heat-curable adhesive used for heat-cured adhesive layer)
・ Adhesive A
The base material TM-K55 of the thermosetting adhesive and the curing agent CAT-10L were mixed at a weight ratio of 17/3, and diluted with ethyl acetate so that the solid content was 30%.
・ Adhesive B
The base material TM-585-60 of the thermosetting adhesive and the curing agent CAT-10L were mixed in a weight ratio of 100/7, and diluted with ethyl acetate so that the solid content was 30%.
・ Adhesive C
The thermosetting adhesive TM-K76 as the main agent and the curing agent CAT-10L were mixed at a weight ratio of 100/7, and diluted with ethyl acetate so that the solid content was 30%.
・ Adhesive D
The thermosetting adhesive TM-K76 as the main agent and the curing agent CAT-RT85 were mixed at a weight ratio of 100/7, and diluted with ethyl acetate so that the solid content was 30%.
＜支持体＞
支持体の粘接着剤層形成用組成物、および基材には、下記の製品を用いた。
・粘接着剤層形成用組成物：トーヨーケム製 オリバインＢＰＳ８１７０
・基材：木材、皮革、硬質塩ビ、ガラス
<Support>
The following products were used for the composition for forming the adhesive layer of the support and the substrate.
-Composition for forming an adhesive layer: manufactured by Toyochem Olivine BPS8170
・ Substrate: wood, leather, hard PVC, glass
［実施例１］
（支持体の作成）
粘接着剤層形成用組成物をアプリケータを使用して、ウェット厚で２００μｍ となるように基材（木材）に均一に塗布し、１００℃で、３分間乾燥させ、粘接着剤層を有する厚みが５ｍｍの支持体を得た。
（電磁誘導加熱用ホットメルト接着シートの作成）
熱可塑性ホットメルト接着剤層に熱硬化しうる接着剤を塗工量Ｄｒｙで３〜１０ｇ／ｍ２になるようにグラビアコーターで塗工した。この時接着剤の温度は３０〜４５℃程度に加熱した。熱硬化しうる接着剤をとばすために、乾燥を行った。乾燥条件は、８０℃１分であった。次に、圧着ロールを用いてアルミ層と熱硬化しうる接着剤の塗工面を接着し、圧着を行った（圧着ロールは、６０℃に加熱した）。その後４０℃４日間の環境下でエージングを行い、アルミ層、熱可塑性ホットメルト接着剤層の順で積層されてなる積層物を得た。なお、コロナ処理については、コロナ処理面が熱硬化性接着剤面と接するように、熱可塑性ホットメルト接着剤層にコロナ処理を行った。
更に上記で得た支持体の粘接着剤層面とアルミ層と、を手で軽く止め、接着させることにより、熱可塑性ホットメルト接着剤層、熱硬化した接着剤層、金属層、支持体の順で積層した電磁誘導加熱用ホットメルト接着シートを得た。
（電磁誘導加熱による接着構造物の作成）
電磁誘導加熱用ホットメルト接着シートを被着体（ＰＥシート）の上に置いて、電磁誘導加熱装置（アキレス社製、オールオーバー接着装置）を、支持体の外側に押し当てて２秒間加熱して、加熱終了後、熱可塑性ホットメルト接着剤層が冷えるまで約５秒程度電磁誘導加熱装置のアプリケータ部（コイル）を押し当てたままにして、電磁誘導加熱用ホットメルト接着シートと被着体とを接着し、接着構造物を得た。
[Example 1]
(Creation of support)
Using the applicator, the composition for forming a pressure-sensitive adhesive layer is uniformly applied to a base material (wood) so as to have a wet thickness of 200 μm, and dried at 100 ° C. for 3 minutes to form a pressure-sensitive adhesive layer. A support having a thickness of 5 mm was obtained.
(Preparation of hot melt adhesive sheet for electromagnetic induction heating)
A thermosetting adhesive was applied to the thermoplastic hot melt adhesive layer with a gravure coater so that the coating amount Dry was 3 to 10 g / m 2 . At this time, the temperature of the adhesive was heated to about 30 to 45 ° C. Drying was performed to skip the heat-curable adhesive. The drying condition was 80 ° C. for 1 minute. Next, the aluminum layer and the coated surface of the thermosetting adhesive were bonded to each other using a pressure bonding roll, and pressure bonding was performed (the pressure bonding roll was heated to 60 ° C.). Then, aging was performed in an environment of 40 ° C. for 4 days to obtain a laminate in which an aluminum layer and a thermoplastic hot melt adhesive layer were laminated in this order. Regarding the corona treatment, the thermoplastic hot melt adhesive layer was subjected to corona treatment so that the corona-treated surface was in contact with the thermosetting adhesive surface.
Further, the tacky adhesive layer surface of the support obtained above and the aluminum layer are lightly stopped by hand and adhered to each other to form a thermoplastic hot-melt adhesive layer, a thermosetting adhesive layer, a metal layer, and a support. A hot melt adhesive sheet for electromagnetic induction heating, which was laminated in order, was obtained.
(Preparation of bonded structure by electromagnetic induction heating)
Place the hot-melt adhesive sheet for electromagnetic induction heating on the adherend (PE sheet), press the electromagnetic induction heating device (Achilles Inc., all-over adhesive device) on the outside of the support and heat for 2 seconds. After completion of heating, the applicator part (coil) of the electromagnetic induction heating device is pressed and held for about 5 seconds until the thermoplastic hot melt adhesive layer cools, and the hot melt adhesive sheet for electromagnetic induction heating is adhered to it. The body was adhered to obtain an adhesive structure.
［実施例２〜２３］
支持体の種類と厚さ、熱可塑性ホットメルト接着剤層の種類、膜厚およびコロナ処理の有無、熱硬化性接着剤層の種類と膜厚、金属層の種類と厚さ、支持体、接着構造物の作成時の加熱時間を表１〜４に記載のとおり変更した以外は、実施例１と同様にして、実施例２〜２３において、接着シート、および接着構造物を得た。
ただし、実施例１９〜２３は参考例である。
[Examples 2 to 23]
Type and thickness of support, type of thermoplastic hot melt adhesive layer, film thickness and presence / absence of corona treatment, type and thickness of thermosetting adhesive layer, type and thickness of metal layer, support, adhesion An adhesive sheet and an adhesive structure were obtained in Examples 2 to 23 in the same manner as in Example 1 except that the heating time at the time of producing the structure was changed as described in Tables 1 to 4.
However, Examples 19 to 23 are reference examples.
［熱可塑性ホットメルト接着剤層、接着シート、および接着構造物の評価］：
下記の評価方法を用いて、実施例１〜２３で作成した熱可塑性ホットメルト接着剤層、接着シート、および接着構造物の評価を行った。表１〜４に記載のとおり、評価結果を得た。
（１）表面粗さＲａの測定方法
Taylar Hobson社製のファームタリサーフシリーズｉ６０を用いて測定した。表面粗さはＲａを用いた。測定条件は下記のとおりであり、５回の測定の平均値をもって値とした。
針の種類；先端２μｍダイヤモンドスタイラス
カットオフ周波数λｃ；８０μｍ
測定長；１ｍｍ
速度；２ｍｍ／ｍｉｎ．
（２−１） 電磁誘導加熱用ホットメルト接着シートと被着体との接着力の測定方法
接着強度は、引張り試験機（株式会社エー・アンド・エー社製、商品名ＲＴＡ−１００）を用いて、剥離速度３００ｍｍ／分でせん断強度を測定した（測定温度：２３℃、湿度５０％）。
剥離力は、１０Ｎ／２５ｍｍ以上（基材破壊含む）を「〇」、１０Ｎ未満５Ｎ以上／２５ｍｍを「△」、５Ｎ／２５ｍｍ未満を「×」とした。
（２−２）接着構造物の外観：
目視で、電磁誘導加熱用ホットメルト接着シートと被着体の接着後の接着構造物を観察した。接着構造物の表面が皺なく、（電磁誘導加熱用ホットメルト接着シートの支持体面）平滑である：「○」、接着構造物の表面が皺あり、（電磁誘導加熱用ホットメルト接着シートの支持体面）凸凹感があり、外観が悪い：「×」。
（３）剥離試験
実施例１〜２３の電磁誘導加熱用ホットメルト接着シートを用いた接着構造体は、それぞれ、接着工程と同様の電磁誘導加熱条件で加熱したところ、いずれも、容易に被着体より剥離できた。
[Evaluation of thermoplastic hot melt adhesive layer, adhesive sheet, and adhesive structure]:
Using the following evaluation methods, the thermoplastic hot melt adhesive layer, the adhesive sheet, and the adhesive structure prepared in Examples 1 to 23 were evaluated. The evaluation results were obtained as described in Tables 1 to 4.
(1) Method of measuring surface roughness Ra
The measurement was performed using a firm Talysurf series i60 manufactured by Taylar Hobson. Ra was used for the surface roughness. The measurement conditions are as follows, and the average value of 5 measurements was taken as the value.
Needle type; Tip 2μm Diamond stylus cutoff frequency λc; 80μm
Measurement length: 1 mm
Speed: 2 mm / min.
(2-1) Method for measuring adhesive force between hot-melt adhesive sheet for electromagnetic induction heating and adherend Use a tensile tester (manufactured by A & A Co., Ltd., trade name RTA-100) for adhesive strength. Then, the shear strength was measured at a peeling speed of 300 mm / min (measurement temperature: 23 ° C., humidity 50%).
For the peeling force, 10 N / 25 mm or more (including substrate breakage) was “◯”, less than 10 N was 5 N or more / 25 mm was “Δ”, and less than 5 N / 25 mm was “X”.
(2-2) Appearance of bonded structure:
The adhesive structure after adhesion of the hot-melt adhesive sheet for electromagnetic induction heating and the adherend was visually observed. The surface of the adhesive structure is smooth without wrinkles (support surface of hot melt adhesive sheet for electromagnetic induction heating): "○", the surface of the adhesive structure is wrinkled, (support for hot melt adhesive sheet for electromagnetic induction heating Body surface) Roughness and poor appearance: “X”.
(3) Peeling Test Each of the bonded structures using the hot melt adhesive sheet for electromagnetic induction heating of Examples 1 to 23 was heated under the same electromagnetic induction heating conditions as in the bonding step. I was able to peel it from my body.
（比較例１）
押出しラミネーター（ムサシノキカイ社製４００Ｍ／ＭテストＥＸＴラミネーター）を用いて、支持体（基材：王子タック製のＰＥＴＣ５０ ポリエチレンテレフタレートフイルム厚さ５０μｍ、粘接着剤層形成用組成物：トーヨーケム製 オリバインＢＰＳ８１７０）の上、に実施例１７に使用した金属層（アルミ２０μｍ）、熱硬化接着剤層（接着剤Ｃ）、熱可塑性接着剤層（変性オレフィン樹脂を５００μｍ）の順で、同様の方法で製膜したところ、電磁誘導加熱用ホットメルト接着シートと被着体との接着が可能となるが、支持体の変性により、接着構造物の表面が皺あり、外観が悪いとなった。
(Comparative Example 1)
Using an extrusion laminator (400M / M test EXT laminator manufactured by Musashino Kikai Co., Ltd.), a support (base material: PETC50 polyethylene terephthalate film thickness 50 μm manufactured by Oji Tuck, composition for forming a viscous adhesive layer: olivine BPS8170 manufactured by Toyochem) A metal layer (aluminum 20 μm) used in Example 17, a thermosetting adhesive layer (adhesive C), and a thermoplastic adhesive layer (modified olefin resin of 500 μm) were used in this order in the order above to form a film by the same method. As a result, the hot melt adhesive sheet for electromagnetic induction heating and the adherend could be bonded, but the surface of the bonded structure was wrinkled due to the modification of the support, resulting in a poor appearance.
Claims (5)
熱可塑性ホットメルト接着剤層（Ｃ）の厚さは、１０μｍ以上５００μｍ以下であり、
金属層（Ａ）の厚さが、１μｍ以上１０００μｍ以下である
電磁誘導加熱用ホットメルト接着剤層を有する積層物。 A support having a thickness of 1 mm or more, a metal layer (A), a thermosetting adhesive layer (B), and a thermoplastic hot melt adhesive layer (C) are laminated in this order,
The thickness of the thermoplastic hot melt adhesive layer (C) is 10 μm or more and 500 μm or less,
A laminate having a hot-melt adhesive layer for electromagnetic induction heating, wherein the metal layer (A) has a thickness of 1 μm or more and 1000 μm or less.
The adhesive structure according to claim 3 is heated by an electromagnetic induction heating device to soften or melt the thermoplastic hot melt adhesive layer (C) to thereby form an adherend and a hot melt adhesive layer (C). How to peel off.
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