JP2019130729A - Sustained-release sheet and method for producing the same - Google Patents
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本発明は、液状成分を除放する除放性シート及びその製造方法に関する。 The present invention relates to a sustained release sheet for releasing a liquid component and a method for producing the same.
従来より、殺虫剤・虫除け剤、殺菌剤、芳香剤といった機能性の液状成分が多く利用されている。これら液状成分は有効な成分が揮発・放出されることで目的とする効果を得るものである。液状成分を利用する方法としては、液体を塗り付けたり、スプレー状に噴霧する等の液状成分を直接塗布する方法があり、使用者が任意の箇所に液状成分を塗ることで、その効果を得ることができる。しかしながら、この方法では、液状成分が簡単に流れ落ちてしまうため、短期間しか効果が得られない。これら液状成分は、より長く効果を持たせることが求められる場合がある。 Conventionally, many functional liquid components such as insecticides / insect repellents, bactericides, and fragrances have been used. These liquid components are intended to obtain the desired effect by volatilizing and releasing effective components. As a method of using a liquid component, there is a method of directly applying a liquid component such as applying a liquid or spraying it in a spray form, and the effect is obtained by applying the liquid component to an arbitrary place by the user. be able to. However, this method is effective only for a short period because the liquid component easily flows down. These liquid components may be required to have a longer effect.
液状成分による効果をより長く持たせようとしたとき、簡単な方法では、液状成分を不織布に含浸させて使用する方法もある。ゆっくりと徐々に放出させて、効果をより長く持たせる方法として、合成樹脂内部に液状成分を練り込む方法も提案されている。例えば、特許文献１に、多孔質シリカに液体香料を吸着させてこれを熱可塑性樹脂中に分散させる方法が記載されている。 When trying to give the effect of the liquid component for a longer time, as a simple method, there is a method in which the liquid component is impregnated into the nonwoven fabric. A method of kneading a liquid component into a synthetic resin has also been proposed as a method of slowly and gradually releasing it to have a longer effect. For example, Patent Document 1 describes a method of adsorbing a liquid fragrance on porous silica and dispersing it in a thermoplastic resin.
不織布に液状成分を含浸させる方法では、多くの液状成分を担持させることは可能であるが、液状成分を放出する量が時間の経過と共に大幅に小さくなる上に、さほど長く効果が持続しない。また、不織布に含浸させる方法は、液状成分が不織布内に留まりにくく、不織布に接触したものに液状成分が移行することで、接触したものにシミをつくるなどの悪影響を及ぼすおそれもある。 In the method of impregnating the non-woven fabric with the liquid component, it is possible to carry a large amount of the liquid component, but the amount of the liquid component released becomes significantly smaller with the passage of time, and the effect does not last so long. Moreover, the method of impregnating a nonwoven fabric has a possibility that a liquid component does not stay in a nonwoven fabric easily, and when a liquid component transfers to what contacted the nonwoven fabric, it may have a bad influence, such as making a stain on the contacted thing.
合成樹脂内部に液状成分を練り込む方法では、押出機を通すために、かなりの高温下でも熱によって液状成分が変質しないことが求められる。仮に押出機を通ったとしても適切に分散し、押出し状態が安定しなければ適切な形状に成型されない。このため、利用できる範囲に大きな制約が生じてしまう。また、樹脂内に液状成分が練り込まれていることで一見長く効果が持続しそうであるが、思いのほか早期に液状成分が表面に染み出してしまい長期に効果が持続しない場合もある。 In the method of kneading the liquid component inside the synthetic resin, it is required that the liquid component does not deteriorate due to heat even at a considerably high temperature in order to pass through an extruder. Even if it passes through an extruder, it will not be properly molded unless it is properly dispersed and the extruded state is stable. For this reason, a big restriction | limiting arises in the range which can be utilized. In addition, the liquid component is kneaded into the resin, and the effect seems to last for a long time. However, the liquid component oozes out on the surface at an early stage, and the effect may not last for a long time.
本発明は、多孔質層によって液状成分が担持され、液状成分による効果が持続する徐放性シート、及びその製造方法を提供することを目的とする。 An object of this invention is to provide the sustained release sheet | seat in which the liquid component is carry | supported by the porous layer and the effect by a liquid component lasts, and its manufacturing method.
本発明は、徐放性シート及びその製造方法による検討結果から得られた知見、すなわち低結晶性ポリオレフィン及び充填材を含む樹脂組成物からなる多孔質層を備えた延伸体における充填材周囲の空隙に液状成分を担持させることが、徐放性シートに好適である、との知見に基づいてなされたものである。すなわち、本発明は以下の通りである。 The present invention relates to the knowledge obtained from the results of the investigation by the sustained release sheet and the production method thereof, that is, the voids around the filler in the stretched body having a porous layer made of a resin composition containing a low crystalline polyolefin and a filler. The liquid component is carried on the basis of the knowledge that it is suitable for the sustained release sheet. That is, the present invention is as follows.
（１）低結晶性ポリオレフィン及び充填材を含む樹脂組成物からなる多孔質層を備えており、該多孔質層は、充填材の周囲に空隙を有する延伸体であり、前記空隙に室温２５℃における蒸気圧が１×１０−４〜１０４Ｐａの液状成分を担持した徐放性シート。
（２）延伸体に粘着層が積層された上記（１）に記載の徐放性シート。
（３）延伸体は、多孔質層に高結晶性樹脂からなる防護層が積層された状態の積層延伸体である上記（１）又は（２）に記載の徐放性シート。
（４）低結晶性ポリオレフィン及び充填材を含む樹脂組成物からなる第一樹脂層の未延伸体の少なくとも一部に液状成分を接触させながら延伸し、充填材の周囲に形成された空隙に液状成分が担持された多孔質層を形成する徐放性シートの製造方法。
（５）前記第一樹脂層と結晶性樹脂組成物からなる第二樹脂層とを共押出して得られた未延伸体を用いて前記延伸を行い、多孔質層に結晶性樹脂組成物からなる防護層を積層する上記（４）に記載の徐放性シートの製造方法。
（６）未延伸体は、円筒フィルム状である上記（４）又は上記（５）に記載の徐放性シートの製造方法。
（７）前記延伸により空隙に液状成分が担持された多孔質層を形成した後、さらに延伸及び／又は熱緩和処理を行う上記（４）から上記（６）のいずれかに記載の徐放性シートの製造方法。
(1) A porous layer made of a resin composition containing a low crystalline polyolefin and a filler is provided, and the porous layer is a stretched body having voids around the filler, and the voids have a room temperature of 25 ° C. Sustained release sheet carrying a liquid component having a vapor pressure of 1 × 10 −4 to 10 4 Pa.
(2) The sustained release sheet according to the above (1), wherein an adhesive layer is laminated on the stretched body.
(3) The sustained-release sheet according to (1) or (2), wherein the stretched body is a laminated stretched body in a state where a protective layer made of a highly crystalline resin is laminated on a porous layer.
(4) The liquid component is stretched in contact with at least a part of the unstretched body of the first resin layer comprising the resin composition containing the low crystalline polyolefin and the filler, and is liquid in the voids formed around the filler. A method for producing a sustained-release sheet, which forms a porous layer carrying a component.
(5) The above-mentioned stretching is performed using an unstretched body obtained by co-extrusion of the first resin layer and the second resin layer composed of the crystalline resin composition, and the porous layer is composed of the crystalline resin composition. The method for producing a sustained-release sheet according to (4) above, wherein a protective layer is laminated.
(6) The method for producing a sustained release sheet according to (4) or (5), wherein the unstretched body has a cylindrical film shape.
(7) The sustained release property according to any one of (4) to (6) above, wherein after the stretching, a porous layer having a liquid component supported in the voids is formed, further stretching and / or thermal relaxation treatment is performed. Sheet manufacturing method.
本発明によれば、多孔質層によって液状成分が担持され、液状成分による効果が持続する徐放性シート、及びその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the liquid component is carry | supported by the porous layer, the sustained release sheet which the effect by a liquid component continues, and its manufacturing method can be provided.
以下、本発明を実施するための好適な実施形態について説明する。 Hereinafter, preferred embodiments for carrying out the present invention will be described.
徐放性シートは、低結晶性ポリオレフィン及び充填材を含む樹脂組成物を第一樹脂層として、これを延伸した多孔質層を少なくとも有する。この低結晶性ポリオレフィンは、結晶性の低いポリオレフィンであって、低密度ポリエチレン、低立体規則性ポリプロピレン、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸アルキル共重合体、エチレン−プロピレン共重合体等を単体又は複数種混合したものをいう。ポリオレフィンを用いる理由には、耐薬品性に優れ、液状成分と反応しにくいことが挙げられる。この観点では、低密度ポリエチレン、低立体規則性ポリプロピレン、エチレン−プロピレン共重合体を用いることが好ましい。延伸を伴うものであることから、線状低密度ポリエチレンを含んでいることがより好ましいといえる。 The sustained release sheet has at least a porous layer obtained by stretching a resin composition containing a low crystalline polyolefin and a filler as a first resin layer. This low crystalline polyolefin is a low crystalline polyolefin, such as low density polyethylene, low stereoregular polypropylene, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, ethylene-propylene copolymer, etc. Means a single substance or a mixture of plural kinds. The reason for using polyolefin is that it is excellent in chemical resistance and hardly reacts with liquid components. From this viewpoint, it is preferable to use low density polyethylene, low stereoregular polypropylene, or ethylene-propylene copolymer. Since it involves stretching, it can be said that it is more preferable that linear low density polyethylene is included.
結晶性の低いポリオレフィンを用いる理由は、その結晶性に応じて液状成分が放出される量が変化するためである。結晶性が低いほど樹脂を通じて液状成分が放出されやすくなり、結晶性が高くなりすぎると液状成分の放出はほとんどなくなる。つまりは、低結晶性ポリオレフィンと高結晶性ポリオレフィンを組み合わせることや、低結晶性ポリオレフィンとより非結晶に近いポリオレフィンを組み合わせることでも、液状成分の放出を調節することができる。低結晶性ポリオレフィンとして、低密度ポリエチレンを用いる場合、密度が低い方が結晶性が低い傾向にあり、その密度が０．８９５〜０．９２５ｇ／ｃｍ３にあるものを含んでいることが好ましい。また、延伸を伴い、加工における液状成分の影響を考慮すると、低温で延伸加工できることが好ましく、低密度ポリエチレンの融点は８０〜１３５℃であることが好ましく、その軟化点は４５〜９０℃であることが好ましい。なお、低結晶性ポリオレフィンと組み合わせる高結晶性ポリオレフィンは、代表的には、アイソタクチックポリプロピレン、高密度ポリエチレン等であり、低密度ポリエチレンと共に混ぜる上では、分散性を考慮して高密度ポリエチレンを使用することが好ましい。 The reason for using polyolefin with low crystallinity is that the amount of liquid component released changes according to its crystallinity. The lower the crystallinity, the easier the liquid component is released through the resin. If the crystallinity is too high, the liquid component is hardly released. In other words, the release of the liquid component can be controlled by combining a low crystalline polyolefin and a high crystalline polyolefin, or by combining a low crystalline polyolefin and a more amorphous polyolefin. When low density polyethylene is used as the low crystalline polyolefin, the lower the density, the lower the crystallinity tends to be, and it is preferable that the density is 0.895 to 0.925 g / cm 3 . In addition, taking into account the influence of the liquid component in processing with drawing, it is preferable that drawing can be carried out at a low temperature. The melting point of low density polyethylene is preferably 80 to 135 ° C, and the softening point thereof is 45 to 90 ° C. It is preferable. High crystalline polyolefins combined with low crystalline polyolefins are typically isotactic polypropylene, high density polyethylene, etc. When mixing with low density polyethylene, high density polyethylene is used in consideration of dispersibility. It is preferable to do.
充填材は、炭酸カルシウム、タルク、シリカ、マイカ、酸化亜鉛、硫酸バリウム、酸化チタン、アルミニウム等の主に無機フィラーをいうが、ポリスチレン、メタクリル樹脂、ポリエステル等、低結晶性ポリオレフィンと非相溶で常温で硬質な性状を示す有機物であってもよい。充填材は、延伸により無数の空隙を形成するためのものであり、この空隙内に液状成分を担持させることになる。そのため充填材は液状成分に侵されにくいものが好ましく、無機フィラーである方が比較的安定している。また、空隙が安定して分布していることが好ましく、粒径の整った無機フィラーを用いることでこれが実現しやすくなる。安価でこれら条件に合うものが入手しやすい観点で炭酸カルシウムを用いることが好ましい。この粒径は特に制限はないが、延伸によって形成される複数の空隙はつながった状態であること、すなわち連通孔であることが好ましい観点から、延伸後の多孔質層の厚みを考慮して選定することが好ましく、多孔質層の厚みの０．１〜４０％の間であることが好ましい。個々の粒径としては、１．０〜１５μｍであれば均一に分散させやすいため好ましい。 Fillers are mainly inorganic fillers such as calcium carbonate, talc, silica, mica, zinc oxide, barium sulfate, titanium oxide, and aluminum, but are incompatible with low crystalline polyolefins such as polystyrene, methacrylic resin, and polyester. It may be an organic substance having a hard property at room temperature. The filler is for forming an infinite number of voids by stretching, and a liquid component is supported in the voids. Therefore, the filler is preferably less susceptible to liquid components, and the inorganic filler is relatively stable. Moreover, it is preferable that the voids are stably distributed, and this is easily realized by using an inorganic filler having a uniform particle diameter. It is preferable to use calcium carbonate from the viewpoint that it is inexpensive and easily available that meets these conditions. This particle size is not particularly limited, but is selected in consideration of the thickness of the porous layer after stretching from the viewpoint that a plurality of voids formed by stretching are in a connected state, that is, a communication hole. Preferably, it is between 0.1 and 40% of the thickness of the porous layer. The individual particle size is preferably 1.0 to 15 μm because it can be easily dispersed uniformly.
充填材は、第一樹脂層の質量の４０質量％以上を占める程度に添加することが好ましい。より好適には第一樹脂層の重量の４０〜７０質量％の範囲である。この範囲で充填材を添加することによって、延伸によって形成される複数の空隙がつながり、多孔質層の内部にまで液状成分を含ませることができ、液状成分を多量に担持させることができる。充填材が第一樹脂層の重量の４０質量％以上を下回ると、空隙がまばらにしか発生しない状態になり、層の表面付近でしか液状成分が担持できなくなる可能性がある。また、充填材が第一樹脂層の重量の７０％を上回る場合、樹脂の重量が３０質量％を下回ることになるため、シートが脆く扱いにくくなる可能性がある。 The filler is preferably added to such an extent that it accounts for 40% by mass or more of the mass of the first resin layer. More preferably, it is the range of 40-70 mass% of the weight of a 1st resin layer. By adding the filler in this range, a plurality of voids formed by stretching are connected, the liquid component can be contained even inside the porous layer, and a large amount of the liquid component can be supported. When the filler is less than 40% by mass of the weight of the first resin layer, voids are generated only sparsely, and there is a possibility that the liquid component can be supported only near the surface of the layer. Moreover, since the weight of resin will be less than 30 mass% when a filler exceeds 70% of the weight of a 1st resin layer, a sheet | seat may become weak and it may become difficult to handle.
第一樹脂層は公知の押出機を用いてフィルム状の未延伸体を形成することができる。このフィルム状の未延伸体は一般的なフィルムを作成する方法で成型してよい。フィルム状に成型後、延伸せずに冷却し、一旦、固化する。固化した後、液状成分と接触させ、これに曝しながら延伸を行う。延伸されて液状成分が空隙に担持される様子を模式図により図１に示す。この延伸は、ロール間の速度比により延伸する公知の延伸であってよい。延伸過程では、図１（ｂ）に示したように、第一樹脂層の充填材周囲に空隙が形成されることになる。ここで形成された空隙は、真空状態で形成されることになり、液状成分に曝しながら延伸している場合、液状成分を吸い上げ、充填材周囲にこれが担持されることになる。充填材周囲に液状成分を担持させる上では、液状成分に曝した状態で延伸がなされていることが極めて重要であり、延伸を開始した段階で、液状成分に曝す前に一旦、空気に曝してしまうと充填材周囲には空気が入ってしまい液状成分を担持できる量は少なくなってしまう。未延伸体にムラなく、多くの液状成分に曝すことを考慮すれば、未延伸体全体を液状成分に浸すことが好ましい。 The first resin layer can form a film-like unstretched body using a known extruder. This film-like unstretched body may be molded by a general method for producing a film. After forming into a film, it is cooled without stretching and solidified once. After solidifying, it is brought into contact with the liquid component and stretched while being exposed to this. FIG. 1 is a schematic view showing a state in which the liquid component is drawn and supported in the voids. This stretching may be a known stretching performed by a speed ratio between rolls. In the stretching process, voids are formed around the filler of the first resin layer as shown in FIG. The void formed here is formed in a vacuum state, and when it is stretched while being exposed to the liquid component, the liquid component is sucked up and supported around the filler. In carrying the liquid component around the filler, it is extremely important that the film is stretched in the state exposed to the liquid component. At the stage where the stretching is started, the film is once exposed to air before being exposed to the liquid component. As a result, air enters the periphery of the filler, and the amount that can carry the liquid component is reduced. In consideration of exposing the unstretched body to many liquid components without unevenness, it is preferable to immerse the entire unstretched body in the liquid component.
延伸して得られたシート状の延伸体の片面に、粘着剤層等を積層したり印刷することを考慮した場合、延伸体の表面に液状成分が残っているとこれらの接着が阻害される方向に働いてしまう。この対策として、片面のみに液状成分を曝すことが望まれる。然るに、徐放性シートの好適な製造方法として、低結晶性ポリオレフィン及び充填材を含む樹脂組成物からなる第一樹脂層を円筒フィルム状にして得られた未延伸体の一部を液状成分を接触させながら延伸することで充填材周囲に形成された空隙に液状成分が担持された多孔質層を形成して製造する方法が挙げられる。例えば、チューブラー方式で円筒フィルム状に未延伸体を形成し、径の両端を折り曲げ、フィルムが二重になる状態で延伸すれば、円筒内面には液状成分を接触させず、円筒外面に十分かつ確実に液状成分に曝すことができる。この方法で円筒フィルム状の未延伸体を得る場合、ブロー比を大きくしたいわゆるインフレーション状態で成形すると成形時に延伸が生じることになるため、ブロー比としては０．５〜１．２倍の範囲に留めることが望ましい。 In consideration of laminating or printing a pressure-sensitive adhesive layer on one side of a sheet-like stretched product obtained by stretching, adhesion of these components is inhibited if liquid components remain on the surface of the stretched product. Work in the direction. As a countermeasure, it is desirable to expose the liquid component to only one side. However, as a preferred method for producing a sustained-release sheet, a liquid component is used as a part of an unstretched body obtained by forming a first resin layer comprising a resin composition containing a low crystalline polyolefin and a filler into a cylindrical film shape. Examples include a method of forming a porous layer in which a liquid component is supported in a void formed around a filler by stretching while being in contact with the filler. For example, if a tubular method is used to form an unstretched body in the form of a cylindrical film, both ends of the diameter are bent, and the film is stretched in a doubled state, liquid components are not brought into contact with the cylindrical inner surface, and the cylindrical outer surface is sufficient. And it can expose to a liquid component reliably. When a cylindrical film-like unstretched body is obtained by this method, if the blow ratio is increased and molding is performed in a so-called inflation state, stretching occurs at the time of molding, so the blow ratio is in the range of 0.5 to 1.2 times. It is desirable to keep it.
上記未延伸体を延伸して得られる延伸体からなる多孔質層の空孔率は２０〜６０％の範囲にあることが好ましい。この範囲で形成されることによって、液状成分を担持できる量や、多孔質層の形状保持がバランスのとれた状態となる。多孔質層の厚みとしては５０〜２，０００μｍであることが好ましい。 The porosity of the porous layer made of a stretched product obtained by stretching the unstretched product is preferably in the range of 20 to 60%. By being formed in this range, the amount capable of supporting the liquid component and the shape retention of the porous layer are balanced. The thickness of the porous layer is preferably 50 to 2,000 μm.
液状成分は、殺虫剤・虫除け剤、殺菌剤、芳香剤、防錆剤、アロマオイル等に例示される生物活性や物理的、化学的作用を奏する成分を放出するものである。室温２５℃における蒸気圧が１×１０−４〜１０４Ｐａの液状成分を徐放性シートに担持させる。この蒸気圧の範囲にあるものは、揮発性が高い部類の液状成分である。本発明ではこのような液状成分でも長期に渡って効果を持たせることができる。 The liquid component is a component that releases biologically active, physical, and chemical components exemplified by insecticides / repellents, bactericides, fragrances, rust inhibitors, aroma oils, and the like. A liquid component having a vapor pressure of 1 × 10 −4 to 10 4 Pa at room temperature of 25 ° C. is supported on the sustained release sheet. Those in this vapor pressure range are a class of liquid components with high volatility. In the present invention, even such a liquid component can have an effect over a long period of time.
徐放性シートでは、延伸で形成される空隙が吸引する力をもって、空隙に液状成分が担持される。しかしながら、多孔質層と液状成分の間の界面張力が大きいと吸引する力に抗い空隙に液状成分が吸収されにくくなる。そのため、一般的にフィルムの延伸で水に曝した状態で延伸することも行われているが、上記の方法で水はほとんど担持しない。界面張力は、液状成分を希釈することで調節することができる。使用する成分の界面張力が大きい場合、例えば、流動パラフィン、イソプロピルアルコール、ｎ−ヘプタン等の希釈溶剤を分散させて、希釈した液状成分とすることで、多孔質層の空隙に多くの液状成分を含ませることができる。希釈溶剤は、これを用いて液状成分濃度を調整することで、シートの変質も防止し得る。なお、このシートの変質は、第一樹脂層に高結晶性ポリオレフィンを配合しておくことでも抑えることができる。 In the sustained-release sheet, a liquid component is supported in the voids with a force that the voids formed by stretching suck. However, if the interfacial tension between the porous layer and the liquid component is large, the liquid component is difficult to be absorbed by the voids that resist the suction force. For this reason, the film is generally stretched in the state of being exposed to water. However, the above method hardly carries water. The interfacial tension can be adjusted by diluting the liquid component. When the interfacial tension of the component to be used is large, for example, by diluting a diluent solvent such as liquid paraffin, isopropyl alcohol, n-heptane, etc., to obtain a diluted liquid component, a large amount of liquid component is added to the voids of the porous layer. Can be included. The diluting solvent can prevent deterioration of the sheet by adjusting the concentration of the liquid component using the diluting solvent. The alteration of the sheet can also be suppressed by adding a highly crystalline polyolefin to the first resin layer.
液状成分が担持された多孔質層には、その空孔に対し、５〜９０％の範囲で液状成分が含有されることが好ましい。この含有率が小さい場合、液状成分があまり含まれていないことになる。この含有率は高い方がより好ましいといえるが、小さい含有率であっても構造上、多孔質層内に液状成分が長く留まり、長期に渡って効果を発揮する。含有率が大きくなりすぎると、多孔質層表面に液状成分が染み出してしまうおそれもある。そのため、液状成分の含有率は５〜５０％とすることがより好ましい。 The porous layer on which the liquid component is supported preferably contains the liquid component in a range of 5 to 90% with respect to the pores. When this content rate is small, a liquid component is not included so much. It can be said that a higher content is more preferable, but even if the content is small, the liquid component stays long in the porous layer due to the structure, and the effect is exhibited over a long period of time. If the content is too high, the liquid component may ooze out on the surface of the porous layer. Therefore, the content of the liquid component is more preferably 5 to 50%.
液状成分が担持された多孔質層を単体で徐放性シートとしてもよいが、第一樹脂層及び／又はこれを延伸して得られる多孔質層に対し、その他の層を積層してもよい。 The porous layer carrying the liquid component may be a single sustained release sheet, but other layers may be laminated on the first resin layer and / or the porous layer obtained by stretching the first resin layer. .
延伸により液状成分が空隙に吸引され、液状成分が担持された多孔質層はほとんどその表面に染み出しがない状態になる。液状成分が表面に染み出している状態では、液状成分が介在することで、積層が困難になるが、多孔質層内部で液状成分が十分に担持されていれば、上記の第一樹脂層及び／又はこれを延伸して得られる多孔質層に対し、その他の層を積層することも可能になる。例えば、粘着剤層を積層すれば、衣服、家具、建具、電化製品等、任意の箇所に貼り付けることが可能であり、防虫効果や芳香効果等を手軽に得られる徐放性シートになる。 The liquid component is sucked into the voids by stretching, and the porous layer on which the liquid component is supported becomes almost free from bleeding on the surface. In a state where the liquid component is oozing out on the surface, the liquid component intervenes, making lamination difficult, but if the liquid component is sufficiently supported inside the porous layer, the first resin layer and Other layers can also be laminated on the porous layer obtained by stretching this. For example, if an adhesive layer is laminated | stacked, it can be affixed on arbitrary places, such as clothes, furniture, fittings, and electrical appliances, and it becomes a sustained release sheet | seat which can obtain an insect-proof effect, an aromatic effect, etc. easily.
粘着剤層を積層し、手軽に貼り付けることが可能な徐放性シートとする観点では、簡単に剥がせることも求められる。剥がし易さを考慮した場合、当然強力な接着力を有する粘着剤は使用できず、アクリル系粘着剤に代表される粘着剤を使用することになる。このとき、液状成分が多孔質層表面に僅かに介在する状態であれば粘着剤層と多孔質層の接着力が落ちることになり、糊残りの原因となる。従って、多孔質層を形成する際、円筒フィルム状に未延伸体を形成した上で、液状成分に接触させて延伸する等、なるべく粘着剤層を積層する面には液状成分を存在させないことが望ましい。なお、円筒フィルム状に未延伸体を形成した上で、液状成分を接触させて延伸した場合は、液状成分を接触させた面同士を接触させて巻き取ることが可能であり、保管中に多少液状成分が染み出すことがあっても、液状成分に接触させていない面に染み出した液状成分が接触することを避けることができる。 From the viewpoint of laminating the pressure-sensitive adhesive layer and making it a sustained release sheet that can be easily attached, it is also required to be easily peeled off. In consideration of ease of peeling, a pressure-sensitive adhesive having a strong adhesive force cannot be used, and a pressure-sensitive adhesive represented by an acrylic pressure-sensitive adhesive is used. At this time, if the liquid component is slightly interposed on the surface of the porous layer, the adhesive force between the pressure-sensitive adhesive layer and the porous layer will be reduced, which will cause adhesive residue. Therefore, when forming the porous layer, after forming an unstretched body in the form of a cylindrical film, the liquid component should not be present on the surface on which the pressure-sensitive adhesive layer is laminated as much as possible, such as stretching in contact with the liquid component. desirable. In addition, when an unstretched body is formed in a cylindrical film shape and then stretched by bringing the liquid component into contact with each other, it can be wound by bringing the surfaces in contact with the liquid component into contact with each other. Even if the liquid component oozes out, it can be avoided that the liquid component oozed out on the surface not in contact with the liquid component.
粘着剤層をより確実に積層する観点では、多孔質層の片面に結晶性樹脂からなる防護層を積層しておき、その防護層に粘着剤層を積層することが好ましい。また、結晶性樹脂で形成した防護層を備えていれば、粘着剤層を設けるか否かに係わらず、防護層側の液状成分の放出が抑えられることで、効果がより持続するし、放出する方向が限定されることで効果を高めることも期待できるし、防護層によって防護層に接触するものと液状成分が放出する成分とが反応し、この接触物が変質する可能性を低減させることができる。つまりは、液状成分が放出する成分と粘着剤が反応し、粘着剤が変質することで生じる糊残り等の可能性も低減させることもできる。 From the viewpoint of more reliably laminating the pressure-sensitive adhesive layer, it is preferable that a protective layer made of a crystalline resin is laminated on one side of the porous layer, and the pressure-sensitive adhesive layer is laminated on the protective layer. In addition, if a protective layer formed of a crystalline resin is provided, the effect of the liquid component on the protective layer side can be suppressed regardless of whether or not the adhesive layer is provided. The effect can be expected to be enhanced by limiting the direction in which the contact is made, and the contact with the protective layer by the protective layer and the component released by the liquid component react to reduce the possibility of the contact material being altered. Can do. That is, it is possible to reduce the possibility of adhesive residue or the like caused by the reaction between the component released from the liquid component and the adhesive, and the adhesive changing in quality.
高結晶性樹脂からなる防護層の積層は、強力な接着剤を使う等、任意の方法で積層できる。より確実な層間接着強力をもって積層する観点では、多孔質層となる第一樹脂層を成型する際に、共押出しにより、延伸後に防護層となる第二樹脂層を予め積層した状態で形成し、この未延伸体を、少なくとも第一樹脂層に液状成分を接触させながら延伸することで、充填材周囲に形成された空隙に液状成分が担持された多孔質層と防護層とを同時に形成することが好ましい。 The protective layer made of a highly crystalline resin can be laminated by any method such as using a strong adhesive. From the viewpoint of laminating with a more reliable interlayer adhesion strength, when molding the first resin layer to be a porous layer, by co-extrusion, formed in a state in which a second resin layer to be a protective layer after stretching is previously laminated, By stretching this unstretched body while bringing the liquid component into contact with at least the first resin layer, a porous layer in which the liquid component is supported in a void formed around the filler and a protective layer are simultaneously formed. Is preferred.
防護層になる樹脂組成物としては、高い結晶性を有する樹脂であれば特に制限されないが、特に第二樹脂層に使用する樹脂組成物としては、結晶性樹脂の内、延伸後に高い結晶性を示す樹脂であることが好ましく、高密度ポリエチレン、アイソタクチックポリプロピレン、ポリアミド６、ポリエチレンテレフタラート、ポリブチレンテレフタラート等が挙げられる。これらは液状成分の特性を考慮して選択がなされる。多孔質層との接着性のみを重視すれば、高密度ポリエチレン、アイソタクチックポリプロピレン等の高結晶性ポリオレフィンを用いることが好ましい。 The resin composition that serves as a protective layer is not particularly limited as long as it has a high crystallinity, but the resin composition used for the second resin layer in particular has a high crystallinity after stretching, among the crystalline resins. Preferably, the resin is high density polyethylene, isotactic polypropylene, polyamide 6, polyethylene terephthalate, polybutylene terephthalate, or the like. These are selected in consideration of the characteristics of the liquid component. If only the adhesiveness with the porous layer is regarded as important, it is preferable to use a highly crystalline polyolefin such as high-density polyethylene or isotactic polypropylene.
防護層と多孔質層の層比は特に制限されるものではないが、上記のように第一樹脂層と第二樹脂層を共押出して得られる未延伸体を延伸する場合、防護層と多孔質層の層比は９５：５〜５０：５０になることが好ましい。多孔質層を得るときの延伸は、比較的低温下で行うために、高温下での延伸が難しい事情がある。第二樹脂層の厚みが厚くなりすぎると、延伸の際の応力が大きく係り延伸が困難になる。そのため、延伸性の改善のために、第二樹脂層の結晶性樹脂に対し、柔軟な合成樹脂を配合してもよい。 The layer ratio of the protective layer and the porous layer is not particularly limited, but when the unstretched body obtained by co-extrusion of the first resin layer and the second resin layer is stretched as described above, the protective layer and the porous layer are porous. The layer ratio of the quality layer is preferably 95: 5 to 50:50. Since the stretching for obtaining the porous layer is performed at a relatively low temperature, there is a situation in which the stretching at a high temperature is difficult. If the thickness of the second resin layer becomes too thick, the stress at the time of stretching becomes large and stretching becomes difficult. Therefore, in order to improve stretchability, a flexible synthetic resin may be blended with the crystalline resin of the second resin layer.
第一樹脂層と第二樹脂層を共押出して得られる未延伸体を延伸する場合や片面のみに液状成分を曝して延伸する場合、片面に集中して液状成分が担持される上に、低い温度下で延伸されることも重なって、その延伸体にはカールが生じやすい。このカールは、表裏で樹脂が異なることで、特に第一樹脂層と第二樹脂層を共押出して得られる未延伸体を延伸する場合に、より大きく反り返りやすい。そのため、液状成分を担持させる延伸を行った後、さらに第二の延伸及び／又は熱緩和処理を行うことが好ましい。これらの処理を行うことで、カールを矯正し、反り返りを大幅に抑制することができる。また、液状成分を担持させる延伸を第一の延伸とすれば、第二の延伸は、第一の延伸で吸い上げきれず多孔質層の表面に付着した液状成分を吸い込み直す効果を有する。熱緩和処理では、空隙を僅かに埋める効果と、低い温度下で伸ばされたことによる伸び戻りを防止する効果を有する。これらの処理によって、徐放性シートからの液状成分の染み出しをより確実に防止すると共に、より長期に渡って液状成分による効果を発揮し続けることになる。なお、この第二の延伸や熱緩和処理は、熱板や熱ロール等で加熱し、ロール間の速度比によって延伸や熱緩和処理をする方法でよい。このときの加熱条件としては、第一の延伸よりも高い温度下で行うことが好ましく、その温度差は２０℃以内でよい。 When stretching an unstretched body obtained by co-extrusion of the first resin layer and the second resin layer, or when exposing and stretching the liquid component only on one side, the liquid component is concentrated on one side and supported. The stretched body overlaps with the stretched temperature, and the stretched body tends to curl. This curl is more likely to warp when the unstretched body obtained by co-extrusion of the first resin layer and the second resin layer is stretched because the resins are different between the front and back surfaces. Therefore, it is preferable to perform the second stretching and / or heat relaxation treatment after the stretching for supporting the liquid component. By performing these treatments, curling can be corrected and warping can be greatly suppressed. Further, if the stretching for supporting the liquid component is the first stretching, the second stretching has an effect of reabsorbing the liquid component that cannot be sucked up by the first stretching and adheres to the surface of the porous layer. The thermal relaxation treatment has an effect of slightly filling the gap and an effect of preventing the elongation from returning due to being stretched at a low temperature. These treatments more reliably prevent the liquid component from oozing out from the sustained-release sheet and continue to exert the effect of the liquid component for a longer period of time. In addition, this 2nd extending | stretching and heat relaxation process may be the method of heating with a hot plate, a hot roll, etc., and performing extending | stretching and a heat relaxation process with the speed ratio between rolls. As heating conditions at this time, it is preferable to carry out under higher temperature than 1st extending | stretching, The temperature difference may be 20 degrees C or less.
上記の第二の延伸及び／又は熱緩和処理の記載は、第二の延伸と熱緩和処理のいずれかのみを行ってもよいことを意味するが、これらは双方共に行うことがより好ましく、第二の延伸を行った後に、熱緩和処理を行うことがさらに好ましい。第一の延伸と第二の延伸を行った後で放置すると伸ばされた樹脂が縮もうとする力が大きいため、この力により、空隙内に担持されていた液状成分が染み出してしまう可能性があるし、第一の延伸直後に熱緩和処理を行うと、強制的に縮めるために、空隙内に担持されていた液状成分が染み出すおそれがある。第二の延伸における延伸倍率は、１．０１〜１．５倍の範囲であることが好ましく、熱緩和処理では５〜２０％の範囲で縮めることが好ましい。 The above description of the second stretching and / or thermal relaxation treatment means that either the second stretching or the thermal relaxation treatment may be performed, but it is more preferable that both of them are performed. More preferably, the thermal relaxation treatment is performed after the second stretching. If left after the first and second stretching, the stretched resin has a large force to shrink, and this force may cause the liquid component carried in the voids to ooze out. However, if the thermal relaxation treatment is performed immediately after the first stretching, the liquid component carried in the voids may ooze out due to forcible shrinkage. The draw ratio in the second drawing is preferably in the range of 1.01 to 1.5 times, and in the thermal relaxation treatment, it is preferably reduced in the range of 5 to 20%.
上記のようにして得られた徐放性シートによる液状成分の放出は、一定の放出量を保ちながら長期に渡って放出するものであり、粘着剤層を備える徐放性シートは、例えば、衣類、家具、電化製品、建具等、任意の様々な場所に貼り付けることができる。例えば、虫除け剤を液状成分として使用したものならば、衣類や窓まわりのサッシ等に貼り付けて手軽に虫除け効果を得られるし、芳香剤を液状成分として使用したものならば、衣類やリビング家具等に貼り付けて芳香スプレーの替わりとして使用することもできる。 The release of the liquid component by the sustained release sheet obtained as described above is a release over a long period of time while maintaining a constant release amount. , Furniture, electrical appliances, joinery, etc. For example, if an insect repellent is used as a liquid component, it can be easily applied by attaching it to clothing or a sash around a window, and if an air freshener is used as a liquid component, clothing or living furniture It can also be used as an alternative to fragrance sprays.
以下、実施例により本発明を更に具体的に説明するが、本発明は以下の実施例のみに限定されない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited only to a following example.
［実施例１］
線状低密度ポリエチレン（密度０．９３２ｇ／ｃｍ３、融点１２３℃、ＭＦＲ３．０ｇ／１０ｍｉｎ（１９０℃、２１６０ｇ荷重））１６質量％、低密度ポリエチレン（密度０．９２３ｇ／ｃｍ３、融点１１２℃、ＭＦＲ１．５ｇ／１０ｍｉｎ（１９０℃、２１６０ｇ荷重））１６質量％、超低密度ポリエチレン（密度０．９００ｇ／ｃｍ３、融点１１５℃、ＭＦＲ２．０ｇ／１０ｍｉｎ（１９０℃、２１６０ｇ荷重））８質量％及び、炭酸カルシウム（平均粒径５μｍ）６０質量％を混合した混合物Ａを、Ｔダイ方式で押出し、チルロールで冷却して、未延伸フィルム１を得た。
[Example 1]
Linear low density polyethylene (density 0.932 g / cm 3 , melting point 123 ° C., MFR 3.0 g / 10 min (190 ° C., 2160 g load)) 16% by mass, low density polyethylene (density 0.923 g / cm 3 , melting point 112 ° C. , MFR 1.5 g / 10 min (190 ° C., 2160 g load)) 16 mass%, ultra-low density polyethylene (density 0.900 g / cm 3 , melting point 115 ° C., MFR 2.0 g / 10 min (190 ° C., 2160 g load)) 8 mass % And 60% by mass of calcium carbonate (average particle size 5 μm) were extruded by a T-die method and cooled with a chill roll to obtain an unstretched film 1.
未延伸フィルム１は、ニップロールを経由した後、延伸用の第一ロール、恒温液槽（液槽温度：６０℃）、及び延伸用の第二ロールを記載した順に通過させ、中間延伸体１を得た。なお、このとき恒温液槽には、液状成分としてメトフルトリン（蒸気圧１．９６×１０−３Ｐａ）を浸しており、第一ロールと第二ロールの速比（延伸倍率）は５倍であり、延伸は当該液状成分に曝された状態で行われるようにした。 After passing through the nip roll, the unstretched film 1 is passed through the first roll for stretching, the thermostatic liquid bath (liquid bath temperature: 60 ° C.), and the second roll for stretching in the order described, and the intermediate stretched body 1 is passed through. Obtained. At this time, methotrelin (vapor pressure 1.96 × 10 −3 Pa) is immersed as a liquid component in the constant temperature bath, and the speed ratio (stretch ratio) of the first roll and the second roll is 5 times. The stretching was performed in a state exposed to the liquid component.
中間延伸体１を得た後、連続して、中間延伸体１に対し、延伸用の複数の熱ロール群（温度：７０℃）からなる第三ロール、及び熱緩和用の複数の熱ロール群（温度：７０℃）からなる第四ロールを通し、巻き取った。第二ロールと第三ロールの最終ロール速比（延伸倍率）は１．３倍であった。第三ロールの最終ロールと第四ロールの最終ロール速比は０．９倍であり、１０％緩和されていた。巻き取られたシート体１を実施例１とした。実施例１の厚みは１８０μｍであった。 After the intermediate stretched body 1 is obtained, a third roll composed of a plurality of heat roll groups for stretching (temperature: 70 ° C.) and a plurality of heat roll groups for heat relaxation are continuously formed on the intermediate stretched body 1. It wound up through the 4th roll which consists of (temperature: 70 degreeC). The final roll speed ratio (stretch ratio) of the second roll and the third roll was 1.3 times. The final roll speed ratio between the final roll of the third roll and the fourth roll was 0.9 times, and was relaxed by 10%. The wound sheet body 1 was taken as Example 1. The thickness of Example 1 was 180 μm.
［実施例２］
実施例１の混合物Ａを、チューブラー方式で押出し、ブロー比０．８で、空冷方式により冷却して、筒状フィルムの未延伸フィルム２を得た。
[Example 2]
The mixture A of Example 1 was extruded by a tubular method and cooled by an air cooling method with a blow ratio of 0.8 to obtain an unstretched film 2 of a tubular film.
未延伸フィルム２は、ニップロールでこれを挟み、幅方向の両端を折り曲げて幅方向中間部分が２枚重ねになった面状とし、以降この状態で延伸等を行ったこと以外は、実施例１と同様にして、中間延伸体２及びシート体２を得た。巻き取られたシート体２は、幅方向の両端を長手方向に沿って切断して１枚のシート体２とし、これを実施例２とした。実施例２の厚みは１８０μｍであった。 The unstretched film 2 is sandwiched between nip rolls, folded at both ends in the width direction so as to have a planar shape in which two intermediate portions in the width direction are overlapped, and thereafter, Example 1 is performed except that stretching or the like is performed in this state. In the same manner as above, an intermediate stretched body 2 and a sheet body 2 were obtained. The wound sheet body 2 was cut at both ends in the width direction along the longitudinal direction to form one sheet body 2, which was designated as Example 2. The thickness of Example 2 was 180 μm.
［実施例３］
高密度ポリエチレン（密度０．９５６ｇ／ｃｍ３、融点１３５℃、ＭＦＲ０．８ｇ／１０ｍｉｎ（１９０℃、２１６０ｇ荷重））７０質量％、低密度ポリエチレン（密度０．９２６ｇ／ｃｍ３、融点１２４℃、ＭＦＲ０．８ｇ／１０ｍｉｎ（１９０℃、２１６０ｇ荷重））３０質量％を混合した混合物Ｂを、実施例１で用いた混合物Ａと共にチューブラー方式で共押出しした。押出されたものをブロー比０．８で、空冷方式により冷却して、筒状フィルムの内側に混合物Ｂ、外側に混合物Ａの層が配置された筒状フィルムの未延伸フィルム３を得た。以降は実施例２と同様にして、中間延伸体３、及びシート体３を得た。ここで得られた１枚のシート体３を実施例３とした。実施例３の厚みは２００μｍ（内混合物Ａの層の厚みは約２０μｍ）であった。
[Example 3]
High density polyethylene (density 0.956 g / cm 3 , melting point 135 ° C., MFR 0.8 g / 10 min (190 ° C., 2160 g load)) 70% by mass, low density polyethylene (density 0.926 g / cm 3 , melting point 124 ° C.,
［比較例１］
エチレン酢酸ビニルコポリマー（酢酸ビニル含有量１４％、融点８９℃、ＭＦＲ１．５ｇ／１０ｍｉｎ）と実施例１の液状成分であるメトフルトリンを混合した混合物Ｂを、Ｔダイ方式で押出し、チルロールで冷却して、未延伸フィルム４を得た。エチレン酢酸ビニルコポリマーとメトフルトリンの混合比は、８０：２０で混合する予定であったが、製膜が安定せず、表面に激しくメトフルトリンが染み出すことから、製膜が安定するまでメトフルトリンの混合比を下げたため、正確な混合比は定かではない。
[Comparative Example 1]
A mixture B obtained by mixing the ethylene vinyl acetate copolymer (vinyl acetate content 14%, melting point 89 ° C., MFR 1.5 g / 10 min) and metfluthrin, which is the liquid component of Example 1, was extruded by a T-die method and cooled by a chill roll. An unstretched film 4 was obtained. The mixing ratio of the ethylene vinyl acetate copolymer and metfurthrin was scheduled to be mixed at 80:20. However, since the film formation was not stable and metfurthrin exuded vigorously on the surface, the mixing ratio of metfurthrin until the film formation was stable. The exact mixing ratio is not clear.
未延伸フィルム４は、ニップロールを経由した後、延伸用の第一ロール、熱板及び延伸用の第二ロールを通過させた。第一ロールと第二ロールの速比（延伸倍率）は５倍であった。ここで得られたシートをシート体４とし、これを比較例１とした。比較例１の厚みは１８０μｍであった。 The unstretched film 4 passed through the first roll for stretching, the hot plate, and the second roll for stretching after passing through the nip roll. The speed ratio (stretch ratio) between the first roll and the second roll was 5 times. The sheet obtained here was designated as a sheet body 4, and this was designated as Comparative Example 1. The thickness of Comparative Example 1 was 180 μm.
［評価試験１：含有率］
実施例１〜３、比較例１について、それぞれ５ｃｍ角に裁断した試験片を作製し、それぞれ、初期重量を測定した後、ヘキサンによる超音波洗浄を６０℃で２０分間行い、洗浄後の重量を測定した。初期重量と洗浄後重量の重量差を液状成分の含有量として求めた後、含有量を初期重量で除して百分率としたものを液状成分の含有率として求めた。
[Evaluation Test 1: Content Rate]
For each of Examples 1 to 3 and Comparative Example 1, specimens cut into 5 cm squares were prepared. After measuring the initial weight, ultrasonic cleaning with hexane was performed at 60 ° C. for 20 minutes, and the weight after cleaning was measured. It was measured. The difference in weight between the initial weight and the weight after washing was determined as the content of the liquid component, and then the content was divided by the initial weight to obtain a percentage as the content of the liquid component.
実施例１、及び実施例２の含有率は、共に１８．５％であり、実施例３の含有率は１４．７％、比較例１の含有率は６．５％であった。 The contents of Examples 1 and 2 were both 18.5%, the contents of Example 3 were 14.7%, and the contents of Comparative Example 1 were 6.5%.
［評価試験２：残存率］
実施例１〜３、比較例１について、それぞれ５ｃｍ角に裁断した試験片を作製し、それぞれ、熱風恒温室槽内（槽温４０℃）で吊下げ、その重量変化を測定することにより、試験片に担持された液状成分の揮発量の変化を確認した。得られた結果をグラフ化し図２に示す。図２では、重量変化量を測定試験１の含有量で除して百分率としたものを残存率として縦軸に示し、横軸は経過時間（ｈｒ）を示す。
[Evaluation Test 2: Residual Rate]
For Examples 1 to 3 and Comparative Example 1, test pieces were cut into 5 cm squares, respectively, suspended in a hot air constant temperature chamber (
実施例１〜３は重量変化が一定量で続いていることから、いずれも液状成分が長期に渡って徐々に揮発している状態が継続しているといえ、中でも実施例３がより長く揮発状態が継続しているといえる。これに対し、比較例１は大幅な重量変化が起こり、残存率０％の状態にすぐに達していることから、樹脂内に液状成分を留まっている期間が短く、すぐに揮発してしまっているといえる。 In Examples 1 to 3, since the weight change continues at a constant amount, it can be said that all of the liquid components are gradually evaporating over a long period of time. It can be said that the state is continuing. On the other hand, in Comparative Example 1, a significant weight change occurred and the residual rate reached 0% immediately, so the period during which the liquid component remained in the resin was short and it volatilized immediately. It can be said that.
［評価試験３：粘着剤層の積層性］
実施例１〜３、比較例１について、それぞれの片面（実施例２、３では液状成分に曝した面と反対側の面）にアクリル系粘着剤を塗布した。
[Evaluation Test 3: Laminating property of pressure-sensitive adhesive layer]
For Examples 1 to 3 and Comparative Example 1, an acrylic pressure-sensitive adhesive was applied to one side (in Example 2 and 3, the side opposite to the side exposed to the liquid component).
実施例１〜３では粘着剤層を形成することができたが、比較例１は液状成分の染み出しにより粘着剤が付着しにくい状態であった。粘着剤層が形成された実施例１〜３について、硬質板に貼り付けて、剥離させることを繰り返したところ、実施例１では糊残りが見られることがあった。 In Examples 1 to 3, the pressure-sensitive adhesive layer could be formed, but in Comparative Example 1, the pressure-sensitive adhesive was difficult to adhere due to the oozing out of the liquid component. About Examples 1-3 in which the pressure-sensitive adhesive layer was formed, the adhesive residue was sometimes seen in Example 1 when it was affixed to a hard plate and repeatedly peeled off.
実施例１〜３を作製する過程で生じる中間延伸体１〜３について、それぞれ１枚状態にした上で、実施例１〜３同様に粘着剤を塗布したところ、中間延伸体１は液状成分の染み出しがみられ、形成された粘着剤層にややムラが生じている状態であった。中間延伸体２も液状成分の染み出しが見られたが、液状成分に曝した面を中心に生じており、その反対面の染み出しはごく僅かであり、粘着剤層のムラはほとんどみられなかった。中間延伸体１、２に生じた染み出しは中間延伸体を作成した直後にはほとんどみられなかったが、粘着剤を塗布するまでの保管中に染み出しが生じていた。中間延伸体３では片面には染み出しが見られない状態であったが、カールが激しい状態であり、非常に使用しにくい状態であった。これに対して、実施例１、実施例２、及び実施例３に係るシート体では、カールもみられず、保管期間を経ても液状成分の明らかな染み出しはみられなかった。実施例１は粘着剤の糊残りがみられたことから粘着剤層とシート体の間に液状成分が僅かに介在している可能性はあるが、実施例２及び実施例３は液状成分がほとんど介在していない状態で粘着剤が塗布できているものと推察される。実施例１から実施例３のシート体は、長期に渡って液状成分の効果が得られるだけでなく、液状成分の染み出しが抑えられ、シート体に接触した物品に液状成分のシミができるなどの悪影響も少ない上に、カールがなく美感に優れており、また粘着剤層を形成したものも壁などの所望の物品に対して貼り付けやすいものであった。
About the intermediate | middle extending | stretching bodies 1-3 produced in the process of producing Examples 1-3, after making each one state, when apply | coating an adhesive similarly to Examples 1-3, the intermediate | middle extending | stretching body 1 is a liquid component. Exudation was observed, and the formed pressure-sensitive adhesive layer was slightly uneven. The intermediate stretched body 2 also showed liquid component exudation, but it occurred mainly on the surface exposed to the liquid component, the exudation on the opposite surface was very slight, and the adhesive layer was hardly uneven. There wasn't. The exudation that occurred in the intermediate stretched bodies 1 and 2 was hardly observed immediately after the intermediate stretched body was prepared, but the exudation occurred during storage until the adhesive was applied. The intermediate stretched body 3 was in a state where no bleeding was seen on one side, but the curl was severe and it was very difficult to use. On the other hand, in the sheet bodies according to Example 1, Example 2, and Example 3, no curling was observed, and no clear leakage of the liquid component was observed even after the storage period. In Example 1, since the adhesive residue of the adhesive was seen, there is a possibility that a liquid component is slightly interposed between the adhesive layer and the sheet body, but in Examples 2 and 3, the liquid component is It is assumed that the adhesive can be applied with almost no intervening state. In the sheet bodies of Examples 1 to 3, not only the effect of the liquid component can be obtained over a long period of time, but also the exudation of the liquid component is suppressed, and the liquid component is stained on the article in contact with the sheet body. In addition, there was little curling, and there was no curling, and it was excellent in aesthetics. Also, the one formed with the pressure-sensitive adhesive layer was easy to affix to a desired article such as a wall.
Claims (7)
該多孔質層は、充填材の周囲に空隙を有する延伸体であり、
前記空隙に室温２５℃における蒸気圧が１×１０−４〜１０４Ｐａの液状成分を担持した徐放性シート。 Comprising a porous layer made of a resin composition comprising a low crystalline polyolefin and a filler;
The porous layer is a stretched body having voids around the filler,
A sustained-release sheet in which a liquid component having a vapor pressure of 1 × 10 −4 to 10 4 Pa at room temperature of 25 ° C. is carried in the void.
充填材の周囲に形成された空隙に液状成分が担持された多孔質層を形成する徐放性シートの製造方法。 Stretching while bringing the liquid component into contact with at least part of the unstretched body of the first resin layer comprising a resin composition containing a low crystalline polyolefin and a filler,
A method for producing a sustained-release sheet, which forms a porous layer in which a liquid component is supported in voids formed around a filler.
多孔質層に結晶性樹脂組成物からなる防護層を積層する請求項４に記載の徐放性シートの製造方法。 Performing the stretching using an unstretched body obtained by co-extrusion of the first resin layer and the second resin layer comprising the crystalline resin composition,
The manufacturing method of the sustained release sheet | seat of Claim 4 which laminates | stacks the protective layer which consists of a crystalline resin composition on a porous layer.
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| JPWO2021060458A1 (en) * | 2019-09-27 | 2021-04-01 |
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| WO2021060458A1 (en) * | 2019-09-27 | 2021-04-01 | 株式会社ユポ・コーポレーション | Laminate, and hot-melt adhesive label |
| JP7232929B2 (en) | 2019-09-27 | 2023-03-03 | 株式会社ユポ・コーポレーション | Laminates and hot-melt adhesive labels |
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