JP4626242B2 - Insect repellent packaging materials and clothing repellents - Google Patents
Insect repellent packaging materials and clothing repellents Download PDFInfo
- Publication number
- JP4626242B2 JP4626242B2 JP2004274830A JP2004274830A JP4626242B2 JP 4626242 B2 JP4626242 B2 JP 4626242B2 JP 2004274830 A JP2004274830 A JP 2004274830A JP 2004274830 A JP2004274830 A JP 2004274830A JP 4626242 B2 JP4626242 B2 JP 4626242B2
- Authority
- JP
- Japan
- Prior art keywords
- insect repellent
- clothing
- layer
- packaging material
- gas barrier
- 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.)
- Active
Links
Description
本発明は、衣料用防虫剤を包装するための衣料用防虫剤用包装材料および該衣料用防虫剤用包装材料により衣料用防虫剤を包装してなる衣料防虫用品に関する。 The present invention relates to an insect repellent packaging material for clothing for packaging an insect repellent for clothing and a clothing insect repellent product obtained by packaging an insect repellent for clothing with the insect repellent packaging material for clothing.
衣料防虫用品とは、衣料を保管している箪笥や押入れなどに設置して衣料を虫の害から防ぐために用いられるものであり、一般的に蒸散性の防虫成分を含む衣料用防虫剤を包装したものが用いられている。衣料防虫用品は高濃度の防虫成分が直接衣料に触れることを防ぐため、予め使用単位毎に衣料用防虫剤を包装材料で包装した衣料防虫用品を用いるので、衣料用防虫剤用包装材料としては、防虫成分が透過する材料が使用されている。
通常このような衣料防虫用品は使用前に防虫成分が蒸散することを防ぐため、流通過程では、使用単位毎に包装された衣料防虫用品を数個程度まとめて、さらにガスバリア性材料によって包装されている。
Clothing insect repellents are used to protect clothing from insect damage by installing it in a basket or closet where clothing is stored, and generally package clothing repellents that contain transpirable insect repellents. Is used. In order to prevent high concentrations of insect repellents from directly touching clothing, clothing repellent products use clothing repellent products that are pre-packaged with a repellent for clothing for each unit used. In addition, materials that are permeable to insect repellents are used.
In general, in order to prevent the insect repellents from evaporating before use, such clothing and insect repellent products are packed together with several gas repellent materials that are packaged for each unit used in the distribution process. Yes.
しかしながら従来のように衣料防虫用品をさらにガスバリア性材料で包装した場合には、防虫成分が衣料用防虫剤用包装材料を透過し、ガスバリア性材料で包装された空間に拡散してしまうため、ガスバリア性材料を取り除いた時に、前記の拡散した防虫成分が空気中に拡散してしまい、ガスバリア性材料で包装する前に衣料防虫用品が含有していた防虫成分の全てを有効に利用できないことが多かった。 However, when a clothing insect repellent product is further packaged with a gas barrier material as in the past, the insect repellent component permeates the clothing insect repellent packaging material and diffuses into the space packed with the gas barrier material. When the insecticidal material is removed, the diffused insect repellent component diffuses into the air, and it is often impossible to effectively use all the insect repellent components contained in the clothing insect repellent product before packaging with the gas barrier material. It was.
このような問題を解決できる包装材料として、内層であるヒートシール層と外層であるガスバリア層とが接着性樹脂で接着されてなり、ガスバリア層及び接着性樹脂からなる中間層の一部と内層とが手で剥離可能である包装材料が開示されている（例えば特許文献１参照）。このような包装材料を用いて衣料用防虫剤を包装して得られる衣料防虫用品は、防虫成分透過層であるヒートシール層とガスバリア層との間に、従来のように防虫成分が拡散する空間がないため、使用前に防虫成分が拡散することがなく、使用時にガスバリア層及び中間層を剥離することによって、本来衣料防虫用品が有する防虫成分を有効に利用できると考えられる。 As a packaging material that can solve such problems, the heat seal layer that is the inner layer and the gas barrier layer that is the outer layer are bonded with an adhesive resin, and a part of the intermediate layer made of the gas barrier layer and the adhesive resin and the inner layer Has disclosed a packaging material that can be peeled off by hand (see, for example, Patent Document 1). A clothing insect repellent product obtained by packaging an insect repellent for clothing using such a packaging material is a space in which an insect repellent component is diffused between a heat seal layer and a gas barrier layer which are insect repellent component permeation layers as in the past. Therefore, the insect repellent component does not diffuse before use, and it is considered that the insect repellent component originally possessed by the clothing insect repellent can be effectively used by peeling the gas barrier layer and the intermediate layer at the time of use.
しかしながら上記構成の包装材料を衣料用防虫剤用包装材料として用いた場合には、衣料用防虫剤に含まれる防虫成分の多くが接着性樹脂からなる中間層に拡散してしまい、ガスバリア層を剥離する際に中間層とともに防虫成分も除去されてしまうため、やはり本来衣料用防虫剤に含まれていた防虫成分を有効に利用できないことが多かった。 However, when the packaging material having the above structure is used as a packaging material for an insect repellent for clothing, most of the insect repellent components contained in the insect repellent for clothing diffuse into the intermediate layer made of an adhesive resin, and the gas barrier layer is peeled off. In this case, since the insect repellent component is also removed together with the intermediate layer, the insect repellent component originally contained in the insect repellent for clothing is often not effectively used.
このようなことから衣料用防虫剤に含まれる防虫成分を有効に利用できる衣料用防虫剤用包装材料を開発すべく検討の結果、本発明に至った。 From the above, as a result of studies to develop a packaging material for an insect repellent for clothing that can effectively use the insect repellent component contained in the insect repellent for clothing, the present invention has been achieved.
すなわち本発明は、防虫成分を含む衣料用防虫剤を包装する衣料用防虫剤用包装材料であって、該衣料用防虫剤用包装材料が、オレフィン系樹脂層と該オレフィン系樹脂層に隣接されてなるガスバリア層とを有し、オレフィン系樹脂層とガスバリア層との剥離強度が０．１〜３Ｎ／１５ｍｍ幅である衣料用防虫剤用包装材料である。
さらに本発明は、２５℃における蒸気圧が１０-5ｍｍＨｇ以上である防虫成分を含む衣料用防虫剤が前記衣料用防虫剤用包装材料によって包装されてなる衣料防虫用品であって、該衣料用防虫剤用包装材料のオレフィン系樹脂層が衣料防虫用品の内面側に位置し、ガスバリア層が衣料防虫用品の外面側に位置する衣料防虫用品である。
That is, the present invention is a packaging material for insect repellents for clothing that packs an insect repellent for clothing containing an insect repellent component, and the packaging material for insect repellents for clothing is adjacent to the olefin resin layer and the olefin resin layer. And an insect repellent packaging material for clothing having a peel strength between the olefin-based resin layer and the gas barrier layer of 0.1 to 3 N / 15 mm width.
Furthermore, the present invention is a clothing / insect repellent product in which an insect repellent for clothing containing a repellent component having a vapor pressure at 25 ° C. of 10 −5 mmHg or more is packaged by the packaging material for a repellent for clothing, The insect repellent product has an olefin resin layer of the insect repellent packaging material located on the inner surface side of the clothing insect repellent product and a gas barrier layer located on the outer surface side of the clothing repellent product.
本発明の衣料用防虫剤用包装材料および衣料防虫用品は、衣料用防虫剤に含まれる防虫成分を有効に利用することができるものである。
The packaging material for clothing insect repellents and the clothing insect repellent products of the present invention can effectively utilize the insect repellent components contained in the clothing insect repellent.
本発明における防虫成分とは、以下の方法において防虫機能を有すると判断される成分である。
防虫機能を有するかどうかを判別すべき成分（Ａ）１０ｍｇを、既に防虫機能を有さないことが確認された他の成分とともに直径３０ｍｍφ、厚さ３ｍｍの錠剤に成形する。
２５±２℃、湿度３０％ＲＨの室内において、衣装箱（縦７２５ｍｍ×横４２７ｍｍ×高さ１５８ｍｍ）内にコイガの卵１０〜１５個を入れた綿製の袋（大きさ４．５ｃｍ×４．５ｃｍ、厚さ０．２ｍｍ）を２つ離して設置し、各袋の上に前記錠剤を１つずつ置き、衣装箱に蓋をして１週間静置した。
１週間後箱内の袋を開封し、コイガの死卵、死虫、生虫の数を数え、（（死卵＋死虫）／（死卵＋死虫＋生虫））×１００で表される死亡率をそれぞれ算出し、２箇所の平均値が８０％以上のものを防虫機能を有する成分とする。
The insect repellent component in the present invention is a component determined to have an insect repellent function in the following method.
10 mg of the component (A) to be discriminated whether or not it has an insect repellent function is formed into a tablet having a diameter of 30 mmφ and a thickness of 3 mm together with other components that have already been confirmed to have no insect repellent function.
In a room at 25 ± 2 ° C and 30% RH, a cotton bag (size: 4.5cm x 4) containing 10-15 eggs of koiga in a costume box (length 725mm x width 427mm x height 158mm) .5 cm, thickness 0.2 mm) were placed apart, one tablet was placed on each bag, the clothes box was covered and left for one week.
One week later, the bag inside the box is opened, and the number of dead eggs, dead insects, and live worms of Koiga are counted, and expressed as ((dead egg + dead insect) / (dead egg + dead insect + live insect)) × 100. The mortality rate is calculated, and those having an average value of 80% or more at two locations are defined as components having an insect repellent function.
防虫成分としては、公知の蒸散性防虫成分が用いられる。蒸散性防虫成分とは、通常２５℃における蒸気圧が１０-5ｍｍＨｇ以上である防虫成分である。
このような防虫成分としては、例えば２，３，５，６−テトラフルオロ−４−メトキシメチルベンジル ３−（１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシラート（蒸気圧 １．４×１０-5ｍｍＨｇ＜２５℃＞）、２，３，５，６−テトラフルオロ−４−メチルベンジル ３−（１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシラート（蒸気圧 ７．７×１０-5ｍｍＨｇ＜２５℃＞）、２，３，５，６−テトラフルオロベンジル ３−（２，２−ジクロロビニル）−２，２−ジメチルシクロプロパンカルボキシラート（蒸気圧 ２．６×１０-5ｍｍＨｇ＜２５℃＞）などが挙げられる。とりわけ蒸散性および防虫能の観点から、２，３，５，６−テトラフルオロ−４−メチルベンジル ３−（１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシラートが好ましく用いられる。防虫成分は常温で液体であってもよく、固体であってもよい。
As the insect repellent component, a known transpiration repellent component is used. The transpirable insect repellent component is an insect repellent component whose vapor pressure at 25 ° C. is usually 10 −5 mmHg or more.
Examples of such insect repellent components include 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate (vapor pressure 1.4 × 10 −5 mmHg <25 ° C.), 2,3,5,6-tetrafluoro-4-methylbenzyl 3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate (vapor pressure 7.7 × 10 − 5 mmHg <25 ° C.), 2,3,5,6-tetrafluorobenzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (vapor pressure 2.6 × 10 −5 mmHg) <25 ° C.>). In particular, 2,3,5,6-tetrafluoro-4-methylbenzyl 3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate is preferably used from the viewpoints of transpiration and insect repellent ability. The insect repellent component may be liquid at room temperature or solid.
本発明の衣料用防虫剤は防虫成分を含んでいればよく、その形状や含有する他の成分などについて特に限定されるものではないが、取り扱いやすさの点から錠剤であることが好ましい。防虫成分が液体である場合には、常温で固体の物質と混合して錠剤に成形することができる。防虫成分が固体である場合には、防虫成分単独で錠剤にしてもよく、他の常温固体物質と混合して錠剤としてもよい。 The insect repellent for clothing of the present invention only needs to contain an insect repellent component, and the shape and other components contained therein are not particularly limited, but a tablet is preferable from the viewpoint of ease of handling. When the insect repellent component is a liquid, it can be mixed with a solid substance at room temperature and formed into a tablet. When the insect repellent component is solid, the insect repellent component alone may be made into a tablet, or may be mixed with another room temperature solid substance to make a tablet.
錠剤を製造する際に防虫成分と混合する常温で固体の物質は、防虫成分の有する防虫能を阻害するものでなければよく、例えば公知の増量剤を使用することができる。使用する増量剤の種類や量は、共に用いる防虫成分が蒸散により減少していく割合と同程度の割合で蒸散するように、防虫成分の種類や量に応じて選択することが好ましい。このような錠剤は、消費者が該錠剤を含む衣料防虫用品の取替え時期を判断しやすい。 The substance that is solid at room temperature to be mixed with the insect repellent component when manufacturing the tablet may be any substance that does not inhibit the insect repellent ability of the insect repellent component, and for example, a known extender can be used. It is preferable to select the type and amount of the bulking agent to be used according to the type and amount of the insect repellent so that the insect repellent used together evaporates at a rate similar to the rate at which the insect repellent decreases. With such a tablet, it is easy for the consumer to determine when to replace the clothing and insect repellent product containing the tablet.
増量剤としては、例えば２，４，６−トリイソプロピル−１，３，５−トリオキサン（蒸気圧 ８．９×１０-2ｍｍＨｇ＜２５℃＞）、ナフタリン（蒸気圧 ８．２５×１０-2ｍｍＨｇ＜２５℃＞）、ｐ−ジクロロベンセン（蒸気圧 １．１ｍｍＨｇ＜２５℃＞）、樟脳（蒸気圧 ８．７８×１０-3ｍｍＨｇ＜２５℃＞）、アダマンタンなどが挙げられる。特に有効成分として２，３，５，６-テトラフルオロ−４−メチルベンジル−３−(１−プロペニル)−２，２−ジメチルシクロプロパンカルボキシラートを選択した場合には、２，４，６−トリイソプロピル−１，３，５−トリオキサンを用いることが好ましい。
増量剤と防虫成分との配合比は特に限定されるものではないが、通常増量剤中の防虫成分量が０．０５〜５重量％程度である。
Examples of the bulking agent include 2,4,6-triisopropyl-1,3,5-trioxane (vapor pressure 8.9 × 10 −2 mmHg <25 ° C.), naphthalene (vapor pressure 8.25 × 10 −2). mmHg <25 ° C.), p-dichlorobenzene (vapor pressure 1.1 mmHg <25 ° C.), camphor (vapor pressure 8.78 × 10 −3 mmHg <25 ° C.), adamantane, and the like. In particular, when 2,3,5,6-tetrafluoro-4-methylbenzyl-3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate is selected as the active ingredient, 2,4,6- It is preferable to use triisopropyl-1,3,5-trioxane.
The blending ratio of the extender and the insect repellent component is not particularly limited, but the amount of the insect repellent component in the extender is usually about 0.05 to 5% by weight.
本発明の衣料用防虫剤用包装材料は、オレフィン系樹脂層および該オレフィン系樹脂層に隣接されてなるガスバリア層を有する。ガスバリア層の組成や厚みなどは特に限定されるものではなく、例えばポリエステル樹脂、ポリアミド樹脂、ポリビニルアルコール、ポリ塩化ビニリデン系樹脂、エチレン−ビニルアルコール共重合体などから構成される層であり、未延伸であってもよく、二軸延伸されていてもよい。ガスバリア性の観点から、エチレン−ビニルアルコール共重合体を用いることが好ましく、特にビニルアルコール由来の構成単位を５０mol％以上含むエチレン−ビニルアルコール共重合体からなる層であることが好ましい。加工性の観点から、エチレン−ビニルアルコール共重合体におけるビニルアルコール由来の構成単位の含有量は８０mol％以下であることが好ましい。 The packaging material for insect repellents of the present invention has an olefin resin layer and a gas barrier layer adjacent to the olefin resin layer. The composition and thickness of the gas barrier layer are not particularly limited. For example, the gas barrier layer is a layer composed of a polyester resin, a polyamide resin, a polyvinyl alcohol, a polyvinylidene chloride resin, an ethylene-vinyl alcohol copolymer, and the like. Or may be biaxially stretched. From the viewpoint of gas barrier properties, it is preferable to use an ethylene-vinyl alcohol copolymer, and a layer made of an ethylene-vinyl alcohol copolymer containing 50 mol% or more of a vinyl alcohol-derived structural unit is particularly preferable. From the viewpoint of processability, the content of structural units derived from vinyl alcohol in the ethylene-vinyl alcohol copolymer is preferably 80 mol% or less.
本発明の衣料用防虫剤用包装材料におけるオレフィン系樹脂層は、衣料用防虫剤に含まれる防虫成分が使用期間を通して有効量が透過可能となるように、その組成や厚みを適宜選択すればよい。オレフィン系樹脂層を構成するオレフィン系樹脂の例としては、ホモポリプロピレン、エチレン−プロピレン共重合体などのプロピレン系樹脂、カルボン酸ビニルエステルおよび不飽和カルボン酸エステルからなる群から選ばれる１種以上のモノマーとエチレンとの共重合体、低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレンなどのエチレン系樹脂が挙げられる。防虫成分の透過性の観点から、オレフィン系樹脂層はカルボン酸ビニルエステルおよび不飽和カルボン酸エステルからなる群から選ばれる１種以上のモノマーとエチレンとの共重合体、低密度ポリエチレン、直鎖状低密度ポリエチレンから選択される1種以上のエチレン系樹脂からなることが好ましい。 The composition and thickness of the olefin-based resin layer in the packaging material for insect repellent for clothing of the present invention may be appropriately selected so that the effective amount of the insect repellent component contained in the insect repellent for clothing can be transmitted throughout the period of use. . Examples of the olefin resin constituting the olefin resin layer include one or more selected from the group consisting of propylene resins such as homopolypropylene and ethylene-propylene copolymers, carboxylic acid vinyl esters and unsaturated carboxylic acid esters. Examples thereof include copolymers of monomers and ethylene, ethylene resins such as low density polyethylene, linear low density polyethylene, and high density polyethylene. From the viewpoint of the permeability of the insect repellent component, the olefin-based resin layer is a copolymer of at least one monomer selected from the group consisting of carboxylic acid vinyl esters and unsaturated carboxylic acid esters with ethylene, low-density polyethylene, linear It is preferably made of at least one ethylene resin selected from low density polyethylene.
オレフィン系樹脂層を構成する樹脂としては、防虫成分が全て蒸散するのと同時に増量剤も全て蒸散するような防虫成分および増量剤の透過性を有するオレフィン系樹脂を選択することが好ましい。このような観点からオレフィン系樹脂層は、カルボン酸ビニルエステルおよび不飽和カルボン酸エステルからなる群から選ばれる1種以上のモノマーとエチレンとの共重合体であって、カルボン酸ビニルエステルおよび不飽和カルボン酸エステルからなる群から選ばれる1種以上のモノマー由来の構成単位の含有量が１０mol％以下である共重合体であることが好ましく、前記構成単位の含有量が１mol％以上である共重合体であることがより好ましい。とりわけ不飽和カルボン酸エステルとエチレンとの共重合体であることが好ましい。エチレン−カルボン酸ビニルエステル共重合体としてはエチレン−酢酸ビニル共重合体（ＥＶＡ）を例示することができ、エチレン−不飽和カルボン酸エステル共重合体としてはエチレン−メタクリル酸メチル共重合体、エチレン−アクリル酸メチル共重合体があげられる。
オレフィン系樹脂層は１種類の樹脂から構成されていてもよく、２種類以上の樹脂から構成されていてもよい。
As the resin constituting the olefin-based resin layer, it is preferable to select an olefin-based resin having the permeability of the insect repellent component and the extender so that all of the repellent component is evaporated and at the same time the extender is also evaporated. From such a viewpoint, the olefin-based resin layer is a copolymer of ethylene with at least one monomer selected from the group consisting of carboxylic acid vinyl esters and unsaturated carboxylic acid esters, and includes carboxylic acid vinyl esters and unsaturated carboxylic acid esters. The copolymer is preferably a copolymer having a content of structural units derived from one or more monomers selected from the group consisting of carboxylic acid esters of 10 mol% or less, and a copolymer having a content of the structural units of 1 mol% or more. More preferably, it is a coalescence. In particular, a copolymer of an unsaturated carboxylic acid ester and ethylene is preferable. Examples of the ethylene-carboxylic acid vinyl ester copolymer include an ethylene-vinyl acetate copolymer (EVA). Examples of the ethylene-unsaturated carboxylic acid ester copolymer include an ethylene-methyl methacrylate copolymer and ethylene. -A methyl acrylate copolymer is mention | raise | lifted.
The olefin resin layer may be composed of one kind of resin or may be composed of two or more kinds of resins.
オレフィン系樹脂層の厚みは、衣料用防虫剤に含まれる防虫成分が使用期間を通して有効量が透過可能となるように設定されるが、強度と透明性の観点から３０〜１００μｍであることが好ましい。衣料防虫用品使用時に、衣料用防虫剤の減少が容易に確認できることから、オレフィン系樹脂層は透明性に優れることが好ましい。 The thickness of the olefin-based resin layer is set so that an effective amount of the insect repellent component contained in the insect repellent for clothing can be transmitted through the period of use, but is preferably 30 to 100 μm from the viewpoint of strength and transparency. . It is preferable that the olefin-based resin layer is excellent in transparency since the decrease in the insect repellent for clothing can be easily confirmed when the clothing insect repellent product is used.
本発明の包装材料は、オレフィン系樹脂層と該オレフィン系樹脂層に隣接されてなるガスバリア層とを有する。オレフィン系樹脂層とガスバリア層との間に接着剤層や粘着剤層を有すると、該接着剤層や粘着剤層に防虫成分が拡散してしまい、ガスバリア層を剥離する際に該接着剤層や粘着剤層も剥離されてしまうため、該層に拡散した防虫成分を衣料防虫のために利用できなくなってしまう。本発明の包装材料はオレフィン系樹脂層とガスバリア層とが隣接されてなる構成とすることにより、使用前には防虫成分が蒸散せず、使用時にガスバリア層を剥離することではじめて防虫成分が蒸散するものであり、かつ剥離する層に防虫成分が拡散していないため、本来衣料用防虫剤が有している防虫成分を無駄なく有効に利用することができるのである。 The packaging material of the present invention has an olefin resin layer and a gas barrier layer adjacent to the olefin resin layer. If an adhesive layer or a pressure-sensitive adhesive layer is provided between the olefin-based resin layer and the gas barrier layer, the insect repellent component diffuses into the adhesive layer or the pressure-sensitive adhesive layer, and the adhesive layer is peeled off when the gas barrier layer is peeled off. And the pressure-sensitive adhesive layer are also peeled off, so that the insect repellent component diffused in the layer cannot be used for clothing insect repellent. The packaging material of the present invention has a configuration in which the olefin resin layer and the gas barrier layer are adjacent to each other, so that the insect repellent component does not evaporate before use, and the insect repellent component does not evaporate until the gas barrier layer is peeled off during use. In addition, since the insect repellent component does not diffuse into the layer to be peeled off, the insect repellent component originally possessed by the insect repellent for clothing can be used effectively without waste.
オレフィン系樹脂層とガスバリア層との剥離強度は０．１〜３Ｎ／１５ｍｍ幅であり、好ましくは０．１〜１Ｎ／１５ｍｍ幅、さらに好ましくは０．１５〜１Ｎ／１５ｍｍ幅である。剥離強度が低すぎる場合には輸送などの流通過程でガスバリア層が剥離してしまい防虫成分が蒸散してしまうことがあり、高すぎる場合には使用時にガスバリア層を剥離、除去する際にオレフィン系樹脂層を破損してしまうことがある。 The peel strength between the olefin-based resin layer and the gas barrier layer is 0.1 to 3 N / 15 mm width, preferably 0.1 to 1 N / 15 mm width, more preferably 0.15 to 1 N / 15 mm width. If the peel strength is too low, the gas barrier layer may be peeled off during the distribution process such as transportation and the insect repellent may evaporate. If it is too high, the gas barrier layer may be stripped and removed during use. The resin layer may be damaged.
本発明における剥離強度とは、次のようにして求められる値である。オレフィン系樹脂層とガスバリア層の層間であらかじめ一部剥離しておき、該剥離部分が一方の端部となるようにして１５ｍｍ巾×２００ｍｍの短冊状に切り出し、測定サンプルとする。オートストレイン型引張試験機の上下のチャック部分にあらかじめ剥離しておいたオレフィン系樹脂層を含む部分とガスバリア層を含む部分とをそれぞれ挟み、引張速度３００ｍｍ／ｍｉｎで上下に引っ張ることにより１８０度剥離させる。５０ｍｍ剥離させたときの平均荷重を求め、その値を剥離強度とする。 The peel strength in the present invention is a value determined as follows. A part of the olefin-based resin layer and the gas barrier layer is peeled off in advance, and the peeled portion is cut into a strip shape of 15 mm width × 200 mm so as to be a measurement sample. 180 degree peeling by sandwiching the part containing the olefin resin layer and the part containing the gas barrier layer that were peeled in advance on the upper and lower chuck parts of the autostrain type tensile tester and pulling it up and down at a pulling speed of 300 mm / min. Let The average load when 50 mm is peeled is determined, and the value is taken as the peel strength.
オレフィン系樹脂層とガスバリア層との剥離強度を制御する方法としては、オレフィン系樹脂層にオレフィン系接着性樹脂を添加する方法や、ガスバリア層にオレフィン系樹脂を添加して剥離強度を制御する方法が挙げられる。ガスバリア層がエチレンと酢酸ビニルとの共重合体をケン化して得られるエチレン−ビニルアルコール共重合体からなる場合には、共重合比率やケン化率を制御する方法などがあげられる。 As a method of controlling the peel strength between the olefin resin layer and the gas barrier layer, a method of adding an olefin adhesive resin to the olefin resin layer or a method of controlling the peel strength by adding an olefin resin to the gas barrier layer Is mentioned. In the case where the gas barrier layer is made of an ethylene-vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl acetate, a method for controlling the copolymerization ratio or the saponification rate can be mentioned.
オレフィン系接着性樹脂としては、低密度ポリエチレンや直鎖状低密度ポリエチレン、エチレン−酢酸ビニル共重合体等のエチレン系樹脂を無水マレイン酸で変性して得られる無水マレイン酸変性エチレン系樹脂や、エチレン−無水マレイン酸共重合体、エチレン−無水マレイン酸−酢酸ビニル共重合体、エチレン−無水マレイン酸−不飽和カルボン酸エステル共重合体、エチレン−不飽和カルボン酸共重合体などが挙げられる。 As olefin adhesive resin, maleic anhydride modified ethylene resin obtained by modifying ethylene resin such as low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer with maleic anhydride, Examples thereof include an ethylene-maleic anhydride copolymer, an ethylene-maleic anhydride-vinyl acetate copolymer, an ethylene-maleic anhydride-unsaturated carboxylic acid ester copolymer, and an ethylene-unsaturated carboxylic acid copolymer.
ガスバリア層がビニルアルコール由来の構成単位を５０mol％以上含むエチレン−ビニルアルコール共重合体からなる場合は、剥離強度制御の観点から、オレフィン系樹脂層は、無水マレイン酸変性エチレン系樹脂をエチレン系樹脂に添加したオレフィン系樹脂組成物からなることが好ましい。
無水マレイン酸変性エチレン系樹脂の添加量は、エチレン系樹脂１００重量部に対し好ましくは５〜４５重量部であり、より好ましくは１０〜４５重量部である。
When the gas barrier layer is made of an ethylene-vinyl alcohol copolymer containing 50 mol% or more of a structural unit derived from vinyl alcohol, from the viewpoint of peel strength control, the olefin resin layer is made of maleic anhydride-modified ethylene resin as an ethylene resin. It is preferable that it consists of the olefin resin composition added to.
The addition amount of the maleic anhydride-modified ethylene resin is preferably 5 to 45 parts by weight, more preferably 10 to 45 parts by weight with respect to 100 parts by weight of the ethylene resin.
本発明の包装材料はオレフィン系樹脂層およびガスバリア層以外の他の層を有していてもよい。他の層としては、接着剤層、樹脂層、金属層、印刷インクなどの無機物を塗工した層などが挙げられる。ただし接着剤層を有する場合には、該包装材料により衣料用防虫剤を包装した場合に、前記接着剤層がガスバリア層より外面側に位置する場合に限られる。
オレフィン系樹脂やポリエステル樹脂などからなる未延伸フィルムや二軸延伸フィルムをガスバリア層上に積層することが、防湿性や、本発明の包装材料を容器と熱シールする時の耐熱性の観点から好ましい。
The packaging material of the present invention may have a layer other than the olefin resin layer and the gas barrier layer. Examples of other layers include an adhesive layer, a resin layer, a metal layer, and a layer coated with an inorganic material such as printing ink. However, when it has an adhesive layer, it is limited to the case where the adhesive layer is positioned on the outer surface side of the gas barrier layer when the insect repellent for clothing is packaged with the packaging material.
From the viewpoint of moisture resistance and heat resistance when heat-sealing the packaging material of the present invention with a container, it is preferable to laminate an unstretched film or a biaxially stretched film made of an olefin resin or a polyester resin on the gas barrier layer. .
本発明の包装材料がオレフィン系樹脂層およびガスバリア層以外の他の層を有する場合には、オレフィン系樹脂層とガスバリア層との剥離強度が、他の層間剥離強度よりも小さいことが必要である。
ガスバリア層の両側にオレフィン系樹脂層が隣接されてなる構成である場合、すなわちオレフィン系樹脂層Ａ／ガスバリア層／オレフィン系樹脂層Ｂである場合には、オレフィン系樹脂層Ａとガスバリア層との剥離強度が０．１〜３Ｎ／１５ｍｍ幅であり、オレフィン系樹脂層Ｂとガスバリア層との剥離強度が、オレフィン系樹脂層Ａとガスバリア層との剥離強度より強ければよい。この場合、オレフィン系樹脂層Ａが内容物側となるように本発明の包装材料を用いる。
When the packaging material of the present invention has a layer other than the olefin resin layer and the gas barrier layer, the peel strength between the olefin resin layer and the gas barrier layer needs to be smaller than the other interlayer peel strengths. .
When the olefin-based resin layer is adjacent to both sides of the gas barrier layer, that is, in the case of the olefin-based resin layer A / gas barrier layer / olefin-based resin layer B, the olefin-based resin layer A and the gas barrier layer The peel strength is 0.1 to 3 N / 15 mm width, and the peel strength between the olefinic resin layer B and the gas barrier layer may be stronger than the peel strength between the olefinic resin layer A and the gas barrier layer. In this case, the packaging material of the present invention is used so that the olefin resin layer A is on the contents side.
本発明の包装材料は、公知のフィルムやシートの成形方法により製造することができ、例えば共押出Ｔダイ成形、共押出インフレ成形などの共押出法により成形できる。オレフィン系樹脂層に隣接してガスバリア層を設ける方法としては、接着剤、アンカーコート剤、粘着剤などを使用しない共押出法や押出ラミネーション法が好ましい。 The packaging material of the present invention can be produced by a known film or sheet molding method, for example, a coextrusion method such as coextrusion T-die molding or coextrusion inflation molding. As a method of providing a gas barrier layer adjacent to the olefin resin layer, a coextrusion method or an extrusion lamination method that does not use an adhesive, an anchor coat agent, an adhesive, or the like is preferable.
本発明の衣料用防虫剤用包装材料はフィルム状またはシート状であり、該包装材料を袋状にして、あるいは予め成形された容器の蓋材として用いることができる。
容器の蓋材として用いる場合、容器はガスバリア性を有することが必要である。容器の形状は特に限定されるものではなく、カップ状、トレー状、丼状など各種形状の容器を用いることができる。容器の成形方法は特に限定されるものではなく、射出成形法や、フィルム状あるいはシート状の成形品を真空成形、圧空成形、真空圧空成形等の方法で成形する方法が挙げられる。
The packaging material for an insect repellent for clothing of the present invention is in the form of a film or a sheet, and the packaging material can be used in the form of a bag or as a lid for a preformed container.
When used as a container lid, the container needs to have gas barrier properties. The shape of the container is not particularly limited, and various shapes such as a cup shape, a tray shape, and a bowl shape can be used. The method of forming the container is not particularly limited, and examples thereof include an injection molding method and a method of forming a film-shaped or sheet-shaped molded product by a method such as vacuum forming, pressure forming, or vacuum / pressure forming.
容器は、蓋材とヒートシールなどの方法で密封できることが好ましいため、少なくとも蓋材とのシール面がヒートシール可能なオレフィン系樹脂からなる層であることが好ましい。容器の構成は特に限定されるものではないが、内面側から順にシール層／ガスバリア層／基材層であることが防虫成分の拡散抑制、蓋材とのヒートシール性、強度の観点から好ましい。 Since it is preferable that the container can be sealed by a method such as heat sealing with a lid material, it is preferable that at least a sealing surface with the lid material is a layer made of an olefin resin that can be heat sealed. The configuration of the container is not particularly limited, but is preferably a seal layer / gas barrier layer / base material layer in order from the inner surface side from the viewpoints of suppressing diffusion of the insect repellent component, heat sealability with the lid, and strength.
容器のシール層を構成する樹脂としては、本発明の包装材料中のオレフィン系樹脂層を構成する樹脂と同様の樹脂を用いることができる。容器のシール層には低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレンなどを用いることが好ましく、ヒートシール性の観点から低密度ポリエチレンを用いることがさらに好ましい。 As resin which comprises the sealing layer of a container, resin similar to resin which comprises the olefin resin layer in the packaging material of this invention can be used. It is preferable to use low density polyethylene, linear low density polyethylene, high density polyethylene or the like for the seal layer of the container, and it is more preferable to use low density polyethylene from the viewpoint of heat sealability.
容器のガスバリア層の組成などは特に限定されるものではなく、例えばポリエステル樹脂、ポリアミド樹脂、エチレン−ビニルアルコール共重合体、ポリビニルアルコール、ポリ塩化ビニリデンなどからなる層であり、未延伸であってもよく、二軸延伸されていてもよい。ガスバリア性および加工性の観点から、エチレン−ビニルアルコール共重合体を用いることが好ましく、特にビニルアルコール由来の構成単位を５０〜８０ｍｏｌ％含むエチレン−ビニルアルコール共重合体を用いることが好ましい。 The composition of the gas barrier layer of the container is not particularly limited. For example, it is a layer made of polyester resin, polyamide resin, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, polyvinylidene chloride, etc. It may be biaxially stretched. From the viewpoint of gas barrier properties and processability, it is preferable to use an ethylene-vinyl alcohol copolymer, and it is particularly preferable to use an ethylene-vinyl alcohol copolymer containing 50 to 80 mol% of a structural unit derived from vinyl alcohol.
容器の基材層には、オレフィン系樹脂やスチレン系樹脂などを用いることができる。基材層の厚みはコストおよび強度の観点から通常２００〜６００μｍである。
防虫成分の容器への拡散を抑制する観点から、容器のガスバリア層よりも内面側の層の合計厚みは薄いほうが好ましく、蓋材とのヒートシール性とのバランスから１０〜１００μｍであることが好ましく、１０〜７０μｍであることがさらに好ましい。容器の好ましい構成は、内面側から順にシール層／ガスバリア層／基材層＝１０〜７０／１０〜５０／１００〜５００μｍである。
An olefin resin, a styrene resin, or the like can be used for the base layer of the container. The thickness of the base material layer is usually 200 to 600 μm from the viewpoint of cost and strength.
From the viewpoint of suppressing the diffusion of the insect repellent component into the container, the total thickness of the inner surface layer is preferably thinner than the gas barrier layer of the container, and is preferably 10 to 100 μm from the balance with the heat sealability with the lid material. 10 to 70 μm is more preferable. A preferable configuration of the container is seal layer / gas barrier layer / base material layer = 10 to 70/10 to 50/100 to 500 μm in order from the inner surface side.
衣料用防虫剤用包装材料によって衣料用防虫剤を包装する場合には、内容物側、すなわち衣料用防虫剤側がオレフィン系樹脂層となるようにして包装する。このようにして得られた衣料防虫用品は、該衣料防虫用品を構成する衣料用防虫剤用包装材料のオレフィン系樹脂層が衣料防虫用品の内面側に位置し、ガスバリア層が衣料防虫用品の外面側に位置するものである。このような衣料防虫用品は、使用前にはガスバリア層により防虫成分の蒸散を防止することができ、使用時にガスバリア層を含む外面側に位置する部分を剥がすことにより、衣料用防虫剤中の防虫成分を極めて有効に利用することができる。
オレフィン系樹脂層はヒートシール性を有することが、袋状とする場合にはオレフィン系樹脂層同士で、蓋材とする場合には容器とヒートシールできることから好ましい。
When packaging the insect repellent for clothing using the packaging material for the insect repellent for clothing, the content side, that is, the insect repellent side for the clothing is packed with the olefin resin layer. The clothing insect repellent product thus obtained has the olefin resin layer of the packaging material for the insect repellent for clothing constituting the clothing insect repellent product on the inner surface side of the clothing insect repellent product, and the gas barrier layer is the outer surface of the clothing insect repellent product. It is located on the side. Such clothing insect repellents can prevent the transpiration of the insect repellent component by the gas barrier layer before use, and peel off the portion located on the outer surface side including the gas barrier layer at the time of use. Ingredients can be used very effectively.
The olefin-based resin layer preferably has heat-sealability because it can be heat-sealed between the olefin-based resin layers in the case of a bag and in the case of a lid.
以下、本発明を実施例に基づき説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to this.
（１）容器の製造
＜バリア容器Ａ＞
シート成形機を用いて、ポリプロピレン（住友化学工業（株）製ノーブレンＦＳ２０１１ＤＧ２）からなる厚み４００μｍ、幅３００ｍｍのプロピレン系樹脂シートを得た。このシートを共押出ラミネーターの第一給紙装置に取付けた。第二給紙装置にエチレン−酢酸ビニル共重合体（ＥＶＡ）フィルム（タマポリ（株）製ＳＢ−５、［ＶＡ］＝５ｗｔ％、厚み５０μｍ）を取付けた。前記フィルムおよびシートを繰り出した後、該フィルムとシートとの間にエチレン−ビニルアルコール共重合体（ＥＶＯＨ）（クラレ（株）製エバールＥ１０５Ａ ビニルアルコール由来の構成単位５６ｍｏｌ％、ケン化度９９ｍｏｌ％以上）とオレフィン系接着性樹脂（三井化学（株）製アドマー ＮＦ５５０ 無水マレイン酸変性直鎖状低密度ポリエチレン）とを、接着性樹脂／ＥＶＯＨ／接着性樹脂＝１／２／１の厚み比で、総厚みが４０μｍとなるように２３０℃で押出してサンドイッチ押出ラミネートし、バリアシートを製造した。該バリアシートを、布施真空（株）製真空成形機を用いてシート表面温度１５０℃で真空成形し、口径６１ｍｍ、フランジ外径７０ｍｍ、深さ８ｍｍ、底径５９ｍｍで、容器内面側がＥＶＡ層であるカップ状容器Ａを得た。
＜バリア容器Ｂ＞
多層シート成形機を用いて、５種５層のバリアシートを製造した。第一層を構成する樹脂には低密度ポリエチレン（住友化学工業（株）製 スミカセンＦ２００）、第二層を構成する樹脂にはオレフィン系接着性樹脂（三井化学（株）製アドマー ＮＦ５５９ 無水マレイン酸変性直鎖状低密度ポリエチレン）、第三層を構成する樹脂にはエチレン−ビニルアルコール共重合体（ＥＶＯＨ）（クラレ（株）製エバールＥ１０５Ａ）、第四層を構成する樹脂にはオレフィン系接着性樹脂（三井化学（株）製アドマー ＱＦ５５１ 無水マレイン酸変性ポリプロピレン）、第五層を構成する樹脂にはポリプロピレン（住友化学工業（株）製ノーブレンＦＳ２０１１ＤＧ２）をそれぞれ用いた。各樹脂を各押出機で２３０℃で溶融混練した後、第一層／第二層／第三層／第四層／第五層＝４０／１５／３０／２５／１９０となる押出比率でシート状に押出し、総厚みが３００μｍのバリアシートを製造した。容器Ａと同様に真空成形により容器内面側が低密度ポリエチレン層であるカップ状容器Ｂを得た。
＜バリア容器Ｃ＞
多層シート成形機を用いて製造した第一層／第二層／第三層／第四層／第五層＝１００／３０／３０／２５／１１５μｍであるバリアシートを用いた以外は容器Ｂと同様にしてカップ状容器Ｃを得た。
(1) Manufacture of containers <Barrier container A>
Using a sheet molding machine, a propylene-based resin sheet having a thickness of 400 μm and a width of 300 mm made of polypropylene (Nobrene FS2011DG2 manufactured by Sumitomo Chemical Co., Ltd.) was obtained. This sheet was attached to the first paper feeder of a coextrusion laminator. An ethylene-vinyl acetate copolymer (EVA) film (SB-5 manufactured by Tamapoly Co., Ltd., [VA] = 5 wt%, thickness 50 μm) was attached to the second paper feeder. After feeding out the film and the sheet, an ethylene-vinyl alcohol copolymer (EVOH) (Eval E105A manufactured by Kuraray Co., Ltd., 56 mol%, a structural unit derived from vinyl alcohol, a saponification degree of 99 mol% or more is provided between the film and the sheet. ) And an olefin-based adhesive resin (Admer NF550 manufactured by Mitsui Chemicals, Inc., maleic anhydride-modified linear low-density polyethylene) at a thickness ratio of adhesive resin / EVOH / adhesive resin = 1/2/1, A barrier sheet was produced by extruding at 230 ° C. and sandwich extrusion lamination so that the total thickness was 40 μm. The barrier sheet was vacuum formed at a sheet surface temperature of 150 ° C. using a vacuum forming machine manufactured by Fuse Vacuum Co., Ltd., having a diameter of 61 mm, a flange outer diameter of 70 mm, a depth of 8 mm, a bottom diameter of 59 mm, and the inner surface of the container being an EVA layer. A cup-shaped container A was obtained.
<Barrier container B>
5 types and 5 layers of barrier sheets were manufactured using a multilayer sheet molding machine. The resin constituting the first layer is low density polyethylene (Sumikasen F200 manufactured by Sumitomo Chemical Co., Ltd.), and the resin constituting the second layer is an olefin-based adhesive resin (Admer NF559 manufactured by Mitsui Chemicals, Inc.) maleic anhydride Modified linear low density polyethylene), ethylene-vinyl alcohol copolymer (EVOH) (Eval E105A manufactured by Kuraray Co., Ltd.) for the resin constituting the third layer, and olefinic adhesive for the resin constituting the fourth layer Resin (Mitsui Chemicals Co., Ltd. Admer QF551 maleic anhydride modified polypropylene), and polypropylene (Nobrene FS2011DG2 manufactured by Sumitomo Chemical Co., Ltd.) were used as the resin constituting the fifth layer. After melt-kneading each resin at 230 ° C. with each extruder, the sheet has an extrusion ratio of first layer / second layer / third layer / fourth layer / fifth layer = 40/15/30/25/190 A barrier sheet having a total thickness of 300 μm was produced. Similarly to the container A, a cup-shaped container B whose inner surface was a low-density polyethylene layer was obtained by vacuum forming.
<Barrier container C>
Container B except that a barrier sheet of the first layer / second layer / third layer / fourth layer / fifth layer = 100/30/30/25/115 μm produced using a multilayer sheet molding machine was used. Similarly, a cup-shaped container C was obtained.
（２）衣料用防虫剤の製造
２０ｍｌスクリュー管に、防虫成分である２，３，５，６−テトラフルオロ−４−メチルベンジル (１Ｒ)−トランス−３−(１−プロペニル（Ｚ／Ｅ＝８／１）)−２，２−ジメチルシクロプロパンカルボキシラート（蒸気圧 ７．７×１０-5ｍｍＨｇ＜２５℃＞）１０ｍｇと、増量剤である２，４，６−トリソプロピル−１，３，５−トリオキサン（蒸気圧 ８．９×１０-2ｍｍＨｇ＜２５℃＞）２．０ｇとを加えてよく攪拌し、得られた混合物を、打錠機で直径３ｃｍ、厚さ３ｍｍの円柱状の錠剤に成形し、衣料用防虫剤とした。
なお、２，３，５，６-テトラフルオロ−４−メチルベンジル (１Ｒ)−トランス−３−(１−プロペニル（Ｚ／Ｅ＝８／１）)−２，２−ジメチルシクロプロパンカルボキシラートの防虫機能は、前記錠剤を用いて以下の方法で確認した。
(2) Manufacture of insect repellent for clothing Into a 20 ml screw tube, 2,3,5,6-tetrafluoro-4-methylbenzyl (1R) -trans-3- (1-propenyl (Z / E = 8/1) ) -2,2-dimethylcyclopropanecarboxylate (vapor pressure 7.7 × 10 −5 mmHg <25 ° C.>) 10 mg and 2,4,6-trisopropyl-1,3 which is a bulking agent , 5-trioxane (vapor pressure 8.9 × 10 −2 mmHg <25 ° C.>) 2.0 g and stirred well, and the resulting mixture was formed into a cylindrical shape having a diameter of 3 cm and a thickness of 3 mm using a tableting machine. To form an insect repellent for clothing.
In addition, 2,3,5,6-tetrafluoro-4-methylbenzyl (1R) -trans-3- (1-propenyl (Z / E = 8/1 ) )-2,2-dimethylcyclopropanecarboxylate The insect repellent function was confirmed by the following method using the tablet.
２５±２℃、湿度３０％ＲＨの室内において、衣装箱（縦７２５ｍｍ×横４２７ｍｍ×高さ１５８ｍｍ）内にコイガの卵１０〜１５個を入れた綿製の袋（大きさ４．５ｃｍ×４．５ｃｍ、厚さ０．２ｍｍ）を２つ離して設置し、各袋の上に錠剤を１つずつ置き、衣装箱に蓋をして１週間静置した。
１週間後箱内の袋を開封し、各場所のコイガの死卵、死虫、生虫の数を数えたところ、（（死卵＋死虫）／（死卵＋死虫＋生虫））×１００で表される死亡率の平均値は１００％であった。このことから２，３，５，６-テトラフルオロ−４−メチルベンジル (１Ｒ)−トランス−３−(１−プロペニル（Ｚ／Ｅ＝８／１）)−２，２−ジメチルシクロプロパンカルボキシラートは防虫機能を有する防虫成分であることが確認された。
In a room at 25 ± 2 ° C and 30% RH, a cotton bag (size: 4.5cm x 4) containing 10-15 eggs of koiga in a costume box (length 725mm x width 427mm x height 158mm) .5 cm, thickness 0.2 mm) were placed apart, one tablet was placed on each bag, the clothes box was covered and left for one week.
After 1 week, open the bag in the box and count the number of dead eggs, dead insects, and live worms at each location. ((Dead egg + dead insect) / (dead egg + dead insect + live insect)) ) The average mortality rate expressed by × 100 was 100%. Therefore, 2,3,5,6-tetrafluoro-4-methylbenzyl (1R) -trans-3- (1-propenyl (Z / E = 8/1 ) )-2,2-dimethylcyclopropanecarboxylate Was confirmed to be an insect repellent component having an insect repellent function.
（３）衣料防虫用品の製造
（１）で製造した容器に（２）で製造した衣料用防虫剤を１個入れ、後述する衣料用防虫剤用包装材料を蓋材として用い、衣料防虫用品を作製した。容器に蓋材をシールする際には、蓋材のオレフィン系樹脂層が容器と接着するようにして、日産工機（株）製小型カップシーラーＳＮＲ−１を用い、ゲージ圧５ｋｇ／ｃｍ2、シールバー温度１８０℃、シール時間１秒で熱封緘した。
(3) Manufacture of clothing / insect repellents One container of the repellent for clothing manufactured in (2) is put in the container manufactured in (1), and a packaging material for the repellent for clothing described later is used as a lid. Produced. When sealing the lid to the container, the olefin resin layer of the lid is adhered to the container, and a small cup sealer SNR-1 manufactured by Nissan Koki Co., Ltd. is used, with a gauge pressure of 5 kg / cm 2 , Heat sealing was performed at a seal bar temperature of 180 ° C. and a seal time of 1 second.
（４）防虫成分量測定方法
（３）で製造した衣料防虫用品を、４０℃のギアオーブン中で１週間保存した後、蓋材を構成する衣料用防虫剤用包装材料を、最も剥離強度の弱い層間で剥離した。剥離した部分を蓋材剥離部とする。次に容器に接着した残りの蓋材を容器から剥がした（蓋材残存部とする）。衣料用防虫剤を取り出し、アセトンで防虫成分の抽出を行なった。容器、蓋材剥離部および蓋材残存部はそれぞれキシレンで防虫成分の抽出を行なった。各抽出液をガスクロマトグラムにて分析し、防虫成分量を測定した。ガスクロマトグラムの条件は以下に示すとおりである。
ＦＩＤ ＥＣＤ
カラム温度： １６０℃ １６０℃
気化室： ２１０℃ ２１０℃
検出器温度： ２１０℃ ２６０℃
(4) After the clothing and insect repellent manufactured by the method (3) for measuring the amount of insect repellent is stored in a gear oven at 40 ° C. for one week, the packaging material for the repellent for clothing constituting the cover material is the most peelable. Peeling between weak layers. Let the part which peeled be a cover material peeling part. Next, the remaining lid material adhered to the container was peeled off from the container (the remaining lid material portion). The insect repellent for clothing was taken out, and the insect repellent components were extracted with acetone. The container, the lid material peeling part and the lid material remaining part were each extracted with insecticide components with xylene. Each extract was analyzed with a gas chromatogram to measure the amount of insect repellent components. The conditions of the gas chromatogram are as shown below.
FID ECD
Column temperature: 160 ° C 160 ° C
Vaporization chamber: 210 ° C 210 ° C
Detector temperature: 210 ° C 260 ° C
（５）衣料用防虫剤用包装材料の剥離強度測定方法
後述する実施例および比較例で製造した衣料用防虫剤用包装材料を、最も剥離強度が小さい層間で予め３０ｍｍ剥がし、剥がした部分を含むようにＭＤ方向（フィルム製造時の押出し方向）×ＴＤ方向（フィルム製造時の押出し方向と垂直方向）＝２００ｍｍ×１５ｍｍの短冊状に切出し、試験片とした。オートストレイン型引張試験機の上下のチャック部分に、予め剥離しておいた部分をそれぞれ挟み、引張速度３００ｍｍ／分で１８０度剥離した。５０ｍｍ剥離したときの平均荷重を剥離強度とした。
(5) Method for measuring peel strength of packaging material for insect repellents for clothing The material for packaging of insect repellents for clothing manufactured in Examples and Comparative Examples which will be described later is peeled off 30 mm in advance between the layers having the smallest peel strength, and the peeled portion is included. Thus, MD direction (extrusion direction at the time of film production) × TD direction (direction perpendicular to the extrusion direction at the time of film production) = 200 mm × 15 mm was cut into a strip and used as a test piece. The previously peeled portions were sandwiched between the upper and lower chuck portions of the autostrain type tensile tester, and peeled 180 degrees at a tensile speed of 300 mm / min. The average load when 50 mm was peeled was defined as peel strength.
（６）死亡率の測定方法（本発明の衣料防虫用品の効果の確認）
２５±２℃、湿度３０％ＲＨの室内において、衣装箱（縦７２５ｍｍ×横４２７ｍｍ×高さ１５８ｍｍ）内にコイガの卵１０〜１５個を入れた綿製の袋（大きさ４．５ｃｍ×４．５ｃｍ、厚さ０．２ｍｍ）を２つ離して設置した。（３）で製造した衣料防虫用品を４０℃のギアオーブン中で１週間保存した後、蓋材を最も剥離強度の弱い層間で剥離して、バリア容器を含む部分を各袋の上に一つずつ置き、衣装箱に蓋をし、１週間静置した。
１週間後箱内の袋を開封し、コイガの死卵、死虫、生虫の数を数え、（（死卵＋死虫）／（死卵＋死虫＋生虫））×１００で表される死亡率を算出し、２箇所の平均値を該衣料防虫用品を用いたときの死亡率とした。なお錠剤を置かなかった場合は死虫および死卵がなく、死亡率はゼロであった。
(6) Mortality measurement method (confirmation of the effect of the clothing insect repellent product of the present invention)
In a room at 25 ± 2 ° C and 30% RH, a cotton bag (size: 4.5cm x 4) containing 10-15 eggs of koiga in a costume box (length 725mm x width 427mm x height 158mm) .5 cm, thickness 0.2 mm) were separated by two. After storing the clothing / insect repellent manufactured in (3) in a gear oven at 40 ° C. for one week, the lid is peeled off between the layers having the weakest peel strength, and one part including the barrier container is placed on each bag. Placed one by one, covered the costume box and left it for a week.
One week later, the bag inside the box is opened, and the number of dead eggs, dead insects, and live worms of Koiga are counted, and expressed as ((dead egg + dead insect) / (dead egg + dead insect + live insect)) × 100. The mortality rate was calculated, and the average value of the two places was defined as the mortality rate when the clothing insect repellent was used. When no tablets were placed, there were no dead insects and dead eggs, and the mortality rate was zero.
[実施例１]
低密度ポリエチレン（ＬＤＰＥ）（住友化学工業（株）製スミカセンＦ２００−０）と無水マレイン酸変性ポリエチレンＡＤ（三井化学（株）製アドマーＮＦ５００）をＬＤＰＥ／ＡＤ＝７０／３０（ｗｔ％）の比で混合したものを、オレフィン系樹脂層を構成する樹脂原料１とし、エチレン−ビニルアルコール共重合体（ＥＶＯＨ）（クラレ（株）性エバールＦ１０１Ａ（酸素透過度０．５ｃｃ／ｍ2・２４ｈｒｓ・ａｔｍ／１５μ） ビニルアルコール由来の構成単位５６ｍｏｌ％ ケン化度９９ｍｏｌ％以上）を、ガスバリア層を構成する樹脂原料２とする。さらに無水マレイン酸変性ポリエチレン（三井化学（株）製アドマーＮＦ５００）を、接着性樹脂層を構成する樹脂原料３とし、これら３種の原料を、共押出Ｔダイに接続された異なる押出機にそれぞれ投入し、オレフィン系樹脂層／ガスバリア層／接着性樹脂層＝４０／１５／１５（μｍ）となるように各押出量を調整して２３０℃で溶融押出し、４０℃に調整した冷却ロールにより冷却して巻き取り、積層フィルムを得た。該積層フィルムの接着性樹脂層表面に表面張力４６ｄｙｎｅ／ｃｍとなるようにコロナ処理を行った。無機層状化合物含有樹脂組成物がＰＥＴフィルムにコーティングされてなるガスバリアフィルム（住友化学工業（株）製セービックス（酸素透過度０．１ｃｃ／ｍ2・２４ｈｒｓ・ａｔｍ／１５μ））のコーティング面と、積層フィルムの接着性樹脂層面とを、接着剤（三井武田ケミカル（株）社製 タケラックＡ５１５：タケネートＡ５０＝１０：１重量比）を用いて接着して積層した後、４０℃で２４時間エージングを行い、衣料用防虫剤用包装材料を得た。該衣料用防虫剤用包装材料を蓋材とし、容器にカップ状容器Ａを用いて衣料防虫用品を製造した。これら衣料用防虫剤用包装材料や衣料防虫用品を用いて、各種評価を行なった。結果を表１に示す。なお剥離強度は、樹脂原料１からなるオレフィン系樹脂層と樹脂原料２からなるガスバリア層との層間の剥離強度を測定した。蓋材剥離部はガスバリア層、接着性樹脂層、接着剤層およびガスバリアフィルムであり、蓋材残存部はオレフィン系樹脂層のみであった。
[Example 1]
Low density polyethylene (LDPE) (Sumitomo Chemical Co., Ltd. Sumikasen F200-0) and maleic anhydride modified polyethylene AD (Mitsui Chemicals Co., Ltd. Admer NF500) ratio of LDPE / AD = 70/30 (wt%) The resin raw material 1 constituting the olefin-based resin layer is used as an ethylene-vinyl alcohol copolymer (EVOH) (Kuraray Co., Ltd. Eval F101A (oxygen permeability 0.5 cc / m 2 · 24 hrs · atm / 15μ) The structural unit derived from vinyl alcohol 56 mol% and the degree of saponification 99 mol% or more) is used as the resin raw material 2 constituting the gas barrier layer. Further, maleic anhydride modified polyethylene (Admer NF500 manufactured by Mitsui Chemicals Co., Ltd.) was used as the resin raw material 3 constituting the adhesive resin layer, and these three raw materials were respectively fed to different extruders connected to a coextrusion T die. The olefin-based resin layer / gas barrier layer / adhesive resin layer = 40/15/15 (μm), each extrusion amount is adjusted, melt extruded at 230 ° C., and cooled by a cooling roll adjusted to 40 ° C. And wound up to obtain a laminated film. The surface of the adhesive resin layer of the laminated film was subjected to corona treatment so that the surface tension was 46 dyne / cm. Laminate coating layer of gas barrier film (sabyx manufactured by Sumitomo Chemical Co., Ltd. (oxygen permeability 0.1 cc / m 2 · 24 hrs · atm / 15 μ)) formed by coating inorganic layered compound-containing resin composition on PET film The adhesive resin layer surface of the film was adhered and laminated using an adhesive (Takelac A515: Takenate A50 = 10: 1 weight ratio manufactured by Mitsui Takeda Chemical Co., Ltd.), and then aged at 40 ° C. for 24 hours. A packaging material for an insect repellent for clothing was obtained. Using the packaging material for the insect repellent for clothing as a lid, a cup-shaped container A was used as a container to produce a clothing insect repellent article. Various evaluations were performed using the packaging material for clothing insect repellents and clothing insect repellent products. The results are shown in Table 1. The peel strength was measured by measuring the peel strength between the olefin resin layer made of the resin raw material 1 and the gas barrier layer made of the resin raw material 2. The lid material peeling part was a gas barrier layer, an adhesive resin layer, an adhesive layer and a gas barrier film, and the lid material remaining part was only an olefin resin layer.
[実施例２]
ＬＤＰＥ（住友化学工業（株）製スミカセンＦ２００−０）と無水マレイン酸変性ポリエチレンＡＤ（三井化学（株）製アドマーＮＦ５００）をＬＤＰＥ／ＡＤ＝８０／２０（ｗｔ％）の比で混合したものを樹脂原料１とした以外は実施例１と同様にして衣料用防虫剤用包装材料を製造した。該衣料用防虫剤用包装材料を蓋材とし、容器にカップ状容器Ａを用いて衣料防虫用品を製造した。これら衣料用防虫剤用包装材料や衣料防虫用品を用いて、各種評価を行なった。評価結果を表１に示す。なお剥離強度は、樹脂原料１からなるオレフィン系樹脂層と樹脂原料２からなるガスバリア層との層間の剥離強度を測定した。蓋材剥離部はガスバリア層、接着性樹脂層、接着剤層およびガスバリアフィルムであり、蓋材残存部はオレフィン系樹脂層のみであった。
[Example 2]
LDPE (Sumitomo Chemical Co., Ltd. Sumikasen F200-0) and maleic anhydride modified polyethylene AD (Mitsui Chemicals Co., Ltd. Admer NF500) mixed at a ratio of LDPE / AD = 80/20 (wt%) A packaging material for an insect repellent for clothing was produced in the same manner as in Example 1 except that the resin raw material 1 was used. Using the packaging material for the insect repellent for clothing as a lid, a cup-shaped container A was used as a container to produce a clothing insect repellent article. Various evaluations were performed using the packaging material for clothing insect repellents and clothing insect repellent products. The evaluation results are shown in Table 1. The peel strength was measured by measuring the peel strength between the olefin resin layer made of the resin raw material 1 and the gas barrier layer made of the resin raw material 2. The lid material peeling part was a gas barrier layer, an adhesive resin layer, an adhesive layer and a gas barrier film, and the lid material remaining part was only an olefin resin layer.
[比較例４]
ＬＤＰＥ（住友化学工業（株）製スミカセンＦ２００−０）を樹脂原料１とした以外は実施例１と同様にして衣料用防虫剤用包装材料を製造した。該衣料用防虫剤用包装材料を蓋材とし、容器にカップ状容器Ａを用いて衣料防虫用品を製造した。これら衣料用防虫剤用包装材料や衣料防虫用品を用いて、各種評価を行なった。評価結果を表１に示す。なお剥離強度は、樹脂原料１からなるオレフィン系樹脂層と樹脂原料２からなるガスバリア層との層間の剥離強度を測定した。蓋材剥離部はガスバリア層、接着性樹脂層、接着剤層およびガスバリアフィルムであり、蓋材残存部はオレフィン系樹脂層のみであった。
[ Comparative Example 4 ]
A packaging material for an insect repellent for clothing was produced in the same manner as in Example 1 except that LDPE (Sumitomo Chemical F200-0 manufactured by Sumitomo Chemical Co., Ltd.) was used as the resin raw material 1. Using the packaging material for the insect repellent for clothing as a lid, a cup-shaped container A was used as a container to produce a clothing insect repellent article. Various evaluations were performed using the packaging material for clothing insect repellents and clothing insect repellent products. The evaluation results are shown in Table 1. The peel strength was measured by measuring the peel strength between the olefin resin layer made of the resin raw material 1 and the gas barrier layer made of the resin raw material 2. The lid material peeling part was a gas barrier layer, an adhesive resin layer, an adhesive layer and a gas barrier film, and the lid material remaining part was only an olefin resin layer.
[実施例４]
エチレン−メタクリル酸メチル共重合体（ＥＭＭＡ）（住友化学工業（株）製アクリフトＷＤ３０１、［ＭＭＡ］＝１０ｗｔ％）と無水マレイン酸変性ポリエチレンＡＤ（三井化学（株）製アドマーＮＦ５２８）をＥＭＭＡ／ＡＤ＝９０／１０（ｗｔ％）の比で混合したものを樹脂原料１とした以外は実施例１と同様にして衣料用防虫剤用包装材料を製造した。該衣料用防虫剤用包装材料を蓋材とし、容器にカップ状容器Ｂを用いて衣料防虫用品を製造した。これら衣料用防虫剤用包装材料や衣料防虫用品を用いて、各種評価を行なった。評価結果を表１に示す。なお剥離強度は、樹脂原料１からなるオレフィン系樹脂層と樹脂原料２からなるガスバリア層との層間の剥離強度を測定した。蓋材剥離部はガスバリア層、接着性樹脂層、接着剤層およびガスバリアフィルムであり、蓋材残存部はオレフィン系樹脂層のみであった。
[Example 4]
An ethylene-methyl methacrylate copolymer (EMMA) (Aclift WD301, [MMA] = 10 wt%, manufactured by Sumitomo Chemical Co., Ltd.) and maleic anhydride-modified polyethylene AD (Admer NF528, manufactured by Mitsui Chemicals, Inc.) A packaging material for an insect repellent for clothing was produced in the same manner as in Example 1 except that the resin raw material 1 was mixed at a ratio of 90/10 (wt%). Using the packaging material for the insect repellent for clothing as a lid, a cup-shaped container B was used as a container to produce a clothing insect repellent article. Various evaluations were performed using the packaging material for clothing insect repellents and clothing insect repellent products. The evaluation results are shown in Table 1. The peel strength was measured by measuring the peel strength between the olefin resin layer made of the resin raw material 1 and the gas barrier layer made of the resin raw material 2. The lid material peeling part was a gas barrier layer, an adhesive resin layer, an adhesive layer and a gas barrier film, and the lid material remaining part was only an olefin resin layer.
[実施例５]
実施例４と同様にして衣料用防虫剤用包装材料を製造した。該衣料用防虫剤用包装材料を蓋材とし、容器にカップ状容器Ｃを用いて衣料防虫用品を製造した。これら衣料用防虫剤用包装材料や衣料防虫用品を用いて、各種評価を行なった。評価結果を表１に示す。なお剥離強度は、樹脂原料１からなるオレフィン系樹脂層と樹脂原料２からなるガスバリア層との層間の剥離強度を測定した。蓋材剥離部はガスバリア層、接着性樹脂層、接着剤層およびガスバリアフィルムであり、蓋材残存部はオレフィン系樹脂層のみであった。
[Example 5]
In the same manner as in Example 4, a packaging material for insect repellent for clothing was produced. A clothing insect repellent product was manufactured using the packaging material for the insect repellent for clothing as a lid and a cup-shaped container C as a container. Various evaluations were performed using the packaging material for clothing insect repellents and clothing insect repellent products. The evaluation results are shown in Table 1. The peel strength was measured by measuring the peel strength between the olefin resin layer made of the resin raw material 1 and the gas barrier layer made of the resin raw material 2. The lid material peeling part was a gas barrier layer, an adhesive resin layer, an adhesive layer and a gas barrier film, and the lid material remaining part was only an olefin resin layer.
[比較例１]
ＬＤＰＥ（住友化学工業（株）製スミカセンＦ２００−０）とＰＰ（住友化学工業（株）製ノーブレンＦＳ２０１１ＤＧ２）を共押出Ｔダイに接続された、異なる押出機にそれぞれ投入し、ＬＤＰＥ／ＰＰ＝５０／２０（μｍ）となるように各押出量を調整し加工温度２３０℃で溶融押出し、４０℃に調整した冷却ロールにより冷却して巻き取り積層フィルムを得た。該積層フィルムのＰＰ層表面に表面張力４６ｄｙｎｅ／ｃｍとなるようにコロナ処理を行った。ガスバリアフィルム（住友化学工業（株）製セービックス（酸素透過度０．１ｃｃ／ｍ2・２４ｈｒｓ・ａｔｍ／１５μ））のコーティング面とＰＰ層とを接着剤（三井武田ケミカル（株）社製 タケラックＡ５１５：タケネートＡ５０＝１０：１重量比）を用いて接着して積層した後、４０℃で２４時間エージングを行い、衣料用防虫剤用包装材料を得た。該衣料用防虫剤用包装材料を蓋材とし、容器にカップ状容器Ａを用いて衣料防虫用品を製造した。なお蓋材と容器とをシールする際には、蓋材のＬＤＰＥ層と容器とをシールした。これら衣料用防虫剤用包装材料や衣料防虫用品を用いて、各種評価を行なった。結果を表２に示す。なお剥離強度は、ＬＤＰＥ層とＰＰ層との層間の剥離強度を測定した。蓋材剥離部はＰＰ層、接着剤層、ガスバリアフィルムであり、蓋材残存部はＬＤＰＥ層のみであった。
[Comparative Example 1]
LDPE (Sumitomo Chemical Co., Ltd. Sumikasen F200-0) and PP (Sumitomo Chemical Co., Ltd. Nobrene FS2011DG2) were respectively charged into different extruders connected to a co-extrusion T die, and LDPE / PP = 50. Each extrusion amount was adjusted to be / 20 (μm), melt-extruded at a processing temperature of 230 ° C., and cooled by a cooling roll adjusted to 40 ° C. to obtain a wound laminated film. The PP film surface of the laminated film was subjected to corona treatment so that the surface tension was 46 dyne / cm. The coating surface of the gas barrier film (Sabitus Chemical Industries Co., Ltd. Savics (oxygen permeability 0.1 cc / m 2 · 24 hrs · atm / 15 μ)) and the PP layer are adhesive (Takelac A515, Mitsui Takeda Chemical Co., Ltd.) : Takenate A50 = 10: 1 weight ratio) and laminated, followed by aging at 40 ° C. for 24 hours to obtain a packaging material for an insect repellent for clothing. Using the packaging material for the insect repellent for clothing as a lid, a cup-shaped container A was used as a container to produce a clothing insect repellent article. When sealing the lid and the container, the LDPE layer of the lid and the container were sealed. Various evaluations were performed using the packaging material for clothing insect repellents and clothing insect repellent products. The results are shown in Table 2. The peel strength was measured by measuring the peel strength between the LDPE layer and the PP layer. The lid material peeling part was a PP layer, an adhesive layer, and a gas barrier film, and the lid material remaining part was only the LDPE layer.
[比較例２]
ガスバリアフィルム（住友化学工業（株）製セービックス）のコーティング面にアクリル系粘着剤を厚み２０μｍとなるように塗布して粘着剤層を形成し、該粘着剤層とＥＶＡフィルム（タマポリ（株）性ＳＢ−５ 厚み５０μｍ）のコロナ面とを積層した後４０℃で２４時間エージングを行い、衣料用防虫剤用包装材料を得た。該衣料用防虫剤用包装材料を蓋材とし、容器にカップ状容器Ａを用いて衣料防虫用品を製造した。これら衣料用防虫剤用包装材料や衣料防虫用品を用いて、各種評価を行なった。なお蓋材と容器とをシールする際には、蓋材のＥＶＡ層と容器とをシールした。結果を表２に示す。なお剥離強度は、ＥＶＡフィルム層とアクリル系粘着剤層との層間の剥離強度を測定した。蓋材剥離部はアクリル系粘着剤層、ガスバリアフィルムであり、蓋材残存部はＥＶＡ層であった。
[Comparative Example 2]
A pressure-sensitive adhesive layer is formed by applying an acrylic pressure-sensitive adhesive to the coating surface of a gas barrier film (Sumitomo Chemical Industries Co., Ltd. Savics) to a thickness of 20 μm. The pressure-sensitive adhesive layer and EVA film (Tamapoly Co., Ltd.) SB-5 (50 μm thick) corona surface was laminated and then aged at 40 ° C. for 24 hours to obtain a packaging material for an insect repellent for clothing. Using the packaging material for the insect repellent for clothing as a lid, a cup-shaped container A was used as a container to produce a clothing insect repellent article. Various evaluations were performed using the packaging material for clothing insect repellents and clothing insect repellent products. When sealing the lid and the container, the EVA layer of the lid and the container were sealed. The results are shown in Table 2. The peel strength was measured by measuring the peel strength between the EVA film layer and the acrylic pressure-sensitive adhesive layer. The lid material peeling part was an acrylic pressure-sensitive adhesive layer and a gas barrier film, and the lid material remaining part was an EVA layer.
[比較例３]
比較例２における粘着剤を接着剤（主剤：三井武田ケミカル（株）社製 タケラックＡ５１５）とした以外は比較例２と同様に行い衣料用防虫剤用包装材料を製造した。該衣料用防虫剤用包装材料を蓋材とし、容器にカップ状容器Ａを用いて衣料防虫用品を製造した。これら衣料用防虫剤用包装材料や衣料防虫用品を用いて、各種評価を行なった。なお蓋材と容器とをシールする際には、蓋材のＥＶＡ層と容器とをシールした。評価結果を表２に示した。なお剥離強度は、ＥＶＡフィルム層と接着剤層との層間の剥離強度を測定した。蓋材剥離部は接着剤層、ガスバリアフィルムであり、蓋材残存部はＥＶＡ層であった。
[Comparative Example 3]
A packaging material for an insect repellent for clothing was produced in the same manner as in Comparative Example 2 except that the adhesive in Comparative Example 2 was changed to an adhesive (main agent: Takelac A515, manufactured by Mitsui Takeda Chemical Co., Ltd.). Using the packaging material for the insect repellent for clothing as a lid, a cup-shaped container A was used as a container to produce a clothing insect repellent article. Various evaluations were performed using the packaging material for clothing insect repellents and clothing insect repellent products. When sealing the lid and the container, the EVA layer of the lid and the container were sealed. The evaluation results are shown in Table 2. The peel strength was measured by measuring the peel strength between the EVA film layer and the adhesive layer. The lid material peeling part was an adhesive layer and a gas barrier film, and the lid material remaining part was an EVA layer.
２）４０℃１週間後保存後の外観を評価した。
外観の変化なし：〇
蓋材を構成する包装材料が層間で剥離：×
３）４０℃１週間保存後の防虫成分残存量（％）＝ １００×（残存量／仕込み量）
４）２５℃１週間保存後の害虫死亡率（単位：％）
No change in appearance: ○ The packaging material that makes up the lid peels off between layers: ×
3) Residual amount of insect repellent after storage at 40 ° C. for 1 week (%) = 100 × (residual amount / preparation amount)
4) Pest mortality after storage at 25 ° C for 1 week (unit:%)
実施例１〜５に示す衣料用防虫剤用包装材料を用いた衣料防虫用品は、保存中に蓋材剥離部に防虫成分が拡散することがなく、衣料用防虫剤が含有する防虫成分を有効に利用することができるものであり、該衣料防虫用品は防虫性能に優れたものであった。一方比較例１〜３に示す衣料用防虫剤用包装材料を用いた衣料防虫用品は、保存中に蓋材剥離部に防虫成分が拡散してしまい、衣料用防虫剤が含有する防虫成分を有効に利用することができず、防虫性能に劣っていた。また比較例２、３に示す衣料防虫用品は、保存中に蓋材が層間で剥離してしまった。これは蓋材の粘着剤層あるいは接着剤層に、防虫成分や増量剤が吸収されたためと思われる。
The clothing and insect repellent article using the packaging material for the insect repellent for clothing shown in Examples 1 to 5 is effective in preventing the insect repellent component from being diffused in the cover peeling part during storage and containing the insect repellent for clothing. The clothing insect repellent product was excellent in insect repellent performance. On the other hand, the insect repellent article using the packaging material for the insect repellent for clothing shown in Comparative Examples 1 to 3 diffuses the insect repellent component in the lid peeling portion during storage, and the insect repellent component contained in the insect repellent for clothing is effective. The insect repellent performance was inferior. Moreover, as for the clothing insect repellent articles shown in Comparative Examples 2 and 3, the lid material was peeled off between the layers during storage. This seems to be because the insect repellent component and the bulking agent were absorbed in the pressure-sensitive adhesive layer or adhesive layer of the lid.
Claims (5)
（１）低密度ポリエチレン
（２）直鎖状低密度ポリエチレン
（３）カルボン酸ビニルエステルおよび不飽和カルボン酸エステルからなる群から選ばれる１種以上のモノマーとエチレンとの共重合体 A packaging material for an insect repellent for clothing that packs an insect repellent for clothing containing an insect repellent component, the wrapping material for an insect repellent for clothing comprising an olefin resin layer and a gas barrier layer adjacent to the olefin resin layer; A wrapping material for an insect repellent for clothing having a peel strength between the olefinic resin layer and the gas barrier layer of 0.27 to 1 N / 15 mm width , wherein the olefinic resin layer comprises the following (1): ~ 100 parts by weight of one or more ethylene resins selected from (3) and an olefin resin composition in which 10 to 45 parts by weight of maleic anhydride-modified ethylene resin is added to 100 parts by weight of the ethylene resin. A packaging material for an insect repellent for clothing, wherein the gas barrier layer comprises an ethylene-vinyl alcohol copolymer containing at least 50 mol% of a structural unit derived from vinyl alcohol.
(1) Low density polyethylene
(2) Linear low density polyethylene
(3) Copolymer of ethylene with one or more monomers selected from the group consisting of carboxylic acid vinyl esters and unsaturated carboxylic acid esters
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004274830A JP4626242B2 (en) | 2003-09-25 | 2004-09-22 | Insect repellent packaging materials and clothing repellents |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003333140 | 2003-09-25 | ||
| JP2004274830A JP4626242B2 (en) | 2003-09-25 | 2004-09-22 | Insect repellent packaging materials and clothing repellents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005119286A JP2005119286A (en) | 2005-05-12 |
| JP4626242B2 true JP4626242B2 (en) | 2011-02-02 |
Family
ID=34622006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004274830A Active JP4626242B2 (en) | 2003-09-25 | 2004-09-22 | Insect repellent packaging materials and clothing repellents |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4626242B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015182321A (en) * | 2014-03-25 | 2015-10-22 | 三菱樹脂株式会社 | Easily peelable multilayer film, laminate multilayer film, and package |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4643402B2 (en) * | 2004-09-09 | 2011-03-02 | 住友化学株式会社 | Pest control agent |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03176131A (en) * | 1989-12-05 | 1991-07-31 | Mitsubishi Plastics Ind Ltd | Laminated film |
| JPH03200704A (en) * | 1989-12-28 | 1991-09-02 | Sumitomo Chem Co Ltd | Medicine sustained release resin form |
| JPH0820503A (en) * | 1994-07-04 | 1996-01-23 | Kobayashi Pharmaceut Co Ltd | Insecticide |
| JPH11970A (en) * | 1997-06-11 | 1999-01-06 | Kuraray Co Ltd | Fragrant substance wrapping body |
| JPH11255604A (en) * | 1997-08-06 | 1999-09-21 | Sumitomo Chem Co Ltd | Insect repellent |
| JP2000159612A (en) * | 1998-09-24 | 2000-06-13 | Sumitomo Chem Co Ltd | Insect repellent for clothing |
| JP2002127334A (en) * | 2000-10-19 | 2002-05-08 | Dainippon Printing Co Ltd | Easily peelable laminate and its manufacturing method |
| JP2003112396A (en) * | 2001-10-03 | 2003-04-15 | Rengo Co Ltd | Package |
-
2004
- 2004-09-22 JP JP2004274830A patent/JP4626242B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03176131A (en) * | 1989-12-05 | 1991-07-31 | Mitsubishi Plastics Ind Ltd | Laminated film |
| JPH03200704A (en) * | 1989-12-28 | 1991-09-02 | Sumitomo Chem Co Ltd | Medicine sustained release resin form |
| JPH0820503A (en) * | 1994-07-04 | 1996-01-23 | Kobayashi Pharmaceut Co Ltd | Insecticide |
| JPH11970A (en) * | 1997-06-11 | 1999-01-06 | Kuraray Co Ltd | Fragrant substance wrapping body |
| JPH11255604A (en) * | 1997-08-06 | 1999-09-21 | Sumitomo Chem Co Ltd | Insect repellent |
| JP2000159612A (en) * | 1998-09-24 | 2000-06-13 | Sumitomo Chem Co Ltd | Insect repellent for clothing |
| JP2002127334A (en) * | 2000-10-19 | 2002-05-08 | Dainippon Printing Co Ltd | Easily peelable laminate and its manufacturing method |
| JP2003112396A (en) * | 2001-10-03 | 2003-04-15 | Rengo Co Ltd | Package |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015182321A (en) * | 2014-03-25 | 2015-10-22 | 三菱樹脂株式会社 | Easily peelable multilayer film, laminate multilayer film, and package |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005119286A (en) | 2005-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI273033B (en) | Atmosphere improving tape for package, package with atmosphere improving tape and method of manufacturing the package, package container with atmosphere improving tape, engaging device, and package with engaging device | |
| EP0665102B1 (en) | Thermoplastic multilayer ethylene polymer sheet for containment of odoriferous product components | |
| JP7050049B2 (en) | Oxygen barrier plastic material | |
| JPH04233984A (en) | Forming web for lining hard container | |
| JP2001502261A (en) | RF sealable pillow pouch | |
| KR101987898B1 (en) | The heat- | |
| JP4626242B2 (en) | Insect repellent packaging materials and clothing repellents | |
| JP2022539476A (en) | Lamination method and product | |
| JP2677176B2 (en) | Laminated body and package formed from the same | |
| JP4008542B2 (en) | Packaging materials and packaging containers | |
| JP3935588B2 (en) | Multilayer laminated heat seal material, laminate using the same, and packaging container | |
| JP3051614B2 (en) | Co-extruded composite film for deep drawing | |
| JP4623275B2 (en) | Exterior packaging bag for oxygen scavenger with oxygen detector | |
| TW202229124A (en) | Packaging system with controlled release of active agent | |
| JP6746879B2 (en) | Sealant film, multilayer film, and package | |
| JP2018162073A (en) | No-extending and co-extruded multi-layered film for lid | |
| JP7320938B2 (en) | Low adsorption moisture absorption film | |
| AU642917B2 (en) | Multi-layered structure for the packaging of products sensitive to oxygen | |
| JP4385689B2 (en) | Laminate with suppressed generation of pinholes and infusion bag package using the laminate | |
| JP4719362B2 (en) | Sealant film with excellent anti-fogging properties | |
| US20200270037A1 (en) | Cover material for blister packs | |
| JP4573015B2 (en) | Oxygen absorber outer packaging | |
| EP1238795A1 (en) | Self-absorbing gas-barrier thermoformable sheet and receptacle for food packaging obtained therefrom | |
| JP2730164B2 (en) | Easy peeling laminated film | |
| JP3946529B2 (en) | Articulating device, packaging body with articulating device, and manufacturing method of articulating device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070808 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20080131 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20080514 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100226 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100316 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100513 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101012 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101025 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131119 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4626242 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131119 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |