JP3810698B2 - Shape retention material - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、小さな力で変形、造形でき、しかも力を除いた後はその変形乃至造形を維持することができる形状保持材料に関する。とくに電線や棒材などの結束や袋詰包装等の袋口の結束に使用されるツイストタイあるいは産業用マスクの鼻金、各種機械保護用ネットなど、形状保持性を必要とする用途に好適な長尺状形状保持材料に関するものであり、とりわけ結束力の大きい結束材とすることが可能な形状保持材料に関する。
【０００２】
【従来の技術】
従来から、菓子等が詰められた袋口の結束、電線や棒材等の結束、栽培植物の支柱への結束などには、使い勝手や見栄えが良くて結束力が強く、捻ることで簡単に止着できるところから、ツイストタイが広く使用されている。また簡易防塵マスクには、装着時の密着性を高めるために鼻金が装着されている。ツイストタイや鼻金には、焼きなました鋼線、２枚のプラスチックフイルムの間に芯材として焼きなました鋼線を挟持させたもの、金属を合成樹脂で被覆したものなどが使用されている。これらの結束効果や保形性は、芯材等に使用されている金属線材の変形塑性により得られるものである。しかし芯材に使用される金属線材は、剛性や弾性に優れるものの、材質が金属であるため錆を発生し易いこと、軽量化が難しいこと、導電性があるため電線の種類によっては、その結束に使用できないこと、端部が鋭利なため取扱い時に怪我をする場合があるなどの欠点があった。
【０００３】
焼きなました鋼線を２枚のプラスチックフイルムの間に芯材として挟持させたものや合成樹脂で被覆したものは、これらいくつかの欠点を補うことはできるものの、製造に複数の工程を要し価格が高くなること、廃棄物として処分する際に分別収集ができない等の欠点がある。また、とくに食品の包装などにおいては、包装後に金属性の異物の混入を検知する目的で製品検査に金属探知機が多く利用されているが、金属線材が探知機の誤作動の原因となるなどの欠点がある。
【０００４】
このような金属材料を使用することによる欠点を回避するものとして、合成樹脂製の塑性変形性材料が知られている。例えば特開昭６１−２８２４１６号や特開平２−２９３４０７号の各公報において、超高分子量ポリオレフィンを塑性変形可能な程度に延伸させて得られるプラスチックワイヤーが提案されている。この提案では、超高分子量ポリオレフィンを使用することに伴い、生産性が低く、安価な製品を得ることが難しいという欠点がある。このような欠点を改善するものとして、特開平７−２３８４１７号公報では、通常分子量のポリエチレンを延伸処理して得られる塑性変形性の糸状又は帯状の材料が提案されている。この提案で具体的に示されているものは、塑性変形性が優れており、１８０度及び９０度折り曲げに対して戻り角度が小さく、形状保持性が優れることが示されている。
【０００５】
【発明が解決しようとする課題】
本発明者らは、この提案における塑性変形性材料について結束材としての利用についてさらに詳細な検討を行った。その結果、確かにこの提案で教示している塑性変形性材料は、結束材として使用することができるが、使用分野によっては結束力が不足して解けることが分かった。そこでさらに検討を行った結果、後記する特定性状のエチレン単独重合体又はエチレン・α−オレフィン共重合体を使用した塑性変形性材料が、塑性変形性に優れると共に塑性変形後の形状保持性に優れ、しかも結束力の大きい結束材として使用可能であることを見出すに至り、本発明に到達した。
【０００６】
【課題を解決するための手段】
すなわち本発明によれば、密度が９５０ｋｇ／ｍ３以上、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）が５〜１５、炭素数３〜６のα−オレフィン含量が２重量％未満であるエチレン単独重合体又はエチレン・α−オレフィン共重合体からなる繊維状又は帯状の成形体であって、９０度曲げによる戻り角度が１２度以下であることを特徴とする形状保持材料が提供される。
【０００７】
このような形状保持材料は、上記エチレン単独重合体又はエチレン・α−オレフィン共重合体の溶融成形によって得られる繊維状又は帯状の成形物を、好ましくは延伸倍率７〜２０倍の範囲であって、塑性変形性を付与できる程度に延伸することによって得ることができる。
【０００８】
上記エチレン・α−オレフィン共重合体においては、α−オレフィンがプロピレンであるものが好ましく、またエチレン単独重合体又はエチレン・α−オレフィン共重合体には、無機充填剤やワックスが少量配合されていることが好ましい。
【０００９】
【発明の実施の形態】
本発明の形状保持材料においては、原料素材としてのエチレン単独重合体又はエチレン・α−オレフィン共重合体は、密度が９５０ｋｇ／ｍ３以上、好ましくは９５５〜９７０ｋｇ／ｍ３、とくに好ましくは９６０〜９７０ｋｇ／ｍ３、ゲル浸透クロマトグラフィ（ＧＰＣ）に基づく分子量分布（重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ））が５〜１５、好ましくは６〜１４、炭素数３〜６のα−オレフィン含量が２重量％未満、好ましくは０．０５〜１．５重量％のものである。すなわち原料素材の成形加工性の点から、エチレン単独重合体よりエチレン・α−オレフィン共重合体の使用が好ましい。このようなエチレン単独重合体又はエチレン・α−オレフィン共重合体としてはまた、１９０℃、２１６０ｇ荷重に基づくメルトフローレートが０．１〜１．０ｇ／１０分、とくに０．２〜０．５ｇ／１０分のものであることが好ましい。さらに上記共重合体としては、重合構成成分であるα−オレフィンとしてはプロピレンのものが好ましい。かかる高密度で適当な分子量分布を有するエチレン単独重合体又はエチレン・α−オレフィン共重合体を使用することにより、塑性変形性、寸法安定性、形状保持性が優れた形状保持材料を容易に得ることができ、また結束強度の大きい結束材として使用することができる。このようなエチレン単独重合体又はエチレン・α−オレフィン共重合体は、中低圧法において、触媒、重合温度、分子量調節剤の使用量などの重合条件を適宜選択することによって１段階で製造するか、あるいは条件を異にして各段で分子量の異なる重合体を多段階で製造することによって得ることができる。
【００１０】
本発明の形状保持材料は、繊維状又は帯状を呈するものであり、９０度曲げによる戻り角度が、１２度以下、好ましくは１０度以下である。ここに戻り角度は、繊維状の場合は、図１（ａ）のように９０度折り曲げて５分間維持して放置したときの（ｂ）で示す戻り角度θが９０度曲げによる戻り角度である。帯状物の戻り角度も、帯を折りたたむように曲げて測定する以外は同様にして測定される。
【００１１】
繊維状物においては、断面が円形のもののみならず、楕円形、三角、四角、五角、六角などの多角形や、星型、歯車型などの異型のものであってもよい。また繊維状物に任意の突状物が設けられたものでもよく、例えば微細な繊維が繊維状物から羽毛状に枝分かれして形成されたものや繊維状物表面に突起が点在して設けられたものであってもよい。さらに帯状物においては、長手方向に伸びる溝あるいは筋が１本以上設けられたものであってもよい。
【００１２】
上記繊維状物あるいは帯状物においては、厚み（最大厚み、断面円形の繊維状物にあっては直径）が０．１〜５ｍｍ、とくに０．２〜２ｍｍであることが好ましい。繊維状物あるいは帯状物がこのような厚みを有することにより、腰が強く、賦形性及び形状保持性に優れたものを容易に得ることができる。
【００１３】
上記性状の形状保持材料を得るためには、上記エチレン・α−オレフィン共重合体から所望形状の繊維状あるいは帯状の原反を溶融成形により製造し、次いで１００℃以下の温度、延伸性の点から好ましくは８５〜１００℃の温度であって、塑性変形性及び形状保持性が発現できる程度に延伸することによって製造することができる。繊維状又は帯状の原反においては、厚み（上記と同じ意）が１〜２０ｍｍ程度、とくに１〜１２ｍｍ程度のものが好ましい。またこのときの延伸倍率は、原反の性状や延伸温度によっても若干異なるが、塑性変形性が発現できる範囲で選択され、通常は降伏点以上破断点以下となるような範囲であって、７〜２０倍程度、好ましくは１０〜１６倍程度である。すなわち延伸倍率が不足すると、塑性変形性及び形状保持性が満足すべきものとはならず、また延伸倍率を大きくしすぎると破断しやすくなる。
【００１４】
上記形状保持材料の製造に際し、エチレン単独重合体又はエチレン・α−オレフィン共重合体には、目的に応じ、本発明の目的を損なわない範囲において、他の熱可塑性樹脂や各種添加剤を配合することができる。このような添加剤としては、例えば加工助剤、着色顔料、帯電防止剤、無機充填剤などを例示することができる。より具体的には、加工助剤として低分子量ポリオレフィン、脂環族ポリオレフィン、カルボキシル基、水酸基などを有する合成油、鉱物油、カルナウバワックスなど植物油からなるワックス、酸化チタン、酸化亜鉛、炭酸カルシウム、硫酸バリウム、シリカのような着色顔料乃至は無機充填剤、各種タイプの界面活性剤からなる帯電防止剤などを例示することができる。これらは、ワックス類や帯電防止剤であれば、例えば５重量％以下、好ましくは１重量％以下の割合で、また着色顔料や無機充填剤であれば、例えば１０重量％以下、好ましくは５重量％以下の割合で、それぞれ配合することができる。ワックス類の添加は、原反の溶融成形や延伸において寸法精度を高めるのに有効であり、また着色顔料や無機充填剤の添加は、着色や増量効果以外に、塑性変形性や形状保持性の改善に寄与する場合がある。
【００１５】
かくして得られる本発明の形状保持材料は、使用時の収縮や寸法変化を紡糸するために１５０℃以下、とくに１２０〜１４０℃でアニールすることが好ましい。
【００１６】
上記繊維状あるいは帯状の形状保持材料は、その状態で結束材や賦形材として使用することができる。より具体的には農業用、園芸用、食品包装用、輸送・梱包用、医療用チューブなどの結束材やマスク、帽子、水引、造花などの賦形材として使用することができる。とりわけ結束力の大きい結束材として使用することができる。また種々の熱可塑性樹脂成形品に固着することにより、該熱可塑性成形品に賦形性、形状保持性を付与することができる。例えば各種ポリオレフィン、ポリエステル、ポリアミドのような熱可塑性樹脂のフイルムあるいはシートの片面あるいは両面に、あるいは２枚のフイルム又はシートに挟持させるように、１本乃至多数本の上記形状保持材料を接着させておくことにより、賦形性、形状保持性に優れたフイルムないしシートを得ることができる。
【００１７】
【実施例】
以下、実施例により本発明をさらに詳細に説明する。
［使用原料］
実施例及び比較例に使用したエチレン単独重合体（ポリエチレンＣ）及びエチレン・プロピレン共重合体（ポリエチレンＡ、Ｂ、Ｄ）の性状を表１に示す。尚、ポリエチレンＡ〜Ｄは低圧法により製造した。
【００１８】
【表１】
［使用原料の物性測定］
（１）コモノマー量：各ポリエチレン中のコモノマー（プロピレン）含量をＮＭＲで測定
（２）メルトフローレート（ＭＦＲ）：ＡＳＴＭ Ｄ１２３８（１９０℃、２１６０ｇ）
（３）分子量分布（Ｍｗ／Ｍｎ）：ゲル浸透クロマトグラフィ（ＧＰＣ）により測定した重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）から算出
（４）密度：ＡＳＴＭ Ｄ１５０５
【００２０】
［実施例１］
ポリエチレンＡを用い、下記条件にて溶融紡糸して得られた繊維状物の延伸を行った。
押出機：３０ｍｍφ（Ｌ／Ｄ＝２８、圧縮比２．３）
ダイ開口：３０ｍｍ×３．６ｍｍ
成形温度（シリンダー及びダイ）：２９０℃
冷却槽：１４００ｍｍ
引取り速度：４ｍ／分
延伸槽：９５℃水槽（長さ１７００ｍｍ）
アニール槽：１４０℃電熱オーブン（長さ２０００ｍｍ）
巻取り速度：５２ｍ／分
得られた繊維状形状保持材料の厚み（最大厚み）をノギスで測定すると共に、図１及び図２に示す方法で、９０度折り曲げ後、５分間保持した後の戻り角度θを測定した。結果を表２に示す。
【００２１】
［実施例２］
ポリエチレンＡの代りにポリエチレンＢを用いた以外は、実施例１と同様に行い繊維状形状保持材料を得た。その評価結果を表２に示す。
【００２２】
［実施例３］
ポリエチレンＢ５０重量部と炭酸カルシウム５０重量部でマスターバッチＡを作成し、ポリエチレンＢ／マスターバッチＡ＝９６／４の割合で混合した樹脂を用い、表２に示す延伸倍率となるように巻取り速度を変えた以外は、実施例１と同様に行い繊維状形状保持材料を得た。その評価結果を表２に示す。
【００２３】
［実施例４］
ポリエチレンＢ７０重量部とカルナウバワックス３０重量部でマスターバッチＢを作成し、ポリエチレンＢ／マスターバッチＢ＝９８／２の割合で混合した樹脂を用いた以外は、実施例１と同様に行い繊維状形状保持材料を得た。その評価結果を表２に示す。
【００２４】
［実施例５］
ポリエチレンＢ／マスターバッチＡ／マスターバッチＢ＝９４／４／２の割合で混合した樹脂を用いた以外は、実施例１と同様に行い繊維状形状保持材料を得た。その評価結果を表２に示す。
【００２５】
［比較例１〜２］
ポリエチレンＣ又はＤを用い、表２に示す延伸倍率となるように巻取り速度を変えた以外は、実施例１と同様に行い繊維状形状保持材料を得た。これらの評価結果を表２に示す。
【００２６】
【表２】
[実施例６、比較例３]
ポリエチレンＢ、Ｃを用いて下記条件にて溶融紡糸して得られた繊維状物の延伸を行った。
押出機：３０ｍｍφ（Ｌ／Ｄ＝２８、圧縮比２．３）
ダイ開口：６ｍｍφ×１０穴
成形温度：２９０℃
冷却槽：１４００ｍｍ
引取り速度：２．６ｍ／分
延伸槽：９５℃水槽
巻取り速度：３９ｍ／分
延伸倍率：１５倍
得られた繊維状形状保持材料（直径：０．７〜０．７５φ）を１０ｃｍに切断したものを、図２（ａ）に示すように３回捻りで結束部を形成し、図示する部位で切断した後、図２（ｂ）で示すように広げ、図示する方向に３００ｍｍ／分の速度で引っ張ることにより結束力を測定した。結果を表３に示す。
【００２８】
【表３】
【００２９】
【発明の効果】
本発明の形状保持材料は、成形性、寸法安定性、塑性変形性、変形後の形状保持性に優れており、そのままであるいは熱可塑性樹脂製品に固着させて、種々の結束材や賦形材として使用することができる。具体的には、農業用、園芸用、果樹用、食品包装用、輸送梱包用、医療用チューブの結束材等に使用することができる。また人形の衣装、玩具・ゲーム用品の結束材等にも使用することができる。さらには人形や玩具・ゲーム用品の収納ケースや台紙への結束材としても使用できる。一方、賦形材としては、マスク、帽子、水引、造花、飾り、装飾品などの芯材を挙げることができる。
【図面の簡単な説明】
【図１】 ９０度折り曲げ後の戻り角度を示す図面である。
【図２】 結束力の測定方法を示す図面である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a shape-retaining material that can be deformed and shaped with a small force and can maintain the deformation or shaping after the force is removed. Especially suitable for applications that require shape retention, such as twist ties used for bundling wires and sticks, bag mouth bundling, industrial mask noses, and various machine protection nets. The present invention relates to a long shape-retaining material, and particularly relates to a shape-retaining material that can be used as a binding material having a large binding force.
[0002]
[Prior art]
Conventionally, it is easy to use, looks good, has a strong binding force, and can be easily stopped by twisting it for bundling bag mouths packed with confectionery, bundling electric wires and rods, and bundling cultivated plants. Twist ties are widely used because they can be worn. In addition, a nosepiece is attached to the simple dust mask in order to improve adhesion at the time of wearing. Twisted ties and noses are made of annealed steel wire, sandwiched annealed steel wire as a core material between two plastic films, or coated metal with synthetic resin. These bundling effects and shape retention are obtained by the deformation plasticity of the metal wire used for the core material and the like. However, although the metal wire used for the core material is excellent in rigidity and elasticity, it is easy to generate rust because the material is metal, it is difficult to reduce the weight, and because it is conductive, it is bound depending on the type of electric wire. However, there are drawbacks such as being injured during handling due to the sharpness of the edges.
[0003]
Annealed steel wire sandwiched between two plastic films or coated with a synthetic resin can compensate for some of these drawbacks, but requires multiple steps to manufacture and costs However, there are disadvantages such as a high collection rate and separate collection when disposing as waste. In addition, especially in food packaging, metal detectors are often used for product inspections to detect the inclusion of metallic foreign objects after packaging, but metal wires can cause the detector to malfunction. There are disadvantages.
[0004]
A plastic deformable material made of a synthetic resin is known as a material for avoiding the drawbacks caused by using such a metal material. For example, in Japanese Patent Laid-Open Nos. 61-282416 and 2-293407, plastic wires obtained by stretching an ultrahigh molecular weight polyolefin to the extent that can be plastically deformed are proposed. This proposal has the disadvantage that it is difficult to obtain an inexpensive product with low productivity due to the use of ultra-high molecular weight polyolefin. In order to remedy such drawbacks, Japanese Patent Application Laid-Open No. 7-238417 proposes a plastically deformable thread-like or belt-like material obtained by stretching a normal molecular weight polyethylene. What is specifically shown in this proposal has excellent plastic deformability, a small return angle with respect to bending at 180 degrees and 90 degrees, and excellent shape retention.
[0005]
[Problems to be solved by the invention]
The inventors of the present invention have made further detailed studies on the use of the plastic deformable material in this proposal as a binding material. As a result, the plastically deformable material taught in this proposal can be used as a binding material, but depending on the field of use, it has been found that the binding force is insufficient. As a result of further investigation, a plastic deformable material using an ethylene homopolymer or ethylene / α-olefin copolymer having specific properties described later is excellent in plastic deformability and shape retention after plastic deformation. And it came to discover that it could be used as a binding material with big binding force, and reached this invention.
[0006]
[Means for Solving the Problems]
That is, according to the present invention, the density is 950 kg / m 3 or more, the weight average molecular weight (Mw) / number average molecular weight (Mn) is 5 to 15, and the α-olefin content of 3 to 6 carbon atoms is less than 2% by weight. Provided is a shape-retaining material, characterized in that it is a fibrous or belt-shaped molded article made of an ethylene homopolymer or an ethylene / α-olefin copolymer, and the return angle by bending at 90 degrees is 12 degrees or less. .
[0007]
Such a shape-retaining material is a fibrous or strip-shaped product obtained by melt molding of the ethylene homopolymer or ethylene / α-olefin copolymer, preferably in a range of a stretch ratio of 7 to 20 times. It can be obtained by stretching to such an extent that plastic deformation can be imparted.
[0008]
In the ethylene / α-olefin copolymer, the α-olefin is preferably propylene, and the ethylene homopolymer or ethylene / α-olefin copolymer contains a small amount of an inorganic filler or wax. Preferably it is.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the shape maintaining material of the present invention, the ethylene homopolymer or ethylene / α-olefin copolymer as the raw material has a density of 950 kg / m 3 or more, preferably 955 to 970 kg / m 3 , particularly preferably 960 to 960. Α-olefin having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 5 to 15, preferably 6 to 14 and 3 to 6 carbon atoms based on gel permeation chromatography (GPC), 970 kg / m 3 The content is less than 2% by weight, preferably 0.05 to 1.5% by weight. That is, from the viewpoint of moldability of the raw material, it is preferable to use an ethylene / α-olefin copolymer rather than an ethylene homopolymer. Such ethylene homopolymer or ethylene / α-olefin copolymer also has a melt flow rate based on a load of 190 ° C. and a load of 2160 g of 0.1 to 1.0 g / 10 min, particularly 0.2 to 0.5 g. / 10 minutes are preferable. Furthermore, as said copolymer, the thing of a propylene is preferable as an alpha olefin which is a polymerization structural component. By using an ethylene homopolymer or ethylene / α-olefin copolymer having an appropriate molecular weight distribution at a high density, a shape-retaining material excellent in plastic deformation, dimensional stability, and shape-retaining properties can be easily obtained. And can be used as a binding material having a high binding strength. Whether such ethylene homopolymer or ethylene / α-olefin copolymer is produced in one stage by appropriately selecting the polymerization conditions such as catalyst, polymerization temperature, amount of use of molecular weight regulator, etc. in the medium-low pressure method. Alternatively, it can be obtained by producing polymers having different molecular weights at each stage in different stages under different conditions.
[0010]
The shape-retaining material of the present invention has a fibrous or belt-like shape, and the return angle by 90-degree bending is 12 degrees or less, preferably 10 degrees or less. Here, in the case of a fiber, the return angle is 90 ° bent as shown in FIG. 1A, and the return angle θ shown in FIG. . The return angle of the strip is also measured in the same manner except that the strip is bent and folded.
[0011]
The fibrous material is not limited to a circular cross section, but may be an elliptical shape, a triangular shape, a quadrangular shape, a pentagonal shape, a hexagonal shape, or a different shape such as a star shape or a gear shape. Also, the fibrous object may be provided with an arbitrary protrusion, for example, a fine fiber branched from a fibrous object in a feather shape or provided with projections scattered on the surface of the fibrous object. It may be what was made. Furthermore, in the belt-like object, one or more grooves or streaks extending in the longitudinal direction may be provided.
[0012]
In the fibrous material or the belt-like material, the thickness (maximum thickness, diameter in the case of a fibrous material having a circular cross section) is preferably 0.1 to 5 mm, particularly preferably 0.2 to 2 mm. When the fibrous or belt-like material has such a thickness, it is easy to obtain a material that is firm and has excellent shapeability and shape retention.
[0013]
In order to obtain a shape-retaining material having the above-mentioned properties, a fibrous or belt-shaped raw material having a desired shape is produced from the ethylene / α-olefin copolymer by melt molding, and then a temperature of 100 ° C. or less and stretchability From this, it can be produced by stretching at a temperature of 85 to 100 ° C. to such an extent that plastic deformability and shape retention can be exhibited. In the fibrous or belt-shaped raw fabric, the thickness (the same meaning as described above) is preferably about 1 to 20 mm, particularly preferably about 1 to 12 mm. Further, the draw ratio at this time is slightly different depending on the properties of the original fabric and the drawing temperature, but is selected within a range in which plastic deformability can be expressed, and is usually in a range such that it is not less than the yield point and not more than the break point. About 20 times, preferably about 10 to 16 times. That is, if the draw ratio is insufficient, the plastic deformability and shape retention are not satisfactory, and if the draw ratio is too large, the film tends to break.
[0014]
In the production of the shape-retaining material, the ethylene homopolymer or ethylene / α-olefin copolymer is blended with other thermoplastic resins and various additives depending on the purpose within a range not impairing the object of the present invention. be able to. Examples of such additives include processing aids, color pigments, antistatic agents, inorganic fillers, and the like. More specifically, low-molecular-weight polyolefin, alicyclic polyolefin, synthetic oil having a carboxyl group, hydroxyl group, etc. as a processing aid, wax made of vegetable oil such as mineral oil, carnauba wax, titanium oxide, zinc oxide, calcium carbonate, Examples thereof include coloring pigments such as barium sulfate and silica, inorganic fillers, and antistatic agents composed of various types of surfactants. These are, for example, 5% by weight or less, preferably 1% by weight or less for waxes or antistatic agents, and for example, 10% by weight or less, preferably 5% by weight for color pigments or inorganic fillers. Each can be blended at a ratio of% or less. The addition of waxes is effective for improving the dimensional accuracy in melt molding and stretching of the original fabric, and the addition of coloring pigments and inorganic fillers is effective for plastic deformation and shape retention in addition to the coloring and increasing effects. May contribute to improvement.
[0015]
The shape-retaining material of the present invention thus obtained is preferably annealed at 150 ° C. or lower, particularly 120 to 140 ° C., in order to spin shrinkage or dimensional change during use.
[0016]
The fibrous or belt-shaped shape-retaining material can be used as a binding material or a shaping material in that state. More specifically, it can be used as a binding material such as agricultural, horticultural, food packaging, transportation / packaging, medical tubing, or a shaping material such as a mask, a hat, water draw, or artificial flower. In particular, it can be used as a binding material having a high binding force. Further, by fixing to various thermoplastic resin molded products, it is possible to impart formability and shape retention to the thermoplastic molded products. For example, one or many of the above shape-retaining materials are bonded so as to be sandwiched between one or both sides of a film or sheet of thermoplastic resin such as various polyolefins, polyesters, and polyamides, or between two films or sheets. Thus, a film or sheet excellent in formability and shape retention can be obtained.
[0017]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[Raw materials]
Table 1 shows the properties of the ethylene homopolymer (polyethylene C) and the ethylene / propylene copolymer (polyethylene A, B, D) used in Examples and Comparative Examples. Polyethylenes A to D were produced by a low pressure method.
[0018]
[Table 1]
[Measurement of physical properties of raw materials used]
(1) Comonomer amount: NMR measurement of comonomer (propylene) content in each polyethylene (2) Melt flow rate (MFR): ASTM D1238 (190 ° C., 2160 g)
(3) Molecular weight distribution (Mw / Mn): calculated from weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (4) Density: ASTM D1505
[0020]
[Example 1]
Polyethylene A was used to stretch a fibrous material obtained by melt spinning under the following conditions.
Extruder: 30 mmφ (L / D = 28, compression ratio 2.3)
Die opening: 30mm x 3.6mm
Molding temperature (cylinder and die): 290 ° C
Cooling tank: 1400mm
Take-off speed: 4 m / min Stretch tank: 95 ° C. water tank (length 1700 mm)
Annealing bath: 140 ° C electric heating oven (length: 2000 mm)
Winding speed: 52 m / min The thickness (maximum thickness) of the obtained fibrous shape-retaining material is measured with a caliper, and after returning 90 degrees by the method shown in FIGS. The angle θ was measured. The results are shown in Table 2.
[0021]
[Example 2]
A fibrous shape-retaining material was obtained in the same manner as in Example 1 except that polyethylene B was used instead of polyethylene A. The evaluation results are shown in Table 2.
[0022]
[Example 3]
A masterbatch A is prepared with 50 parts by weight of polyethylene B and 50 parts by weight of calcium carbonate, and a winding speed is used so that the draw ratio shown in Table 2 is obtained using a resin mixed in a ratio of polyethylene B / masterbatch A = 96/4. A fibrous shape-retaining material was obtained in the same manner as in Example 1 except that the above was changed. The evaluation results are shown in Table 2.
[0023]
[Example 4]
A master batch B was prepared with 70 parts by weight of polyethylene B and 30 parts by weight of carnauba wax, and the same procedure as in Example 1 was performed except that a resin mixed in a ratio of polyethylene B / master batch B = 98/2 was used. A shape retaining material was obtained. The evaluation results are shown in Table 2.
[0024]
[Example 5]
A fibrous shape-retaining material was obtained in the same manner as in Example 1 except that a resin mixed at a ratio of polyethylene B / master batch A / master batch B = 94/4/2 was used. The evaluation results are shown in Table 2.
[0025]
[Comparative Examples 1-2]
A fibrous shape-retaining material was obtained in the same manner as in Example 1 except that polyethylene C or D was used and the winding speed was changed so that the draw ratio shown in Table 2 was obtained. These evaluation results are shown in Table 2.
[0026]
[Table 2]
[Example 6, Comparative Example 3]
The fibrous material obtained by melt spinning using polyethylene B and C under the following conditions was stretched.
Extruder: 30 mmφ (L / D = 28, compression ratio 2.3)
Die opening: 6mmφ x 10 holes Molding temperature: 290 ° C
Cooling tank: 1400mm
Take-up speed: 2.6 m / min Stretch tank: 95 ° C. Water tank take-up speed: 39 m / min Stretch ratio: 15 times Cut the obtained fibrous shape-retaining material (diameter: 0.7-0.75φ) to 10 cm After forming the bundled portion by twisting three times as shown in FIG. 2 (a) and cutting at the site shown in the figure, it is spread out as shown in FIG. 2 (b) and 300 mm / min in the direction shown in the figure. The binding force was measured by pulling at a speed. The results are shown in Table 3.
[0028]
[Table 3]
[0029]
【The invention's effect】
The shape-retaining material of the present invention is excellent in moldability, dimensional stability, plastic deformability, and shape-retaining property after deformation, and is used as it is or fixed to a thermoplastic resin product as various binding materials and shaping materials. Can be used as Specifically, it can be used for agricultural, horticultural, fruit tree, food packaging, transport packaging, medical tube binding materials, and the like. It can also be used as doll costumes, binding materials for toys and game equipment. Furthermore, it can also be used as a binding material for dolls, toys, game equipment storage cases and mounts. On the other hand, examples of the shaping material include core materials such as a mask, a hat, a water draw, artificial flowers, a decoration, and an ornament.
[Brief description of the drawings]
FIG. 1 is a drawing showing a return angle after bending by 90 degrees.
FIG. 2 is a drawing showing a method for measuring the binding force.
Claims (10)
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| JP2002080419A JP3810698B2 (en) | 2002-03-22 | 2002-03-22 | Shape retention material |
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| JP2002080419A JP3810698B2 (en) | 2002-03-22 | 2002-03-22 | Shape retention material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016202657A (en) * | 2015-04-24 | 2016-12-08 | 有限会社 ケイティ商事 | Curtain interlining and curtain cloth |
| KR20170054325A (en) | 2014-09-16 | 2017-05-17 | 세키스이 세이케이, 리미티드. | Shape retaining material and method for manufacturing same |
| US9874908B2 (en) | 2014-12-24 | 2018-01-23 | Samsung Electronics Co., Ltd. | Electronic devices |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005111184A (en) * | 2003-10-10 | 2005-04-28 | Mitsui Chemicals Inc | Openable and closable container |
| JP2008179417A (en) * | 2006-12-26 | 2008-08-07 | Kyodo Printing Co Ltd | Lid material and packaging material using the same |
| WO2011135860A1 (en) * | 2010-04-30 | 2011-11-03 | 三井化学株式会社 | Shape-retaining film, process for producing same, laminate for packaging, packaging material and process for producing same, shape-retaining fiber, and anisotropic heat-conductive film |
| CN103068576B (en) * | 2010-08-25 | 2015-03-11 | 三井化学株式会社 | Shape retaining film and production method therefor, laminated filmtape, self-adhesive filmtape, anisotropic thermal conductive film, and shape retaining fiber |
| JP2021031063A (en) * | 2019-08-14 | 2021-03-01 | 凸版印刷株式会社 | Tube container |
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2002
- 2002-03-22 JP JP2002080419A patent/JP3810698B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170054325A (en) | 2014-09-16 | 2017-05-17 | 세키스이 세이케이, 리미티드. | Shape retaining material and method for manufacturing same |
| US9657163B2 (en) | 2014-09-16 | 2017-05-23 | Sekisui Seikei, Ltd. | Shape retaining material and method for producing the same |
| US9874908B2 (en) | 2014-12-24 | 2018-01-23 | Samsung Electronics Co., Ltd. | Electronic devices |
| JP2016202657A (en) * | 2015-04-24 | 2016-12-08 | 有限会社 ケイティ商事 | Curtain interlining and curtain cloth |
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| JP2003278026A (en) | 2003-10-02 |
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